JPH09194448A - Production of diamine-type polyamino acid by connection of bimolecular amino acid and biodegradable chelating agent containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject compound having biodegradability, excellent chelating force and widely useful as a detergent composition, a detergent builder or a peroxide stabilizer, etc., at a high yield in a high purity. SOLUTION: Bimolecular amino acid e.g. obtained from L-aspartic acids is reacted with a unimolecular dihaloalkane derivative (e.g. dichloropropane) or epichlorohydrin in a solvent (e.g. diethylene glycol) in the presence of a metal ion (e.g. magnesium hydroxide) and under the alkaline condition by using sodium hydroxide at pH9-12 and at 50-160 deg.C. After the reaction, the reacted solution is treated with a mineral acid to obtain the objective diamine-type polyamino acid and an alkali metal salt thereof.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a diamine-type polyamino acid and a metal salt thereof from two molecules of amino acid and one molecule of dihaloalkane derivative or epichlorohydrin, and more specifically, sarcosine,
Two amino acid molecules such as taurine and aspartic acid are treated with dihaloethane, dihalopropane, 2,3-dihalosuccinic acid,
The present invention relates to a method for producing a diamine-type polyamino acid excellent in chelating ability and biodegradability and a metal salt thereof by linking to one molecule of a dihaloalkane derivative such as 2,4-dihaloglutaric acid. These diamine-type polyamino acids and alkali metal salts are widely used as a biodegradable chelating agent in detergent compositions, detergent builders, sequestering agents, peroxide stabilizers, and the like.

[0002]

Conventionally, various chelate compounds have been used for the above applications. For example, sodium tripolyphosphate, which has excellent chelating and dispersing ability and has been used in detergent builders, contains phosphorus and is one of the eutrophication of rivers or lakes when released into the environment. Cause Zeolite is used as a detergent builder currently used, but it has poor chelating and dispersing power,
Further, since it is an inorganic substance, it is not biodegradable, and furthermore, since the used zeolite is insoluble in water, there is a problem that it sticks to a drain pipe or the like.

On the other hand, as a chelate compound having a sufficient chelating power, there are aminopolycarboxylic acids, and representative examples thereof include ethylenediaminetetraacetic acid and nitrilotriacetic acid. Ethylenediaminetetraacetic acid has an extremely stable chelating power and is used in a wide range of applications, but since it is not biodegradable, it accumulates in the environment and toxic heavy metals are solubilized and brought back into the water supply. Causing problems. Although nitrilotriacetic acid has biodegradability, it has been reported that it has teratogenicity, that is, heavy metal complexes such as iron have carcinogenicity. It costs.

As a compound having a practical level of chelating power and biodegradability, there is, for example, L, L-ethylenediaminedisuccinic acid. As its synthesis, two molecules of (L) -aspartic acid are converted into one molecule of dichloroethane (Ch
m. Zvesti, 1966, vol. 20, p. 414) or dibromoethane (Inorganic Chemistry, 1968, vol. 7, vol. 2405).
A method of connecting using (Page) is known.

Thus, the method of linking two molecules of amino acid with one molecule of dihaloalkane derivative or epichlorohydrin is a powerful means for synthesizing a diamine type polyamino acid excellent in chelating ability and biodegradability. Nevertheless, it is difficult to say that it is widely used as a general method and there are few application examples due to obstacles such as a large amount of by-products and poor reactivity.

[0006]

SUMMARY OF THE INVENTION The present invention has been made to solve these problems of the prior art, and a method of reacting two molecules of amino acid with one molecule of dihaloalkane derivative or epichlorohydrin, Yield, high purity,
An object is to provide a diamine-type polyamino acid having excellent chelating ability and biodegradability.

[0007]

Means for Solving the Problems As a result of intensive research to solve the above problems, the present inventors have found that when a metal ion is present in the reaction system during the reaction between an amino acid and a dihaloalkane derivative or epichlorohydrin, A stable complex is formed with a diamine-type polyamino acid that accumulates as a target product in the reaction system, side reactions are significantly suppressed, and the presence of an organic solvent in the reaction system significantly improves the reaction rate. It was found that the yield of diamine-type polyamino acid was remarkably improved by the above.

Furthermore, the present inventors have found that the production method according to the present invention is widely applicable to the reaction of various amino acids with various dihaloalkane derivatives or epichlorohydrin, and moreover, it is a diamine type polyamine obtained as a target product. The present invention was achieved by finding out that many amino acids are compounds having excellent chelating ability and biodegradability.

That is, the first invention of the present invention is characterized by reacting two molecules of amino acid with one molecule of a dihaloalkane derivative or epichlorohydrin in the presence of a metal ion under alkaline conditions. The gist is a method for producing a polyamino acid and a metal salt thereof.

A second invention of the present invention is characterized in that two molecules of amino acid are reacted with one molecule of dihaloalkane derivative or epichlorohydrin under alkaline conditions in the presence of a metal ion and an organic solvent. The gist is a method for producing a polyamino acid and a metal salt thereof.

[0011]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in detail below.

Amino acids used in the method of the present invention include glycine, N-methylglycine, taurine,
N-methyl taurine, taurine-N-monoacetic acid, (L)-
Aspartic acid, N-methyl- (L) -aspartic acid, N-methyl- (L) -glutamic acid, (L) -aspartic acid-N-monoacetic acid, (L) -glutamic acid-N
-Monoacetic acid, aspartic acid-N-monoacetic acid, 1-amino-
1,2,3-propanetricarboxylic acid, 2-amino-
1,2,3-propanetricarboxylic acid, N-methyl-1
-Amino-1,2,3-propanetricarboxylic acid, N-
Methyl-2-amino-1,2,3-propanetricarboxylic acid and the like are preferably used.

When the amino acid used in the present invention has an asymmetric carbon such as aspartic acid or glutamic acid, a racemic form can be used, but from the viewpoint of biodegradability, a natural optical isomer is used. Particularly preferred. Amino-
When there are positional isomers such as 1,2,3-propanetricarboxylic acid, it is desirable to use each isomer alone, but depending on the availability of amino acids, it may be used as an isomer mixture. It is also possible. Also,
The acidic residue of an amino acid is not necessarily limited to a carboxylic acid group, and for example, an amino acid having a sulfonic acid group such as taurine, an amino acid having a phenol group or a phosphoric acid group,
In some cases, the desired diamine-type polyamino acid may be provided with characteristic performance. Further, aspartic acid-N-monoacetic acid and glutamic acid-N-monoacetic acid are monoamine-type biodegradable chelating agents, and are synthesized by subjecting aspartic acid and glutamic acid to a carboxymethylation reaction.

The amino acid may be in any form such as an acid solid, an alkali metal salt solid or an aqueous solution as long as it can be industrially used. When using aspartic acid-N-monoacetic acid or glutamic acid-N-monoacetic acid, the alkaline reaction solution obtained by subjecting aspartic acid or glutamic acid to carboxymethylation may be used as it is or after being appropriately concentrated and desalted. It is possible. In any case, the purity of the amino acid is 7% in the organic component.
It is desired to be 0% by weight or more, preferably 95% by weight or more. Moreover, the concentration of the aqueous solution of the alkali metal salt of the amino acid used in the reaction step is 50 to 50 in terms of acid.
400 g / L, preferably 100 to 260 g / L. Alkali metal salts include lithium, sodium,
Although either potassium or rubidium salt may be used, sodium or potassium salt is industrially used. Preferably sodium salt is used.

The dihaloalkane derivative used in the present invention includes dichloroethane, dichloropropane, 2,3
-Dichlorosuccinic acid, dimethyl 2,3-dichlorosuccinate, 2,3-dichloropropionic acid, methyl 2,3-dichloropropionate, 2,3-dichloropropionitrile, 2,4-dichloroglutaric acid, 2, Dimethyl 4-dichloroglutarate, dibromoethane, dibromopropane, 2,3-dibromosuccinic acid, dimethyl 2,3-dibromosuccinate, 2,3-dibromopropionic acid, 2,3
-Methyl dibromopropionate, 2,3-dibromopropionitrile, 2,4-dibromoglutaric acid, 2,4-
Dimethyl dibromoglutarate and the like are preferably used.
Dihaloethane and the like are used as raw materials with excellent availability.
-Dihalosuccinic acid and the like are used as a raw material that imparts excellent chelating power to the target diamine-type polyamino acid. Both dichloro and dibromo compounds can be used, but the dichloro compound is preferred from the viewpoints of raw material, availability and wastewater treatment. The dibromo compound is excellent in reactivity and has an advantage that it does not necessarily require addition of an organic solvent in the reaction step, but it requires careful handling because it is highly toxic.

In the present invention, for the purpose of linking two amino acids, epichlorohydrin is a raw material excellent in availability and reactivity in addition to the dihaloalkane derivative. When epichlorohydrin and a raw material are used, the amino group of the amino acid basically has a different reaction mode from that of the dihaloalkane derivative, which is a nucleophilic addition to two halides of the dihaloalkane derivative, and a 2-hydroxy-1, 3-
A diamino-type polyamino acid is obtained.

The amount of the dihaloalkane derivative or epichlorohydrin used in the present invention is 0.5 to 10 times mol, preferably 1 to 5 times the amount of the amino acid which is the other raw material.
Double mole is better. In particular, an addition method that is excellent in reactivity and is gradually added dropwise to the reaction system is desirable in order to suppress the concurrent hydrolysis. When dichloroethane, dichloropropane, etc. are used, they can be used in a large excess in order to improve the reaction rate, and after the completion of the reaction, unreacted components can be recovered by distillation or two-layer separation and reused. .

In the method of the present invention, the pH at the start of the reaction
Is adjusted by adding an alkali metal hydroxide or an aqueous solution thereof. Examples of the alkali metal hydroxide used include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide and the like. Of these, an aqueous solution of sodium hydroxide is preferably used industrially. When an alkali metal salt of an amino acid is used, it is desirable to use the same alkali metal salt as the alkali metal hydroxide used for pH adjustment.

Examples of the organic solvent used in the method of the present invention include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, diethylene glycol, diethylene glycol monoalkyl ethers and triethanolamine. Ethylene glycol and triethylene glycol are preferable.

The effect of adding the organic solvent in the present invention is that dihaloethane, dihalopropane, dimethyl 2,3-dihalosuccinate, methyl 2,3-dihalopropionate, 2,3
-It is particularly remarkable when a non-polar dihaloalkane derivative such as dihalopropionitrile or dimethyl 2,4-dihaloglutarate is used, and the reaction rate is greatly improved.
On the other hand, when the dihaloalkane derivative is 2,3-dihalosuccinic acid, 2,3-dihalopropionic acid, 2,4-dihaloglutaric acid or the like which has excellent alkali water solubility, addition of an organic solvent is not always necessary. There is also. When the dihaloalkane derivative has an ester group or a nitrile group, these groups are finally hydrolyzed in the reaction to give a carboxyl group.

The amount of the organic solvent used is in the range of 5 to 40% by volume, preferably 10 to 30% by volume, based on the aqueous solution of the alkali metal salt of L-aspartic acid. The added organic solvent can be recovered and reused after the reaction.

The pH of the reaction step in the present invention is 9 to 1
The range of 2 is preferable, and the range of 9.5 to 11.5 is preferable. Strict control of the pH in the reaction step maintains an appropriate reaction rate and prevents unnecessary hydrolysis of the dihaloalkane derivative or epichlorohydrin,
Extremely important.

The reaction temperature is in the range of 50 to 160 ° C. Normally, it is carried out at 110 ° C or lower at normal pressure,
A method of performing the reaction at 100 ° C. or higher in a pressure reaction vessel is also an effective means for reducing the reaction time.

In the present invention, the operation of the reaction step is carried out as follows. That is, it is carried out by a method in which an aqueous solution of an alkali metal is added dropwise to a reaction solution containing an amino acid, a dihaloalkane derivative or epichlorohydrin, an organic solvent and a metal ion so as to keep a predetermined pH constant.

The metal ions used in the method of the present invention are Fe (II), Fe (III), Cu (II), Zn (II), N.
heavy metals such as i (II), Co (II), Mn (II), Al (III),
It is selected from alkaline earth metals such as Mg (II), Ca (II) and Ba (II). Although the chelate stability constant of the target diamine-type polyamino acid varies depending on the compound, it generally tends to be large for heavy metals and small for alkaline earth metals. In the method of the present invention, when the crystals of the diamine-type polyamino acid are obtained by acid precipitation crystallization after the reaction,
It is preferable to use an alkaline earth metal because the decomposition of the complex is easy.

The metal ion used in the method of the present invention has an important meaning to protect the desired diamine-type polyamino acid, which accumulates in the system as the reaction proceeds, as a stable metal complex from side reactions. For example, in the reaction of dichloropropane and (L) -aspartic acid in the present invention,
If no metal ion is added, the target propanediamine-N, N-disuccinic acid reacts with another molecule of dichloropropane to produce 3-hydroxypropyl-propanediamine-N, N-disuccinic acid as a by-product. Will end up.

The addition effect of the metal ion used in the method of the present invention is as follows: N-methylglycine, N-methyltaurine, N-methyl- (L) -aspartic acid, N-methyl- (L) -glutamic acid, (L ) -Aspartic acid-
N-methyl-1-amino-1,2,3-propanetricarboxylic acid, N-methyl-2-, such as N-monoacetic acid, (L) -glutamic acid-N-monoacetic acid, aspartic acid-N-monoacetic acid Glycine, taurine, (L) -aspartic acid, more than when an amino acid having a disubstituted amino group such as amino-1,2,3-propanetricarboxylic acid is used.
When an amino acid having a mono-substituted amino group such as (L) -glutamic acid, 1-amino-1,2,3-propanetricarboxylic acid and 2-amino-1,2,3-propanetricarboxylic acid is used as a raw material, Provides greater side reaction suppression.

The metal ion may be added to the reaction solution as various metal salts. The type of metal ion is selected from hydroxide, sulfate, hydrochloride, nitrate, acetate, carbonate, etc., preferably hydroxide or sulfate, and more preferably hydroxide. The metal ions may be added all at once at the start of the reaction, or may be added gradually as the reaction progresses.

After the reaction using the metal ions, the reaction solution is treated with a mineral acid to obtain the desired diamine-type polyamino acid. The metal ions used in the reaction must be removed after the reaction and prior to the acid precipitation step. Particularly when heavy metal ions are used as the metal ions, it is necessary to remove and recover the metal ions from the viewpoint of pollution prevention. However, when the purpose is to produce a heavy metal complex,
A metal ion suitable for the target metal salt can be selected, and after completion of the reaction, the reaction solution can be concentrated to obtain the target metal salt.

On the other hand, when an alkaline earth metal is used, the alkaline earth metal is easily desorbed from the diamine-type polyamino acid complex under acidic conditions. The steps can be carried out.

Mineral acids used in the acid precipitation crystallization step include sulfuric acid, hydrochloric acid and nitric acid, and sulfuric acid is preferably used. The concentration of sulfuric acid is 60, which is industrially available.
A material of up to 98% is preferably used. The pH of the reaction solution is
It is desirable to adjust the concentration within the range of 0.5 to 3.0, preferably within the range of 1.5 to 2.5, and to add the mineral acid dropwise within the temperature range of the reaction solution of 40 to 80 ° C. Mineral acid addition time is 1-2
Time is preferred.

In the acid precipitation step, after the addition of mineral acid, 0 to 50 ° C.
After aging at a temperature of 20 to 40 ° C. for 0 to 72 hours, preferably 1 to 5 hours, the precipitated crystals are isolated by an operation such as suction filtration or centrifugation. Since the separated crystals are usually of high purity that does not need to be subjected to a separate purification treatment, they are washed with a small amount of water and then dried by an operation such as warm air drying to obtain the desired diamine-type poly Amino acids can be obtained.

[0033]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited to the following examples.

Example 1 Water (1017 kg) was charged into a pressure reactor equipped with a stirrer, a thermometer, a pH meter, a dropping funnel and a distillation device, and the mixture was cooled to 9
7 wt% sodium hydroxide (150 kg) and L-aspartic acid (500 kg) were continuously added and dissolved. Dichloropropane (373 kg), diethylene glycol (110 kg) and 30 wt% magnesium hydroxide slurry (254 kg) were added to this solution, the pH of the reaction solution was adjusted to 11 with stirring, and then the solution temperature was raised. Then, the distillation was started at 78 ° C. While maintaining the reaction liquid as it was at a temperature of 78 ° C. and a pH of 11, 48% by weight aqueous sodium hydroxide solution (380 kg) was added over time with stirring. The progress of the reaction was monitored using HPLC, and the reaction was stopped when the raw material L-aspartic acid was consumed. After 98% by weight sulfuric acid (601 kg) was added to the reaction solution to adjust the pH to 2, the mixture was aged at 40 ° C. for 1 hour, and the precipitated crystals were separated by centrifugation. After washing the wet crystals with water,
Blow drying at 121 ° C. gave L, L-propanediaminedisuccinic acid (541 kg) as white crystals. As a result of HPLC analysis, this crystal had a chemical purity of 10 and an optical purity of 10.
It was 0%. The results are shown in Table 1.

Example 2 A pressure reactor equipped with a stirrer, a thermometer, a pH meter, a dropping funnel and a distillation apparatus was charged with water (1017 kg) and charged to 9
7 wt% sodium hydroxide (150 kg) and L-aspartic acid (500 kg) were continuously added and dissolved. To this solution, 30 wt% magnesium hydroxide slurry (254 kg) was added, and the pH of the reaction solution was adjusted to 11 with stirring.
Then, the liquid temperature was raised to 60 ° C. While maintaining the reaction liquid as it is at a temperature of 60 ° C. and a pH of 11,
With stirring, a 48 wt% sodium hydroxide aqueous solution (160
kg) and epichlorohydrin (305 kg) were added over time. The progress of the reaction was monitored using HPLC, and when the raw material L-aspartic acid was consumed, the addition of the aqueous sodium hydroxide solution and epichlorohydrin was stopped. 98 wt% sulfuric acid (456 kg) was added to this reaction solution to adjust the pH to 2, and the mixture was aged at 40 ° C. for 1 hour, and the precipitated crystals were separated by centrifugation. After washing the wet crystals with water,
Blow drying at 121 ° C to obtain L, L-2-hydroxy-1,
3-Propanediamine disuccinic acid (575 kg) was obtained as white crystals. As a result of HPLC analysis, this crystal was 100% in both chemical purity and optical purity. The results are shown in Table 1.

Examples 3 to 32 The reaction was carried out in the same stoichiometry as in Examples 1 and 2, except that the starting dihaloalkane derivative or epichlorohydrin was changed to the combination shown in Table 1. The results are shown in Table 1.
The structure of the desired diamine-type polyamino acid in each example is shown below.

Compounds of Example 1 and Comparative Example 1

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Comparative Examples 1-83 The same reactions as in Examples 1-83 were carried out except that the addition of diethylene glycol and magnesium hydroxide was omitted. The results are shown in Table 1.

[0121]

[0122]

According to the method of the present invention, diamine type polyamino acids having biodegradability and excellent chelating ability can be obtained in high yield.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C07C 309/14 7419-4H C07C 309/14 C09K 3/00 108 C09K 3/00 108C C11D 3/33 C11D 3/33

Claims (7)

[Claims] 1. A method for producing a diamine-type polyamino acid and a metal salt thereof, which comprises reacting two molecules of an amino acid with one molecule of a dihaloalkane derivative or epichlorohydrin in the presence of a metal ion under alkaline conditions. . 2. A diamine-type polyamino acid and a metal salt thereof, which comprises reacting two molecules of an amino acid with one molecule of a dihaloalkane derivative or epichlorohydrin under alkaline conditions in the presence of a metal ion and an organic solvent. Manufacturing method. 3. The amino acid is glycine, N-methylglycine, taurine, N-methyltaurine, taurine-N-.
Monoacetic acid, (L) -aspartic acid, N-methyl- (L)
-Aspartic acid, N-methyl- (L) -glutamic acid, (L) -aspartic acid-N-monoacetic acid, (L)-
Glutamic acid-N-monoacetic acid, Aspartic acid-N-monoacetic acid, 1-amino-1,2,3-propanetricarboxylic acid, 2-amino-1,2,3-propanetricarboxylic acid, N-methyl-1-amino -1,2,3-propanetricarboxylic acid, N-methyl-2-amino-1,2,3-
It is propane tricarboxylic acid, The manufacturing method of the diamine type polyamino acid and its metal salt of Claim 1 or 2 characterized by the above-mentioned. 4. The dihaloalkane derivative is dihaloethane, dihalopropane, 2,3-dihalosuccinic acid, 2,3.
-Dimethyl dihalosuccinate, 2,3-dihalopropionic acid, methyl 2,3-dihalopropionate, 2,3-dihalopropionitrile, 2,4-dihaloglutaric acid, 2,
It is dimethyl 4-dihaloglutarate, The manufacturing method of the diamine type polyamino acid and its metal salt of Claim 1 or 2 characterized by the above-mentioned. 5. The metal ion is at least one metal ion selected from the group consisting of iron, copper, zinc, nickel, cobalt, aluminum, manganese, magnesium and calcium.
Alternatively, the method for producing the diamine-type polyamino acid according to 2 or a metal salt thereof. 6. The organic solvent is at least one selected from ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, diethylene glycol monoalkyl ethers, and triethanolamine. Item 3. A method for producing a diamine-type polyamino acid and a metal salt thereof according to Item 2. 7. At least one selected from a diamine-type polyamino acid synthesized by the reaction of the bimolecular amino acid according to claim 3 and one dihaloalkane or epichlorohydrin molecule according to claim 4 and a metal salt thereof as an active ingredient. Biodegradable chelating agent contained.