Method for preparing chelatable eddha

Abstract

To provide a preparation method capable of preparing high-purity chelatable EDDHA with an excellent yield.SOLUTION: A method for preparing chelatable EDDHA comprises: a step (S1) of mixing phenol, ethylenediamine, glyoxylic acid and sodium hydroxide; a step of (S2) synthesizing a product by reacting the mixture at 75°C to 80°C; a step (S3) of collecting the product by heating the product to 55°C to 65°C; and a step (S4) of washing the collected product using a cleaning solution including deionized water.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing chelate-binding EDDHA, and more particularly to a method that allows for the production of chelate-binding EDDHA with high purity and in excellent yield. [Background technology]

[0002] EDDHA, typified by ethylenediamine-N,N'-bis(2-hydroxyphenylacetic acid), is a chelating agent and a hexadentate ligand that binds metal ions using six binding sites: two amines, two phenolate centers, and two carboxylates.

[0003] A conventional method for synthesizing EDDHA involves reacting a reactant containing phenol, ethylenediamine, glyoxylic acid, and sodium hydroxide at 70-75°C, followed by precipitation at room temperature for 72 hours or more (Structure and fertilizer properties of byproducts formed the synthesis of EDDHA, Journal of agricultural and food chemistry, 2006, 54, 4355-4363).

[0004] However, this reaction requires a relatively long process time, requiring at least three days of precipitation to collect the product after synthesis, making it difficult to produce chelate-binding EDDHA on an economical and industrial scale. In addition, the product produced by this method contains many residues and other by-products, and additional organic solvents must be used to purify it, resulting in the generation of additional waste liquid.

[0005] In addition, chelate-binding EDDHA has a strong affinity for specific metal ions and is used in semiconductor processes as substrate surface cleaners, resist strippers, chemical mechanical polishing slurries, etching agents, etc. However, since semiconductor processes are significantly affected by impurities, the EDDHA produced must be synthesized as a high-purity compound that does not contain unnecessary metals in order to be used in these semiconductor processes.

[0006] Therefore, there is a need for a new method for producing EDDHA that can produce high-purity chelate-binding EDDHA in good yield. Summary of the Invention [Problem to be solved by the invention]

[0007] The present invention aims to provide a manufacturing method for synthesizing chelate-binding EDDHA in good yield and high purity.

[0008] According to the present invention, by synthesizing EDDHA by heating a mixture of substituted or unsubstituted phenol, ethylenediamine, glyoxylic acid, and sodium hydroxide to a predetermined temperature, sufficient thermal energy required for the synthesis reaction is added, allowing EDDHA to be synthesized in excellent yield. Furthermore, by precipitation by heating at a constant temperature, the recovery rate of the product is increased, allowing chelate-binding EDDHA to be produced economically and on an industrial scale.

[0009] Furthermore, the chelate-binding EDDHA prepared by the above method has a low metal content in the product, and can be used for various purposes in semiconductor processes. [Means for solving the problem]

[0010] The present invention can provide a method for producing chelate-binding EDDHA, which includes the steps of: (S1) mixing substituted or unsubstituted phenol, ethylenediamine, glyoxylic acid, and sodium hydroxide; (S2) reacting the mixture at 75°C to 80°C to synthesize a product; (S3) heating the product to 55°C to 65°C to recover the product; and (S4) washing the recovered product with a washing solution containing deionized water.

[0011] In the step (S2), the mixture can be reacted at 75°C to 80°C for 2 to 4 hours to synthesize a product.

[0012] In the step (S3), the product can be recovered by heating the product at 55°C to 65°C for 30 minutes to 2 hours.

[0013] The concentration of the sodium hydroxide may be 35 to 50 wt %.

[0014] The synthesis yield of the product by the above production method may be 18% or more.

[0015] The product of the method may have an Al and Fe content of 5 ppm or less.

[0016] The product obtained by the above production method may have a K and Ca content of 5 ppm or less.

[0017] The product produced by the above production method may have a Na content of 40 ppm or less.

[0018] The cleaning solution may further comprise an additive selected from the group consisting of an organic solvent including acetone, an organic base including NH4OH, an inorganic acid including HNO3 and HCl, and combinations thereof.

[0019] The cleaning solution may contain deionized water and an additive selected from the group consisting of an organic solvent including acetone, an organic base including NHOH, an inorganic acid including HNO and HCl, and combinations thereof, in a weight ratio of 5:1 to 20:1. [Effects of the Invention]

[0020] When the method for producing chelating EDDHA provided by the present invention is used, it is possible to produce chelating EDDHA of high purity in excellent yield.

[0021] Furthermore, the EDDHA produced by the above method has a low metal content in the product, making it suitable for various applications in semiconductor processes. DETAILED DESCRIPTION OF THE INVENTION

[0022] Unless otherwise defined herein, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terms used to describe the present invention are merely for the purpose of effectively describing specific embodiments and are not intended to limit the present invention.

[0023] As used herein, the singular forms "a," "an," and "the" include the plural forms as well, unless the context clearly dictates to the contrary.

[0024] As used herein, the meaning of "comprising" embodies certain properties, regions, integers, steps, operations, elements and / or components, and does not exclude the presence or addition of other certain properties, regions, integers, steps, operations, elements, components and / or groups.

[0025] Although the present invention can be embodied in various forms through various modifications, specific embodiments will be described in detail below by way of example, but it should be understood that this is not intended to limit the present invention to the specific disclosed embodiments, and that the present invention encompasses all modifications, equivalents, and alternatives within the spirit and technical scope of the present invention.

[0026] In this specification, when the positional relationship of two parts is described using, for example, "above," "on top," "below," or "to the side," one or more other parts may be located between the two parts, unless the expressions "directly" or "immediately" are used.

[0027] In this specification, when a temporal relationship is described using, for example, "after," "following," "next," or "before," the expressions "directly" or "immediately" are not used, and therefore non-consecutive cases may also be included.

[0028] As used herein, the term "at least one" should be understood to include all possible combinations of one or more associated items.

[0029] The method for producing chelate-binding EDDHA according to a specific embodiment of the invention is described in more detail below.

[0030] According to one embodiment of the invention, there is provided a method for producing chelate-binding EDDHA, comprising the steps of: (S1) mixing substituted or unsubstituted phenol, ethylenediamine, glyoxylic acid, and sodium hydroxide; (S2) reacting the mixture at 75°C to 80°C to synthesize a product; (S3) heating the product to 55°C to 65°C to recover the product; and (S4) washing the recovered product with a washing solution containing deionized water.

[0031] EDDHA can be industrially produced by a Mannich-like reaction between substituted or unsubstituted phenol, ethylenediamine, glyoxylic acid, and sodium hydroxide, as shown in Reaction Scheme 1 below. [ka]

[0032] In this case, the synthesis of EDDHA produces A as the main component along with a mixture of positional isomers identified as B and C, and other by-products are produced in varying amounts depending on the reaction conditions.

[0033] The A is ethylenediamine-N,N'-bis(2-hydroxyphenylacetic acid) (o,o-EDDHA), which is a chelating EDDHA that can bind to metal ions to form a hexadentate ligand.

[0034] The compound B is 2-((2-((carboxy(2-hydroxyphenyl)methyl)amino)ethyl)amino)-2-(4-hydroxyphenyl)acetic acid, also known as o,p-EDDHA, which has a structure in which a hydroxy group is substituted ortho to the phenyl group and is capable of chelating with metal ions.

[0035] The C is 2,2'-(ethane-1,2-diylbis(azanediyl))bis(2-(4-hydroxyphenyl)acetic acid), also known as p,p-EDDHA, which has a structure in which all hydroxy groups on the phenyl group are substituted in the para-direction, and is therefore unable to chelate with metal ions.

[0036] In other words, A, B, and C are all compounds called EDDHA, but only A and B can chelate with metal ions, and the chelate-binding EDDHA to be produced in this invention refers to A and B excluding C.

[0037] In the conventional method for synthesizing EDDHA, a reactant containing phenol, ethylenediamine, glyoxylic acid, and sodium hydroxide was reacted at 70 to 75°C, and then the product was precipitated at room temperature for 72 hours or more to obtain the product.

[0038] However, this reaction requires a relatively long process time, requiring at least 3 days (72 hours) of precipitation to obtain the synthesized product. In addition, the product produced by this method contains a large amount of residues and other by-products, and additional organic solvents must be used to purify it, resulting in the generation of additional waste liquid.

[0039] In order to solve the above-mentioned problems, the present inventors have confirmed that EDDHA can be synthesized in a better yield by synthesizing a mixture of substituted or unsubstituted phenol, ethylenediamine, glyoxylic acid, and sodium hydroxide at a predetermined temperature by heating it to provide sufficient thermal energy required for the synthesis reaction, and that high-purity chelate-binding EDDHA can be produced economically and on an industrial scale by increasing the recovery rate of the product through precipitation by heating at a constant temperature, thereby completing the present invention.

[0040] According to the present invention, when substituted or unsubstituted phenol, ethylenediamine, glyoxylic acid, and sodium hydroxide are mixed (step S1), and then the mixture is reacted at 75°C to 80°C to synthesize a product (step S2), EDDHA can be produced in a higher yield than when the reaction is carried out at 70°C to 75°C as conventionally known.

[0041] This is thought to be due to the fact that the reaction proceeds at an average temperature about 5°C higher than the conventionally known temperature of 70°C to 75°C, which allows for sufficient thermal energy to be obtained for the reaction, and that the high reaction temperature causes the water contained in the reactants to evaporate, resulting in a decrease in the water content.

[0042] If the reaction temperature exceeds 80°C, the thermal energy required for the reaction is sufficient, but the heat added is excessive, which may result in thermal decomposition of the synthesized compound or an increase in the amount of other addition products, thereby reducing the yield of the chelate-binding EDDHA to be synthesized.

[0043] In this case, the step (S2) of reacting the mixture at 75°C to 80°C to synthesize a product may be carried out for about 2 hours to 4 hours, preferably about 2 hours 30 minutes to 3 hours 30 minutes, and more preferably about 3 hours.

[0044] If the reaction time is less than 2 hours, the reaction yield may decrease because there is not enough time for the product to be synthesized, and if it exceeds 4 hours, EDDHA will polymerize and turn into unusable by-products, which is undesirable.

[0045] At this time, the concentration of the sodium hydroxide may be 35 to 50 wt %, preferably 40 to 50 wt %.

[0046] While conventional methods use a 30 wt% aqueous solution of sodium hydroxide, the present invention uses a 35-50 wt% aqueous solution of sodium hydroxide. Specifically, sodium hydroxide cannot exist at more than 30 wt% at room temperature, but the heat generated in the process of mixing sodium hydroxide with water allows for the production of a 50 wt% aqueous solution of sodium hydroxide without additional energy, thereby improving synthesis efficiency.

[0047] On the other hand, the reaction may be carried out at a pH of about 8 to 10 by adding sodium hydroxide to a mixture of substituted or unsubstituted phenol, ethylenediamine, glyoxylic acid, and sodium hydroxide.

[0048] In the synthesis reaction of step (S2), chelate-binding EDDHA containing o,o-EDDHA and o,p-EDDHA is synthesized and remains dissolved in the solvent, which can be recovered by heating to 55°C to 65°C (step S3).

[0049] Conventionally, in order to remove the organic solvent during the process of separating the product, the product has been separated by leaving the mixture at room temperature for 72 hours or more to obtain a precipitate, which is then filtered to obtain the product. However, this method is uneconomical because it takes a long time to obtain the product, and the organic solvent is not sufficiently removed during the process of separating the product, making it difficult to produce high-purity EDDHA on an industrial scale.

[0050] The present inventors have confirmed that when the product synthesized in step (S2) is heated at 55°C to 65°C for a certain period of time, the recovery time of the product can be significantly shortened.

[0051] That is, when the product is recovered at about 55°C to 65°C, preferably about 60°C, the organic solvent can be removed at a high speed without decomposing the synthesized product, while maintaining thermal stability, and in this process, by-products and contaminants are also removed, allowing a high-purity product to be recovered.

[0052] For example, dichloromethane (CH2Cl2) can be used as an organic solvent in the process of recovering the synthesized product by layer separation. When heated to 55-65°C, the remaining dichloromethane boils and can be removed. Unreacted phenol can also be removed by increasing its volatility when heated to 55-65°C.

[0053] In this case, the step (S3) of heating the product to 55°C to 65°C and recovering the product may be carried out for about 30 minutes to 2 hours, preferably about 1 hour to 1 hour and 30 minutes, and more preferably about 1 hour.

[0054] If the recovery time is less than 30 minutes, the organic solvent is not removed sufficiently, and the product cannot be obtained in sufficient quantity. If the recovery time exceeds 2 hours, the product may be decomposed, which is not preferable.

[0055] The method for producing chelating EDDHA of the present invention includes a step (S4) of washing the recovered product with a washing solution containing deionized water.

[0056] The step (S4) additionally removes metals and synthetic residues present in the product, thereby producing chelate-binding EDDHA with higher purity.

[0057] In this case, the cleaning solution may further include an additive selected from the group consisting of an organic solvent including acetone, an organic base including NH4OH, an inorganic acid including HNO3 and HCl, and combinations thereof.

[0058] The additive serves to remove metal contaminants and may be present in ionic form.

[0059] Specifically, the deionized water and an additive selected from the group consisting of an organic solvent including acetone, an organic base including NH4OH, an inorganic acid including HNO3 and HCl, and combinations thereof can be mixed in a weight ratio of 5:1 to 20:1, preferably a weight ratio of 7:1 to 15:1, and more preferably a weight ratio of 8:1 to 12:1.

[0060] According to the production method of the present invention, chelate-binding EDDHA products can be produced with excellent yields of 18% or more, preferably 19% or more, and more preferably 20% or more, and with high purity of 90% or more, preferably 95% or more, and more preferably 97% or more.

[0061] According to the production method of the present invention, a mixture of substituted or unsubstituted phenol, ethylenediamine, glyoxylic acid, and sodium hydroxide is heated to a predetermined temperature for synthesis, whereby sufficient thermal energy necessary for the synthesis reaction is applied to reduce the amount of by-products, and by-products and contaminants are removed by precipitation due to heating at a constant temperature, thereby producing a high-purity product.

[0062] For example, the Al and Fe contents of the product obtained by the above-described manufacturing method may each be 5 ppm or less, preferably 3 ppm or less, and more preferably 2 ppm or less.

[0063] The K and Ca contents of the product obtained by the above production method may be 5 ppm or less, preferably 4 ppm or less, and more preferably 3 ppm or less.

[0064] The Na content of the product obtained by the above production method may be 40 ppm or less, preferably 35 ppm or less, and more preferably 30 ppm or less.

[0065] Since sodium hydroxide is used as a reactant in the synthesis of EDDHA, the produced EDDHA contains sodium metal as an impurity. However, when EDDHA is synthesized using the production method of the present invention, the sodium content of the product can be reduced to 40 ppm or less, which is preferable.

[0066] That is, the chelate-binding EDDHA prepared by the above method has a low metal content in the product and can be used for various purposes in semiconductor processes. [Example]

[0067] Hereinafter, the embodiments of the present invention will be described in more detail with reference to the following examples. However, the following examples are merely illustrative of the embodiments of the present invention, and the scope of the present invention is not limited to the following examples.

[0068] (1) Example 1 Phenol (100.0 g, 1.063 mol) was dissolved at 40–45 °C in a two-neck round-bottom flask equipped with a reflux condenser and a magnetic stir bar, after which dry ethylenediamine (2.46 g, 40.9 mmol) was added and the mixture was stirred for 10 min.

[0069] To the stirred mixture was slowly added dropwise 50% NaOH (3.33 g, 40.9 mmol) and 50% glyoxylic acid (12.12 g, 81.8 mmol).

[0070] The mixture was heated at 75-80°C for 3 hours to synthesize the product. After reaching room temperature, water (120 mL) and CH2Cl2 (240 mL) were added, and the resulting mixture was stirred for 10 minutes.

[0071] Thereafter, the mixture was heated in a thermostatic water bath at 60°C for 1 hour, and the precipitated product was collected by filtration.

[0072] Deionized water and the synthesized product were mixed in a weight ratio of 10:1 and mixed for 20 minutes, then separated, washed, and dried at 60°C to obtain 3.45 g of a mixture of o,o-EDDHA and o,p-EDDHA.

[0073] (2) Example 2 A mixture of o,o-EDDHA and o,p-EDDHA (3.45 g) was obtained in the same manner as in Example 1, except that a mixture of deionized water and acetone (Sigma-Aldrich) was used in a weight ratio of 10:1.

[0074] (3) Example 3 3 g of a mixture of o,o-EDDHA and o,p-EDDHA was obtained in the same manner as in Example 1, except that 33% NaOH (5 g, 40.9 mmol) was used as sodium hydroxide.

[0075] (4) Comparative Example 1 A mixture of o,o-EDDHA and o,p-EDDHA (2.4 g) was obtained in the same manner as in Example 1, except that the mixture of phenol, ethylenediamine, glyoxylic acid, and sodium hydroxide was heated at 70 to 75°C for 3 hours.

[0076] (5) Comparative Example 2 A mixture of o,o-EDDHA and o,p-EDDHA (2.1 g) was obtained in the same manner as in Example 1, except that the mixture of phenol, ethylenediamine, glyoxylic acid, and sodium hydroxide was heated at 80 to 85°C for 3 hours.

[0077] (6) Comparative Example 3 A mixture of o,o-EDDHA and o,p-EDDHA (1.95 g) was obtained in the same manner as in Example 1, except that the mixture of phenol, ethylenediamine, glyoxylic acid, and sodium hydroxide was heated at 85 to 90°C for 3 hours.

[0078] (7) Comparative Example 4 Phenol (100.0 g, 1.063 mol) was dissolved at 40–45 °C in a two-neck round-bottom flask equipped with a reflux condenser and a magnetic stir bar, after which dry ethylenediamine (2.46 g, 40.9 mmol) was added and the mixture was stirred for 10 min.

[0079] To the stirred mixture was slowly added dropwise 33% NaOH (4.97 g, 40.9 mmol) and 50% glyoxylic acid (12.12 g, 81.8 mmol).

[0080] The mixture was heated at 75-80°C for 3 hours to synthesize the product. After reaching room temperature, water (120 mL) and CH2Cl2 (240 mL) were added, and the resulting mixture was stirred for 10 minutes.

[0081] After that, the mixture was left at room temperature for 72 hours (3 days), and then the precipitated product was filtered.

[0082] Deionized water and the synthesized product were mixed in a weight ratio of 10:1 and mixed for 20 minutes, then separated, washed, and dried at 60°C to obtain 1.65 g of a mixture of o,o-EDDHA and o,p-EDDHA.

[0083] The room temperature means the natural temperature without heating or cooling, and usually refers to the range of 20±5°C.

[0084] (8) Comparative Example 5 2.1 g of a mixture of o,o-EDDHA and o,p-EDDHA was obtained in the same manner as in Comparative Example 4, except that the resulting mixture was allowed to stand at room temperature for 168 hours (7 days).

[0085] The yield and purity of each product in the examples and comparative examples were calculated and are shown in Table 1 below. The purity of the product can be confirmed by NMR and IR analysis, and in the case of IR, it can be confirmed by the matching rate (%) based on peak matching.

[0086] [Table 1]

[0087] From Table 1, it was confirmed that when chelating EDDHA is produced by the production method of the present invention, sufficient thermal energy required for the synthesis reaction is supplied by heating a mixture of substituted or unsubstituted phenol, ethylenediamine, glyoxylic acid, and sodium hydroxide to a predetermined temperature, thereby synthesizing high-purity EDDHA with excellent yield and purity, and that EDDHA can be produced at a high rate by increasing the product recovery rate through precipitation by heating at a constant temperature.

[0088] (9) Comparative Example 6 Phenol (100.0 g, 1.063 mol) was dissolved at 40–45 °C in a two-neck round-bottom flask equipped with a reflux condenser and a magnetic stir bar, after which dry ethylenediamine (2.46 g, 40.9 mmol) was added and the mixture was stirred for 10 min.

[0089] To the stirred mixture was slowly added dropwise 50% NaOH (3.33 g, 40.9 mmol) and 50% glyoxylic acid (12.12 g, 81.8 mmol).

[0090] The mixture was heated at 75-80°C for 3 hours to synthesize the product. After reaching room temperature, water (120 mL) and CH2Cl2 (240 mL) were added, and the resulting mixture was stirred for 10 minutes.

[0091] Thereafter, the mixture was heated in a thermostatic water bath at 60°C for 1 hour, and the precipitated product was filtered to obtain 3.45 g of a mixture of o,o-EDDHA and o,p-EDDHA.

[0092] (10) Comparative Example 7 Phenol (100.0 g, 1.063 mol) was dissolved at 40–45 °C in a two-neck round-bottom flask equipped with a reflux condenser and a magnetic stir bar, after which dry ethylenediamine (2.46 g, 40.9 mmol) was added and the mixture was stirred for 10 min.

[0093] To the stirred mixture was slowly added dropwise 50% NaOH (3.33 g, 40.9 mmol) and 50% glyoxylic acid (12.12 g, 81.8 mmol).

[0094] The mixture was heated at 70-75°C for 3 hours to synthesize the product. After reaching room temperature, water (120 mL) and CH2Cl2 (240 mL) were added, and the resulting mixture was stirred for 10 minutes.

[0095] After that, the mixture was left at room temperature for 72 hours (3 days), and the precipitated product was filtered to obtain 1.6 g of a mixture of o,o-EDDHA and o,p-EDDHA.

[0096] The metal contents in the products obtained in Example 1, Comparative Example 6 and Comparative Example 7 were analyzed and are shown in Table 2 below.

[0097] The metal content in EDDHA was analyzed after wet digestion using the following method: Specifically, 0.1g of EDDHA was digested with 10ml of 70% nitric acid using an Anton Parr MULTIWAVE 5000 60Hz PACKAGE 24HVT80, and then recovered with 3% nitric acid and analyzed using an ICP-MS 8900.

[0098] [Table 2]

[0099] From Table 2, it was confirmed that when chelate-binding EDDHA is produced by the production method of the present invention, metals and synthetic residues present in the product are additionally removed, thereby producing chelate-binding EDDHA of higher purity.

Claims

1. A step (S1) of mixing phenol, ethylenediamine, glyoxylic acid and sodium hydroxide; Step (S2) of reacting the mixture at 75°C to 80°C to synthesize a product; (S3) heating the product to 55°C to 65°C and recovering the product; and (S4) washing the recovered product with a washing solution containing deionized water. Method for producing chelateable EDDHA.

2. 2. The method for producing chelating EDDHA according to claim 1, wherein in step (S2), the mixture is reacted at 75 to 80°C for 2 to 4 hours to synthesize the product.

3. 2. The method for producing chelating EDDHA according to claim 1, wherein in step (S3), the product is heated at 55°C to 65°C for 30 minutes to 2 hours to recover the product.

4. 2. The method for producing chelating EDDHA according to claim 1, wherein the concentration of the sodium hydroxide is 35-50 wt %.

5. The method for producing chelating EDDHA according to claim 1, wherein the synthesis yield of the product produced by the method is 18% or more.

6. 2. The method for producing chelating EDDHA according to claim 1, wherein the Al and Fe contents of the product of said method are each 5 ppm or less.

7. 2. The method for producing chelating EDDHA according to claim 1, wherein the K and Ca contents of the product obtained by said method are each 5 ppm or less.

8. 2. The method for producing chelating EDDHA according to claim 1, wherein the Na content of the product obtained by said method is 40 ppm or less.

9. The cleaning solution is an organic solvent containing acetone, NH ４ Organic bases containing OH, HNO ３ 2. The method of claim 1, further comprising an additive selected from the group consisting of inorganic acids, including HCl, and HCl, and combinations thereof.

10. 10. The method for producing chelating EDDHA according to claim 9, wherein the washing solution comprises deionized water:additive in a weight ratio of 5:1 to 20:1.

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