Industrial-grade organic carboxylic acid compound purification method and product

Abstract

The invention provides a purification method of an industrial-grade organic carboxylic acid compound and a product. The purification method comprises the following steps: mixing and dissolving an industrial-grade organic carboxylic acid compound, organic alkali, an acidic chelating agent and water, and filtering to remove insoluble substances to obtain a first solution; enabling the first solution to pass through an adsorption resin column bed at a first flow rate until resin adsorption is saturated; eluting the column bed by using an electronic-grade organic alkali aqueous solution, an electronic-grade organic acid aqueous solution and ultrapure water in sequence; eluting with an electronic-grade eluent, and collecting the eluent; and carrying out rotary evaporation, recrystallization, filtration and drying on the eluent to obtain a purified organic carboxylic acid compound solid. According to the method, metal ion impurities in the organic carboxylic acid compound can be removed, the purification efficiency is high, universality is achieved, the process is simple, and large-scale production is easy to achieve.

Description

Technical Field

[0001] This invention relates to the field of organic compound purification, specifically to an industrial-grade method and product for purifying organic carboxylic acid compounds. Background Technology

[0002] Formulated wet electronic chemicals are key materials throughout the entire chip manufacturing process. Organic carboxylic acid compounds, due to their structural characteristics, possess certain unique functions, such as adjusting solution pH, accelerating etching of specific media, and selectively chelating or coordinating with certain metals and dielectric materials to inhibit corrosion. Therefore, organic carboxylic acid compounds are frequently used as functional additives in the formulation development of formulated wet electronic chemicals.

[0003] Compared to general industrial chemicals, chemicals used in microelectronics (also known as electronic chemicals) have stringent requirements regarding purity, metal ions, anions, and particulate matter, especially metal ions. The presence of metal ion impurities directly affects the reliability and threshold voltage of components, leading to low breakdown and defects. Metal ion impurities in wet electronic chemicals often need to be controlled at the ppb or ppt level; therefore, the removal of metal ion impurities is one of the technical barriers to product development.

[0004] Traditional separation and purification methods include various techniques such as reaction, distillation, absorption, adsorption, and extraction. Distillation and absorption methods offer high purification efficiency, but for most organic carboxylic acid compounds, side reactions at higher temperatures can easily introduce impurities, or the compounds may have high boiling points, making conventional methods unsuitable. Extraction purification often requires multiple purification steps, resulting in low efficiency, and some extractants are highly toxic. These problems lead to commercially available organic carboxylic acid compounds having high metal ion content, failing to meet the requirements for electronic chemicals, and rendering traditional purification methods unsuitable. Summary of the Invention

[0005] To address the issue of sourcing electronic-grade organic carboxylic acid compounds, this invention provides an improved purification method for organic carboxylic acid compounds. This method effectively reduces metal ion impurities in organic carboxylic acid compounds, avoids degradation or deterioration of compounds due to purification methods, and ensures that the compounds meet the requirements for use in formulated wet electronic chemicals.

[0006] The first aspect of this application provides a method for purifying industrial-grade organic carboxylic acid compounds, comprising: (1) Mix and dissolve industrial-grade organic carboxylic acid compound, organic base, acidic chelating agent and water, filter to remove insoluble matter, and obtain the first solution; (2) Pass the first solution through the adsorption resin column bed at a first flow rate until the resin is saturated; (3) The column bed was rinsed sequentially with electronic-grade organic base aqueous solution, electronic-grade organic acid aqueous solution, and ultrapure water; (4) Elute with electronic grade eluent and collect the eluent; (5) The eluent obtained in step (4) is subjected to rotary evaporation, recrystallization, filtration and drying to obtain a purified solid organic carboxylic acid compound.

[0007] According to the purification method of the first aspect, in step (1), the organic base is selected from one or more of the following: tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, ammonia, ethanolamine, isopropanolamine, diethylenetriamine, 1,3-propanediamine, ethylamine, diethanolamine, triethanolamine, diethylene glycolamine, n-butylamine; and / or The acidic chelating agent is an organic compound having a chelating group, wherein the chelating group is selected from one or more of the following: carboxyl, hydroxyl, sulfonic acid, amino, amide. Preferably, the acidic chelating agent is selected from one or more of the following: carboxylic acid chelating agents, β-dicarbonyl compounds, hydroxyquinoline compounds, organophosphate chelating agents, and sulfonic acid chelating agents.

[0008] According to the purification method of the first aspect, the mass ratio of the industrial-grade organic carboxylic acid compound, organic base, acidic chelating agent, and water is 1:(0.01~100):(0.01~100):(0.01~100).

[0009] According to the purification method of the first aspect, in step (2), the first flow rate is 1~200 mL / min, preferably 5~50 mL / min.

[0010] According to the purification method of the first aspect, in step (2), the adsorption resin is a pyridine resin; Preferably, the adsorbent resin is cross-linked polyvinylpyridine resin.

[0011] According to the purification method of the first aspect, in step (3), the electronic-grade organic base is selected from one or more of the following: tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, ammonia, ethanolamine, isopropanolamine, diethylenetriamine, 1,3-propanediamine, ethylamine, diethanolamine, triethanolamine, diethylene glycolamine, n-butylamine; and / or The electronic-grade organic acid is selected from formic acid and / or acetic acid, preferably acetic acid.

[0012] According to the purification method of the first aspect, in step (3), the mass ratio of the adsorption resin, electronic grade organic base aqueous solution, electronic grade organic acid aqueous solution and ultrapure water packed in the column bed is 1:(1~10):(1~10):(1~10). The mass percentage concentration of the electronic-grade organic base aqueous solution is 0.01%~1%; The mass percentage concentration of the electronic-grade organic acid aqueous solution is 0.1% to 5%.

[0013] According to the purification method of the first aspect, in step (4), the electronic-grade eluent is selected from one or more of the following: ethanol, ethylene glycol, glycerol, tetrahydrofuran, ethyl acetate, dichloromethane, chloroform, dimethyl sulfoxide, N , N -Dimethylformamide, N , N -Dimethylacetamide, N -Methylpyrrolidone.

[0014] According to the purification method of the first aspect, in step (5), the recrystallization temperature is 35~90℃; and / or The drying temperature is 45~90℃.

[0015] The second aspect of this application provides an electronic-grade organic carboxylic acid compound obtained by purification using the method of the first aspect; Preferably, the content of a single metal ion in the electronic-grade organic carboxylic acid compound is less than 100 ppb.

[0016] The purification method of this application has, but is not limited to, the following beneficial effects: The method for purifying organic carboxylic acid compounds of the present invention can remove metal ion impurities from organic carboxylic acid compounds with high purification efficiency and broad applicability, and the metal ion impurities can be controlled at the ppb level. The method of this application can purify organic carboxylic acid compounds from industrial grade to electronic grade, with the residual amount of a single metal ion less than 100 ppb and a high yield. The method is simple and easily scaled up for mass production. Detailed Implementation

[0017] The present application will be further described in detail below through embodiments. Through these descriptions, the features and advantages of the present application will become clearer and more apparent.

[0018] The term “exemplary” as used herein means “serving as an example, embodiment, or illustration.” Any embodiment illustrated herein as “exemplary” is not necessarily to be construed as superior to or better than other embodiments.

[0019] Furthermore, the technical features involved in the different embodiments of this application described below can be combined with each other as long as they do not conflict with each other.

[0020] This application provides a method for purifying organic carboxylic acid compounds, comprising: (1) Mix and dissolve industrial-grade organic carboxylic acid compound, organic base, acidic chelating agent and water, filter to remove insoluble matter, and obtain the first solution; (2) Pass the first solution through the adsorption resin column bed at a first flow rate until the resin is saturated; (3) The column bed was rinsed sequentially with electronic-grade organic base aqueous solution, electronic-grade organic acid aqueous solution, and ultrapure water; (4) Elute with electronic grade eluent and collect the eluent; (5) The eluent obtained in step (4) is subjected to rotary evaporation, recrystallization, filtration and drying to obtain a purified solid organic carboxylic acid compound.

[0021] In one embodiment, in step (2), the adsorbent resin is a pyridine resin; Preferably, the adsorption resin is a cross-linked polyvinylpyridine resin. The adsorption of organic carboxylic acid compounds by pyridine resins is mainly achieved by the interaction between functional groups. The interaction is mainly: (1) electrostatic adsorption, under acidic conditions, organic carboxylic acids are protonated, and at the same time, the nitrogen atom of the pyridine ring can be protonated to form a positively charged pyridinium ion (-PyH). + (1) The two can be combined through ion exchange or electrostatic attraction; (2) The nitrogen atom of the pyridine ring or the protonated pyridinium ion can form hydrogen bonds with hydroxyl (-OH) or carboxyl (-COOH) groups. At the same time, the aromatic structure of the pyridine ring and the benzene ring of the aromatic carboxylic acid will be stacked in π-π, which will enhance the adsorption. After the pyridine resin adsorbs the organic carboxylic acid compound, the metal ion impurities can be selectively removed by elution. At the same time, the adsorption of organic carboxylic acid by pyridine can inhibit the ionization of organic carboxylic acid, reduce the competition between carboxylic acid and metal ions, and the chelating agent can combine with the metal ions to achieve efficient removal.

[0022] The removal of trace metal impurities from ionic compounds has always been a challenge in the production of electronic chemicals. This invention utilizes the π-π intermolecular interactions and / or electrostatic forces between the pyridine ring and the organic carboxylic acid compound to immobilize the organic carboxylic acid compound molecules onto a resin. Then, a chelating agent is used to remove polyvalent metal ions, and finally, an organic base is used to wash away any remaining monovalent metal ions, thereby removing the metal ions from the organic carboxylic acid compound. The method of this application can purify organic carboxylic acid compounds from industrial grade to electronic grade, with a single metal ion residue of less than 100 ppb and a high yield. This method is simple and easily scalable for mass production.

[0023] In one embodiment, in step (1), the organic base is selected from one or more of the following: tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, ammonia, ethanolamine, isopropanolamine, diethylenetriamine, 1,3-propanediamine, ethylamine, diethanolamine, triethanolamine, diethylene glycolamine, n-butylamine; and / or The acidic chelating agent is an organic compound having a chelating group, wherein the chelating group is selected from one or more of carboxyl, hydroxyl, sulfonic acid, amino, and amide groups. Preferably, the acidic chelating agent is a carboxylic acid chelating agent, an organophosphate chelating agent, a β-dicarbonyl compound, a hydroxyquinoline compound, or a sulfonic acid chelating agent.

[0024] The purification effect of different types of chelates is affected by the interaction between the chelating agent and the resin. The compound to be purified has different purification efficiencies when interacting with different chelating agents. Taking 3,5-dihydroxybenzoic acid as an example, the purification efficiency is the highest when citric acid is used as the chelating agent.

[0025] The acidity in the acidic chelating agent described in this application refers to its function as a proton donor in the sense of a Brønsted acid and / or as an electrophilic electron acceptor in the form of a Lewis acid. It is not limited to compounds having carboxylic acid groups, sulfonic acid groups, etc., but can also be compounds having β-dicarbonyl groups or phenolic hydroxyl groups.

[0026] In one embodiment, in step (1), the mass ratio of the industrial-grade organic carboxylic acid compound, organic base, acidic chelating agent and water is 1:(0.01~100):(0.01~100):(0.01~100).

[0027] In some specific embodiments, in step (1), when the mass part of the industrial-grade organic carboxylic acid compound is 1, the mass part of the organic base can be a value within the range of 0.01, 0.05, 0.1, 0.2, 0.5, 0.8, 1, 2, 5, 8, 10, 20, 50, 80, 100 or any two of these; the mass part of the acidic chelating agent can be a value within the range of 0.01, 0.05, 0.1, 0.2, 0.5, 0.8, 1, 2, 5, 8, 10, 20, 50, 80, 100 or any two of these; and the mass part of the water can be a value within the range of 0.01, 0.05, 0.1, 0.2, 0.5, 0.8, 1, 2, 5, 8, 10, 20, 50, 80, 100 or any two of these.

[0028] In one embodiment, in step (2), the first flow rate is 1~200 mL / min, preferably 5~50 mL / min.

[0029] In some specific embodiments, in step (2), the first flow rate can be a value within the range of 1 mL / min, 5 mL / min, 10 mL / min, 20 mL / min, 30 mL / min, 50 mL / min, 100 mL / min, 150 mL / min, 200 mL / min, or any combination thereof. In one embodiment, in step (3), the electronic-grade organic base is selected from one or more of the following: tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, ammonia, ethanolamine, isopropanolamine, diethylenetriamine, 1,3-propanediamine, ethylamine, diethanolamine, triethanolamine, diethylene glycolamine, n-butylamine; and / or The electronic-grade organic acid is selected from formic acid and / or acetic acid, preferably acetic acid.

[0030] In one specific implementation, the organic base can be removed by a subsequent concentration step.

[0031] Specifically, the same organic base as in step (1) can be selected to simplify the subsequent concentration steps.

[0032] In one embodiment, in step (3), the mass ratio of the adsorption resin, electronic-grade organic base aqueous solution, electronic-grade organic acid aqueous solution, and ultrapure water packed in the column bed is 1:(1~10):(1~10):(1~10). The mass percentage concentration of the electronic-grade organic base aqueous solution is 0.01%~1%; The mass percentage concentration of the electronic-grade organic acid aqueous solution is 0.1% to 5%.

[0033] In some specific embodiments, in step (3), when the mass fraction of the adsorption resin packed in the column bed is 1, the mass fraction of the electronic-grade organic base aqueous solution can be a value within the range of 1, 2, 5, 8, 10 or any two of them, the mass fraction of the electronic-grade organic acid aqueous solution can be a value within the range of 1, 2, 5, 8, 10 or any two of them, and the mass fraction of the ultrapure water can be a value within the range of 1, 2, 5, 8, 10 or any two of them.

[0034] In step (3), the electronic-grade organic base aqueous solution, electronic-grade organic acid aqueous solution, and ultrapure water used for rinsing the column bed can be of the same or different qualities.

[0035] In some specific embodiments, the mass percentage concentration of the electronic-grade organic base aqueous solution can be a value within the range of 0.01%, 0.005%, 0.1%, 0.15%, 0.2%, 0.5%, 0.8%, 1%, or any two of these.

[0036] In some specific embodiments, the mass percentage concentration of the electronic-grade organic acid aqueous solution can be a value within the range of 0.1%, 0.2%, 0.5%, 0.8%, 1%, 2%, 3%, 4%, 5%, or any two of these.

[0037] In one embodiment, in step (4), the electronic-grade eluent is selected from one or more of the following: ethanol, ethylene glycol, glycerol, tetrahydrofuran, ethyl acetate, dichloromethane, chloroform, dimethyl sulfoxide, ... N , N -Dimethylformamide, N , N -Dimethylacetamide, N- Methylpyrrolidone.

[0038] In one embodiment, in step (5), the recrystallization temperature is 35~90°C; and / or The drying temperature is 45~90℃.

[0039] In some specific embodiments, in step (5), the recrystallization temperature can be a value within the range of 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, or any two of these.

[0040] In some specific implementations, in step (5), the drying temperature can be a value within the range of 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, or any two of these.

[0041] In some specific embodiments, in step (5), the volume ratio of the concentrate obtained after rotary evaporation to the eluent can be 1:10, removing about 90% of the solvent.

[0042] In some specific embodiments, the drying method in step (5) is vacuum drying.

[0043] This application also provides an electronic-grade organic carboxylic acid compound prepared using the aforementioned purification method; Preferably, the content of a single metal ion in the electronic-grade organic carboxylic acid compound is less than 100 ppb.

[0044] This invention does not impose any special restrictions on the source of any raw materials; unless otherwise specified, they are all conventional products that can be obtained commercially.

[0045] The adsorption resin used in the following examples is cross-linked polyvinylpyridine resin, and the cross-linking agent is divinylbenzene.

[0046] Example 1 (1) Mix and dissolve 10 g of industrial grade 3,5-dihydroxybenzoic acid (95%), 5 g of 1,3-propanediamine, 0.5 g of oxalic acid and 84.5 mL of water, filter to remove insoluble matter to obtain the first solution; (2) The first solution was passed through the adsorption resin column bed at a flow rate of 20 mL / min until the resin adsorption was saturated; (3) The column bed packed with 500 g of resin was rinsed sequentially with 1000 g of electronic grade 1,3-propanediamine aqueous solution (0.1%), 1000 g of electronic grade acetic acid aqueous solution (0.5%), and 1000 g of ultrapure water. (4) Elute with 100 mL of electronic-grade tetrahydrofuran and collect the eluent; (5) Remove 90% of tetrahydrofuran by rotary evaporation, add 100 mL of ultrapure water, recrystallize at 60°C, filter, and vacuum dry at 60°C to obtain the purified product.

[0047] Example 2 (1) Mix and dissolve 10 g of industrial grade salicylic acid (95%), 5 g of 1,3-propanediamine, 0.5 g of oxalic acid, and 84.5 mL of water, filter to remove insoluble matter to obtain the first solution; (2) The first solution was passed through the adsorption resin column bed at a flow rate of 20 mL / min until the resin adsorption was saturated; (3) The column bed packed with 500 g of resin was rinsed sequentially with 1000 g of electronic grade 1,3-propanediamine aqueous solution (0.1%), 1000 g of electronic grade acetic acid aqueous solution (0.5%), and 1000 g of ultrapure water. (4) Elute with 100 mL of electronic-grade tetrahydrofuran and collect the eluent; (5) Remove 90% of tetrahydrofuran by rotary evaporation, add 100 mL of ultrapure water, recrystallize at 60°C, filter, and vacuum dry at 60°C to obtain the purified product.

[0048] Example 3 (1) Mix and dissolve 10 g of industrial grade m-hydroxybenzoic acid (95%), 5 g of 1,3-propanediamine, 0.5 g of oxalic acid and 84.5 mL of water, filter to remove insoluble matter to obtain the first solution; (2) The first solution was passed through the adsorption resin column bed at a flow rate of 20 mL / min until the resin adsorption was saturated; (3) The column bed packed with 500 g of resin was rinsed sequentially with 1000 g of electronic grade 1,3-propanediamine aqueous solution (0.1%), 1000 g of electronic grade acetic acid aqueous solution (0.5%), and 1000 g of ultrapure water. (4) Elute with 100 mL of electronic-grade tetrahydrofuran and collect the eluent; (5) Remove 90% of tetrahydrofuran by rotary evaporation, add 100 mL of ultrapure water, recrystallize at 60°C, filter, and vacuum dry at 60°C to obtain the purified product.

[0049] Example 4 (1) Mix and dissolve 10 g of industrial grade m-1-hydroxy-2-naphthoic acid (95%), 5 g of 1,3-propanediamine, 0.5 g of oxalic acid and 84.5 mL of water, filter to remove insoluble matter to obtain the first solution; (2) The first solution was passed through the adsorption resin column bed at a flow rate of 20 mL / min until the resin adsorption was saturated; (3) The column bed packed with 500 g of resin was rinsed sequentially with 1000 g of electronic grade 1,3-propanediamine aqueous solution (0.1%), 1000 g of electronic grade acetic acid aqueous solution (0.5%), and 1000 g of ultrapure water. (4) Elute with 100 mL of electronic-grade tetrahydrofuran and collect the eluent; (5) Remove 90% of tetrahydrofuran by rotary evaporation, add 100 mL of ultrapure water, recrystallize at 60°C, filter, and vacuum dry at 60°C to obtain the purified product.

[0050] Example 5 (1) Mix and dissolve 10 g of industrial grade m-3,5-dihydroxybenzoic acid (95%), 5 g of 1,3-propanediamine, 0.5 g of sulfosalicylic acid and 84.5 mL of water, filter to remove insoluble matter to obtain the first solution; (2) The first solution was passed through the adsorption resin column bed at a flow rate of 20 mL / min until the resin adsorption was saturated; (3) The column bed packed with 500 g of resin was rinsed sequentially with 1000 g of electronic grade 1,3-propanediamine aqueous solution (0.1%), 1000 g of electronic grade acetic acid aqueous solution (0.5%), and 1000 g of ultrapure water. (4) Elute with 100 mL of electronic-grade tetrahydrofuran and collect the eluent; (5) Remove 90% of tetrahydrofuran by rotary evaporation, add 100 mL of ultrapure water, recrystallize at 60°C, filter, and vacuum dry at 60°C to obtain the purified product.

[0051] Example 6 (1) Mix and dissolve 10 g of industrial grade m-3,5-dihydroxybenzoic acid (95%), 5 g of 1,3-propanediamine, 0.5 g of 8-hydroxyquinoline and 84.5 mL of water, filter to remove insoluble matter to obtain the first solution; (2) The first solution was passed through the adsorption resin column bed at a flow rate of 20 mL / min until the resin adsorption was saturated; (3) The column bed packed with 500 g of resin was rinsed sequentially with 1000 g of electronic grade 1,3-propanediamine aqueous solution (0.1%), 1000 g of electronic grade acetic acid aqueous solution (0.5%), and 1000 g of ultrapure water. (4) Elute with 100 mL of electronic-grade tetrahydrofuran and collect the eluent; (5) Remove 90% of tetrahydrofuran by rotary evaporation, add 100 mL of ultrapure water, recrystallize at 60°C, filter, and vacuum dry at 60°C to obtain the purified product.

[0052] Example 7 (1) Mix and dissolve 10 g of industrial grade m-3,5-dihydroxybenzoic acid (95%), 5 g of 1,3-propanediamine, 0.5 g of acetylacetone and 84.5 mL of water, filter to remove insoluble matter to obtain the first solution; (2) The first solution was passed through the adsorption resin column bed at a flow rate of 20 mL / min until the resin adsorption was saturated; (3) The column bed packed with 500 g of resin was rinsed sequentially with 1000 g of electronic grade 1,3-propanediamine aqueous solution (0.1%), 1000 g of electronic grade acetic acid aqueous solution (0.5%), and 1000 g of ultrapure water. (4) Elute with 100 mL of electronic-grade tetrahydrofuran and collect the eluent; (5) Remove 90% of tetrahydrofuran by rotary evaporation, add 100 mL of ultrapure water, recrystallize at 60°C, filter, and vacuum dry at 60°C to obtain the purified product.

[0053] Example 8 (1) Mix and dissolve 10 g of industrial grade m-3,5-dihydroxybenzoic acid (95%), 5 g of n-butylamine, 0.5 g of oxalic acid and 84.5 mL of water, filter to remove insoluble matter to obtain the first solution; (2) The first solution was passed through the adsorption resin column bed at a flow rate of 20 mL / min until the resin adsorption was saturated; (3) The column bed packed with 500 g of resin was rinsed sequentially with 1000 g of electronic grade n-butylamine aqueous solution (0.1%), 1000 g of electronic grade acetic acid aqueous solution (0.5%), and 1000 g of ultrapure water; (4) Elute with 100 mL of electronic-grade tetrahydrofuran and collect the eluent; (5) Remove 90% of tetrahydrofuran by rotary evaporation, add 100 mL of ultrapure water, recrystallize at 60°C, filter, and vacuum dry at 60°C to obtain the purified product.

[0054] Example 9 (1) Mix and dissolve 10 g of industrial grade m-3,5-dihydroxybenzoic acid (95%), 5 g of ethanolamine, 0.5 g of oxalic acid and 84.5 mL of water, filter to remove insoluble matter to obtain the first solution; (2) The first solution was passed through the adsorption resin column bed at a flow rate of 20 mL / min until the resin adsorption was saturated; (3) The column bed packed with 500 g of resin was rinsed sequentially with 1000 g of electronic grade ethanolamine aqueous solution (0.1%), 1000 g of electronic grade acetic acid aqueous solution (0.5%), and 1000 g of ultrapure water; (4) Elute with 100 mL of electronic-grade tetrahydrofuran and collect the eluent; (5) Remove 90% of tetrahydrofuran by rotary evaporation, add 100 mL of ultrapure water, recrystallize at 60°C, filter, and vacuum dry at 60°C to obtain the purified product.

[0055] Example 10 (1) Mix and dissolve 10 g of industrial grade m-3,5-dihydroxybenzoic acid (95%), 5 g of 1,3-propanediamine, 0.5 g of oxalic acid and 84.5 mL of water, filter to remove insoluble matter to obtain the first solution; (2) The first solution was passed through the adsorption resin column bed at a flow rate of 20 mL / min until the resin adsorption was saturated; (3) The column bed packed with 500 g of resin was rinsed sequentially with 1000 g of electronic grade 1,3-propanediamine aqueous solution (0.1%), 1000 g of electronic grade acetic acid aqueous solution (0.5%), and 1000 g of ultrapure water. (4) Elute with 100 mL of electronic grade dimethyl sulfoxide and collect the eluent; (5) Remove 90% of tetrahydrofuran by rotary evaporation, add 100 mL of ultrapure water, recrystallize at 60°C, filter, and vacuum dry at 60°C to obtain the purified product.

[0056] Example 11 (1) Mix and dissolve 10 g of industrial grade m-3,5-dihydroxybenzoic acid (95%), 5 g of 1,3-propanediamine, 0.1 g of oxalic acid and 84.5 mL of water, filter to remove insoluble matter to obtain the first solution; (2) The first solution was passed through the adsorption resin column bed at a flow rate of 20 mL / min until the resin adsorption was saturated; (3) The column bed packed with 500 g of resin was rinsed sequentially with 1000 g of electronic grade 1,3-propanediamine aqueous solution (0.1%), 1000 g of electronic grade acetic acid aqueous solution (0.5%), and 1000 g of ultrapure water. (4) Elute with 100 mL of electronic grade ethanol and collect the eluent; (5) Remove 90% of the ethanol by rotary evaporation, add 100 mL of ultrapure water, recrystallize at 60°C, filter, and vacuum dry at 60°C to obtain the purified product.

[0057] Example 12 (1) Mix and dissolve 10 g of industrial grade 3,5-dihydroxybenzoic acid (95%), 5 g of 1,3-propanediamine, 0.1 g of oxalic acid and 84.5 mL of water, filter to remove insoluble matter to obtain the first solution; (2) The first solution was passed through the adsorption resin column bed at a flow rate of 5 mL / min until the resin adsorption was saturated; (3) The column bed packed with 500 g of resin was rinsed sequentially with 1000 g of electronic grade 1,3-propanediamine aqueous solution (0.1%), 1000 g of electronic grade acetic acid aqueous solution (0.5%), and 1000 g of ultrapure water. (4) Elute with 100 mL of electronic-grade tetrahydrofuran and collect the eluent; (5) Remove 90% of tetrahydrofuran by rotary evaporation, add 100 mL of ultrapure water, recrystallize at 60°C, filter, and vacuum dry at 60°C to obtain the purified product.

[0058] Example 13 (1) Mix and dissolve 10 g of industrial grade 3,5-dihydroxybenzoic acid (95%), 5 g of 1,3-propanediamine, 0.5 g of oxalic acid and 84.5 mL of water, filter to remove insoluble matter to obtain the first solution; (2) The first solution is passed through the adsorption resin column bed at a flow rate of 50 mL / min until the resin adsorption is saturated; (3) The column bed packed with 500 g of resin was rinsed sequentially with 1000 g of electronic grade 1,3-propanediamine aqueous solution (0.1%), 1000 g of electronic grade acetic acid aqueous solution (0.5%), and 1000 g of ultrapure water. (4) Elute with 100 mL of electronic-grade tetrahydrofuran and collect the eluent; (5) Remove 90% of tetrahydrofuran by rotary evaporation, add 100 mL of ultrapure water, recrystallize at 60°C, filter, and vacuum dry at 60°C to obtain the purified product.

[0059] Comparative Example 1 (1) Mix and dissolve 10 g of industrial grade 3,5-dihydroxybenzoic acid (95%), 5 g of 1,3-propanediamine, 0.5 g of oxalic acid and 84.5 mL of water, filter to remove insoluble matter to obtain the first solution; (2) The first solution was passed through the adsorption resin column bed at a flow rate of 20 mL / min until the resin adsorption was saturated; (3) The column bed packed with 500 g of resin was rinsed sequentially with 1000 g of electronic grade 1,3-propanediamine aqueous solution (0.1%), 1000 g of electronic grade acetic acid aqueous solution (0.5%), and 1000 g of ultrapure water. (4) Elute with 100 mL of tetrahydrofuran (AR, analytical grade) and collect the eluent; (5) Remove 90% of tetrahydrofuran by rotary evaporation, add 100 mL of ultrapure water, recrystallize at 60°C, filter, and vacuum dry at 60°C to obtain the purified product.

[0060] Comparative Example 2 (1) Mix and dissolve 10 g of industrial grade 3,5-dihydroxybenzoic acid (95%), 5 g of 1,3-propanediamine and 85 mL of water, filter to remove insoluble matter to obtain the first solution; (2) The first solution was passed through the adsorption resin column bed at a flow rate of 20 mL / min until the resin adsorption was saturated; (3) The column bed packed with 500 g of resin was rinsed sequentially with 1000 g of electronic grade 1,3-propanediamine aqueous solution (0.1%), 1000 g of electronic grade acetic acid aqueous solution (0.5%), and 1000 g of ultrapure water. (4) Elute with 100 mL of electronic-grade tetrahydrofuran and collect the eluent; (5) Remove 90% of tetrahydrofuran by rotary evaporation, add 100 mL of ultrapure water, recrystallize at 60°C, filter, and vacuum dry at 60°C to obtain the purified product.

[0061] The yield, purity, and metal ion impurity content of the products obtained in Examples 1-13 and Comparative Example 1 were tested respectively, and the test results are shown in Table 1 and Table 2.

[0062] in, Yield (%) = (Actual product mass / Expected product mass) × 100% The metal ion impurity content (ppb) is μg / kg.

[0063] The content of metal ion impurities was tested using an Agilent 8900, in accordance with the "SJ / T 11637-2016 General Rules for Inductively Coupled Plasma Mass Spectrometry of Electronic Chemicals".

[0064] Table 1

[0065] Table 2. Concentrations of various metal ions in the examples and comparative examples.

[0066] The results above show that the methods in Examples 1-13, using the method of this application, purified different industrial organic carboxylic acids, and the concentrations of single metal ions in the products were all below 100 ppb. Comparative Example 1 used analytical grade tetrahydrofuran as the eluent. Because analytical grade tetrahydrofuran itself contains metal impurities, it contaminated the purified product, resulting in a high concentration of metal ion impurities. Comparative Example 2, because it did not use a chelating agent, could not compete for the polyvalent metal ions chelated with 3,5-dihydroxybenzoic acid, resulting in a high concentration of metal ions in the product. Therefore, the methods in Comparative Examples 1 and 2 cannot purify industrial organic carboxylic acids into electronic-grade organic carboxylic acids with single metal ion concentrations all below 100 ppb.

[0067] The present application has been described above with reference to preferred embodiments; however, these embodiments are merely exemplary and illustrative. Various substitutions and modifications can be made to the present application based on these embodiments, all of which fall within the protection scope of the present application.

Claims

1. A method for purifying an industrial grade organic carboxylic acid compound, characterized by The method comprises: (1) mixing, dissolving, filtering and removing insoluble substances to obtain a first solution, wherein the industrial-grade organic carboxylic acid compound, the organic base, the acidic chelating agent and water are mixed and dissolved; (2) passing the first solution through a column bed of adsorption resin at a first flow rate until the resin is saturated with adsorption; (3) sequentially using electronic-grade aqueous organic base, electronic-grade aqueous organic acid and ultrapure water to elute the column bed; (4) using electronic-grade eluent to elute and collect the eluent; (5) performing rotary evaporation, recrystallization, filtration and drying on the eluent obtained in step (4) to obtain a purified organic carboxylic acid compound solid.

2. The purification method of claim 1, wherein, In step (1), the organic base is selected from one or more of the following: tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, aqueous ammonia, ethanolamine, isopropanolamine, diethylenetriamine, 1,3-propanediamine, ethylamine, diethanolamine, triethanolamine, diglycolamine and n-butylamine; and / or The acidic chelating agent is an organic compound having a coordination group selected from one or more of the following: carboxyl, hydroxyl, sulfonic acid group, amino and amide group.

3. The purification method of claim 2, wherein, The acidic chelating agent is selected from one or more of the following: carboxylic acid chelating agent, β-dicarbonyl compound, hydroxyquinoline compound, organic phosphoric acid chelating agent and sulfonic acid chelating agent.

4. The purification method of claim 1, wherein, In step (1), the mass ratio of the industrial-grade organic carboxylic acid compound, the organic base, the acidic chelating agent and water is 1:(0.1-1):(0.01-0.1):(1-20).

5. The purification method of claim 1, wherein, In step (2), the first flow rate is 1-50 mL / min.

6. The method of claim 5, wherein, In step (2), the first flow rate is 5-50 mL / min.

7. The purification method of claim 1, wherein, In step (2), the adsorption resin is a pyridine resin.

8. The purification method of claim 7, wherein, In step (2), the adsorption resin is a cross-linked polyvinylpyridine resin.

9. The purification method of claim 1, wherein, In step (3), the electronic-grade organic base is selected from one or more of the following: tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, aqueous ammonia, ethanolamine, isopropanolamine, diethylenetriamine, 1,3-propanediamine, ethylamine, diethanolamine, triethanolamine, diglycolamine and n-butylamine; and / or The electronic-grade organic acid is selected from formic acid and / or acetic acid.

10. The purification method of claim 9, wherein, The electronic-grade organic acid is acetic acid.

11. The purification method of claim 1, wherein, In step (3), the mass ratio of the adsorption resin, the electronic-grade aqueous organic base, the electronic-grade aqueous organic acid and the ultrapure water packed in the column bed is 1:(1-10):(1-10):(1-10); The mass percentage concentration of the electronic-grade aqueous organic base is 0.01%-1%; The mass percentage concentration of the electronic-grade aqueous organic acid is 0.1%-5%.

12. The purification method of claim 1, wherein, In step (4), the electronic grade eluent is selected from one or more of the following: ethanol, ethylene glycol, glycerol, tetrahydrofuran, ethyl acetate, dichloromethane, chloroform, dimethyl sulfoxide, N , N dimethylformamide, N , N dimethylacetamide, N methylpyrrolidone.

13. The purification method of claim 1, wherein, In step (5), the temperature for recrystallization is 35-90°C; and / or The temperature for drying is 45-90°C.

14. An electronic-grade organic carboxylic acid compound obtained by purification using the purification method of any one of claims 1-9.

15. The electronic-grade organic carboxylic acid compound according to claim 14, wherein, The content of single metal ions in the electronic-grade organic carboxylic acid compound is less than 100 ppb.

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