CN114075124A

CN114075124A - Preparation method of electronic grade guanidine salt

Info

Publication number: CN114075124A
Application number: CN202010841622.2A
Authority: CN
Inventors: 丁姜宏; 刘兵; 彭洪修
Original assignee: Anji Microelectronics Shanghai Co Ltd
Current assignee: Anji Microelectronics Shanghai Co Ltd
Priority date: 2020-08-20
Filing date: 2020-08-20
Publication date: 2022-02-22

Abstract

The invention provides a preparation method of electronic grade guanidine salt, which comprises the following steps of (1) preparing a guanidine salt aqueous solution by using ultrapure water; (2) adding an anti-solvent to the aqueous guanidinium solution to obtain a wet precipitate; (3) and drying the precipitate to obtain the electronic grade guanidine salt. The preparation method provided by the invention is simple to operate and high in recovery rate; the method is carried out at room temperature, is safe and reliable, and has no potential safety hazard; the raw materials are low in price, so that the production cost can be effectively reduced; the purity of the obtained product is high, and the purity of the obtained guanidine salt can reach the content of more than 99.5 percent and the metal ion content of less than 1 ppm.

Description

Preparation method of electronic grade guanidine salt

Technical Field

The invention relates to the field of chemical industry, and in particular relates to a preparation method of an electronic grade guanidine salt

Background

The recrystallization is a purification process with simple operation and low equipment cost. Recrystallization is carried out by utilizing solubility difference of different temperatures, for example, in a preparation process of methimazole disclosed in CN105523998A, the methimazole is recrystallized by adopting solvents such as methanol, ethanol, isopropanol and the like through temperature rise and temperature reduction, and finally, a product with HPLC purity of more than 99% and common metal ions of less than 1ppm is obtained. CN110606820A adopts toluene, ethanol and water which are mixed according to a certain proportion as a crystallization solvent to recrystallize N-ethyl carbazole, and the obtained final product has impurities less than 0.1 percent and metal ion content less than 100 ppm. However, the alcohol adopted by the method is a low-flash-point solvent (flash point is less than 15 ℃), and the temperature is high (>50 ℃) in the operation process, so that potential safety hazards exist. CN1850590A discloses a method for producing electronic grade phosphoric acid, which can obtain electronic grade phosphoric acid with total content of metal ions not more than 0.6ppm by a gradient temperature reduction method, but the production process needs to be strictly controlled, and the efficiency needs to be improved. CN101781185A discloses a method for removing metal ions in polyhydroxy benzophenone synthesis, metal ions are reduced by adding a metal ion chelating agent in the recrystallization process, the content of the metal ions in the product is reduced to below 100ppb, but the added metal ion chelating agent is inevitably wrapped in the product, and the purity of the product is lower.

Similarly, recrystallization can also be achieved by using a difference in solubility between different solvents, i.e., by anti-solvent recrystallization. After the anti-solvent is added, the material to be purified is quickly supersaturated and separated out. Such a method is commonly used in pharmaceutical purification, such as the purification of terephthalaldehyde mentioned in CN101006044A, which finally yields a product with a purity of > 99.6%. The method for purifying urapidil by using an anti-solvent recrystallization method mentioned in CN102267951A finally obtains a product with the purity of more than 99.82%. CN108272867A discloses a process for producing high-purity buckwheat flavone by an anti-solvent crystallization method, wherein the purity can reach more than 99% at most, and the yield can reach more than 94%. However, these patents do not disclose metal ion concentration.

Guanidine salts are also indispensable in semiconductor cleaning and polishing solutions, such as the chemical mechanical polishing solutions mentioned in CN101970595A and CN103834306A, and are indispensable important components because of their obvious inhibition effect on corrosion of specific metals. Also, the guanidine salt plays an important role in cleaning the plasma etching residues as mentioned in CN102051281A, CN101657531A and CN 102827708A.

No patents are currently available on the process for the preparation of electronic grade guanidinium salts. Guanidine salts such as guanidine nitrate have oxidative, toxic properties, and can decompose and explode at high temperatures, and thus the use of temperature-raising and temperature-lowering recrystallization methods has potential safety hazards, especially the use of the low-flash alcohols mentioned in the above-mentioned patents as solvents. Therefore, how to obtain the guanidine salt with the content and the metal ion reaching the standard at room temperature through simple steps becomes a difficult problem to be solved urgently in the field.

Disclosure of Invention

In order to solve the problems, the invention provides a preparation method of electronic grade guanidine salt, which is characterized in that the guanidine salt with the content of 99.5 percent and the metal ion content of less than 1ppm is obtained by recrystallization and one-step purification through an anti-solvent method, the operation is simple, the yield is high, and simultaneously, all the steps are operated at room temperature, and the safety is good.

Specifically, the invention provides a preparation method of an electronic grade guanidine salt, which comprises the following steps:

(1) preparing a guanidine salt aqueous solution by using ultrapure water;

(2) adding an anti-solvent to the aqueous guanidinium solution to obtain a wet precipitate;

(3) and drying the precipitate to obtain the electronic grade guanidine salt.

Preferably, the aqueous solution of guanidine salt is a saturated aqueous solution of guanidine salt.

Preferably, the preparing the aqueous guanidinium solution includes filtering insoluble materials in the aqueous guanidinium solution.

Preferably, the anti-solvent is a water-soluble organic solvent.

Preferably, the water-soluble organic solvent is an alcohol, a ketone, and an ether.

Preferably, the mass ratio of the antisolvent to the guanidine salt aqueous solution is 0.01: 1-10: 1.

Preferably, the step (3) includes washing the wet precipitate again with an anti-solvent.

Preferably, the anti-solvent has a metal ion content of less than 1 ppm.

Compared with the prior art, the invention has the advantages that: the preparation method provided by the invention is simple to operate and high in recovery rate; the method is carried out at room temperature, is safe and reliable, and has no potential safety hazard; the raw materials are low in price, so that the production cost can be effectively reduced; the purity of the obtained product is high, and the purity of the obtained guanidine salt can reach the content of more than 99.5 percent and the metal ion content of less than 1 ppm.

Detailed Description

The advantages of the invention are explained in detail below with reference to specific embodiments.

Example 1:

(1) adding 3kg of guanidine carbonate into 7kg of ultrapure water, stirring to completely dissolve the guanidine carbonate, and filtering to obtain a 30% guanidine carbonate aqueous solution;

(2) adding 14kg of methanol, supersaturating guanidine carbonate, separating out and separating to obtain a guanidine carbonate wet material;

(3) washing the wet guanidine carbonate material with methanol and drying to obtain electronic grade guanidine carbonate.

Example 2:

(1) adding 1.5kg of guanidine phosphate into 8.5kg of ultrapure water, stirring to completely dissolve the guanidine phosphate, and filtering to obtain a 10% guanidine nitrate aqueous solution;

(2) adding 1.0kg of ethanol, supersaturating, separating out and separating guanidine nitrate to obtain a guanidine phosphate wet material;

(3) and washing the wet guanidine phosphate material with acetone, and drying to obtain the electronic grade guanidine phosphate.

Example 3:

(1) adding 1kg of guanidine acetate into 9kg of ultrapure water, stirring to completely dissolve the guanidine acetate, and filtering to obtain a 10% guanidine acetate aqueous solution;

(2) adding 15kg of isopropanol, supersaturating, separating out and separating guanidine nitrate to obtain a guanidine nitrate wet material;

(3) and washing the guanidine nitrate wet material with methanol and then drying to obtain the electronic grade guanidine acetate.

Example 4:

(1) adding 1kg of guanidine nitrate into 9kg of ultrapure water, stirring to completely dissolve the guanidine nitrate, and filtering to obtain a 10% guanidine nitrate aqueous solution;

(2) adding 15kg of butanone, and supersaturating, separating out and separating guanidine nitrate to obtain a guanidine nitrate wet material;

(3) and washing the wet guanidine nitrate material with isopropanol, and drying to obtain the electronic grade guanidine nitrate.

Example 5:

(1)10kg of guanidine nitrate is added into 5kg of ultrapure water, stirred and dissolved completely, and then filtered to obtain 66.7 percent guanidine nitrate aqueous solution;

(2) adding 5kg of ether, supersaturating, separating out and separating guanidine nitrate to obtain a guanidine nitrate wet material;

(3) and washing the wet guanidine nitrate material with diethyl ether, and drying to obtain the electronic grade guanidine nitrate.

Comparative example 1:

(2) adding 5kg of reagent grade ether, supersaturating, separating out and separating guanidine nitrate to obtain a guanidine nitrate wet material;

(3) and washing the wet guanidine nitrate material with reagent grade ether, and drying to obtain the purified guanidine nitrate.

Comparative example 2:

(1) adding 10kg of guanidine nitrate into 5kg of distilled water, stirring to completely dissolve the guanidine nitrate, and filtering to obtain 66.7% guanidine nitrate aqueous solution;

According to the preparation methods in the above examples, the products were obtained separately. The metal ion content in the raw materials and the product is tested by using an ICP-OES method, and the content of guanidine salt in the product is measured by using an acid-base titration test. The test results are shown in table 1:

table 1: test results of examples 1 to 5 and comparative examples 1 to 2

From examples 1 to 5, it can be seen that, for different guanidinium salts, the metal ions contained in the product can be less than 1ppm and the guanidinium salt content can be > 99.5% by using the preparation method of the present invention. The method shows that metal ion impurities and other impurities in the guanidine salt can be removed simultaneously through one-step recrystallization, so that the purity of the guanidine salt reaches the electronic grade.

In comparative example 1, an aqueous solution of guanidine salt was prepared using ultrapure water, the anti-solvent used was reagent grade diethyl ether, and the sodium ion content of guanidine salt was reduced from 410ppm to 84ppm after the anti-solvent crystallization process; in comparative example 2, an aqueous solution of guanidinium salt was prepared using distilled water, and the anti-solvent used was reagent-grade diethyl ether, and the content of sodium ions contained in the guanidinium salt was reduced from 410ppm to 228ppm after the anti-solvent crystallization process was performed. The data in comparative example 1, comparative example 2 were compared with example 5: example 5 the content of sodium ions in the guanidine salt after crystallization by the anti-solvent can be reduced from 410ppm to 0.80ppm by using ultrapure water to prepare the guanidine salt water solution and using pure diethyl ether as the anti-solvent. Analysis shows that when common distilled water or a reagent grade antisolvent is used, because the distilled water and the reagent grade antisolvent still contain impurities, trace impurities enter the guanidinium to be purified in the recrystallization process, so that the purity of the guanidinium is influenced, and the purified guanidinium still cannot reach the expected purity.

The embodiments of the present invention have been described in detail, but the embodiments are merely examples, and the present invention is not limited to the embodiments described above. Any equivalent modifications and substitutions to those skilled in the art are also within the scope of the present invention. Accordingly, equivalent changes and modifications made without departing from the spirit and scope of the present invention should be covered by the present invention.

Claims

1. A preparation method of electronic grade guanidine salt is characterized by comprising the following steps:

(1) preparing a guanidine salt aqueous solution by using ultrapure water;

(3) and drying the precipitate to obtain the electronic grade guanidine salt.

2. The process for preparing an electronic grade guanidinium salt of claim 1 wherein,

the guanidine salt aqueous solution is a guanidine salt saturated aqueous solution.

3. The process for preparing an electronic grade guanidinium salt of claim 1 wherein,

the preparing the aqueous guanidinium solution includes filtering insoluble materials in the aqueous guanidinium solution.

4. The process for preparing an electronic grade guanidinium salt of claim 1 wherein,

the anti-solvent is a water-soluble organic solvent.

5. The process for preparing an electronic grade guanidinium salt of claim 4 wherein,

the water-soluble organic solvent is alcohol, ketone and ether.

6. The process for preparing an electronic grade guanidinium salt of claim 1 wherein,

the mass ratio of the antisolvent to the guanidine salt aqueous solution is 0.1: 1-10: 1.

7. The process for preparing an electronic grade guanidinium salt of claim 1 wherein,

step (3) further comprises washing the wet precipitate again with an anti-solvent.

8. The method of preparing an electronic grade guanidinium salt of any of claims 1-7 wherein the anti-solvent has a metal ion content of less than 1 ppm.