CN112778313A - Electronic-grade tetramethoxymethyl glycoluril and preparation method thereof - Google Patents
Electronic-grade tetramethoxymethyl glycoluril and preparation method thereof Download PDFInfo
- Publication number
- CN112778313A CN112778313A CN202011637637.3A CN202011637637A CN112778313A CN 112778313 A CN112778313 A CN 112778313A CN 202011637637 A CN202011637637 A CN 202011637637A CN 112778313 A CN112778313 A CN 112778313A
- Authority
- CN
- China
- Prior art keywords
- grade
- electronic
- tetramethoxymethyl glycoluril
- reaction
- exchange resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of electronic-grade tetramethoxymethyl glycoluril, which comprises the following steps: mixing AR-grade tetramethylolglycoluril and an electronic-grade methanol solvent to obtain a reaction solution, and adding an electronic-grade catalyst into the reaction solution; after the reaction solution reacts at a preset temperature for a preset time, cooling to room temperature, and adding an organic base to adjust the pH value to be neutral; and separating and purifying the regulated reaction liquid to obtain the electronic-grade tetramethoxymethyl glycoluril. The invention also provides electronic-grade tetramethoxymethyl glycoluril. The methanol solution and the catalyst added in the reaction system are both electronic grade reagents, so that the introduction of metal impurities is reduced, and after the reaction is finished, organic alkali is used for replacing the traditional inorganic alkali to adjust the pH value, so that the introduction of the metal impurities is also greatly reduced. Therefore, the tetramethoxymethyl glycoluril prepared by the preparation method has little metal residue and high purity, and can be used as a cross-linking agent in negative photoresist.
Description
Technical Field
The invention belongs to the technical field of chemistry, and particularly relates to electronic-grade tetramethoxymethyl glycoluril and a preparation method thereof.
Background
Since the development of powder coatings for more than half a century, particularly since the 21 st century, human protection of the environment has been more important, the limit of Volatile Organic Compounds (VOC) to the emission of the atmosphere has become more strict, and the concern of how to save energy for limited resources has been increasing. The paint industry has classified powder paint, water-based paint and high-solid paint as three major pillars of resource-saving, energy-saving and pollution-free paint, and has obtained rapid development.
However, powder coatings develop much less rapidly than waterborne coatings and high solids coatings, especially epoxy powder coatings. The powder coatings have declined throughout the coating market due to the development of other types of coatings and technological advances. The powder coating has the characteristics of wide application, excellent performance and the like, so that the improvement of various performances of the epoxy powder coating by adopting an improved process and a new formula is necessary to expand the application field. Tetramethoxymethyl glycoluril is a novel epoxy powder coating crosslinking agent developed under the circumstances, and the application of the crosslinking agent enables the performance of the epoxy powder coating to be obviously improved.
Tetramethoxymethyl glycoluril is excellent in properties, can be reacted with a polymer having a functional group such as a hydroxyl group, a carboxyl group, an amide group, a carbamate group, a thiol group, etc., and is crosslinked to be cured, and also is a non-sticky, non-blocking and easily pulverized solid having a high melting point, so that it is particularly suitable for the preparation of outdoor type durable powder coatings.
On the other hand, tetramethyloxymethylglycoluril is used as a cross-linking agent for a negative photoresist, but strict requirements are imposed on non-metal ions and metal ions in tetramethyloxymethylglycoluril, and impurity metal ions cause problems in the quality of the photoresist and further cause short circuits between electronic components in a chip, so that the purity and cleanliness of the tetramethyloxymethylglycoluril cross-linking agent directly affect the yield, electrical properties and reliability of devices.
The existing method for producing the tetramethoxymethyl glycoluril cross-linking agent often introduces a large amount of metal impurities, and meanwhile, the purification efficiency is low, so that the purity requirement of the cross-linking agent in the negative photoresist can not be met.
Disclosure of Invention
The embodiment of the invention provides a preparation method of electronic-grade tetramethoxymethyl glycoluril, and aims to solve the technical problems that a large amount of metal impurities are introduced, the purification efficiency is low, and the purity requirement of a cross-linking agent in a negative photoresist cannot be met in the traditional preparation method.
The embodiment of the invention is realized in such a way that the preparation method of the electronic-grade tetramethoxymethyl glycoluril comprises the following steps:
mixing AR-grade tetramethylolglycoluril and an electronic-grade methanol solvent to obtain a reaction solution, and adding an electronic-grade catalyst into the reaction solution;
after the reaction solution reacts at a preset temperature for a preset time, cooling to room temperature, and adding an organic base to adjust the pH value to be neutral;
and separating and purifying the regulated reaction liquid to obtain the electronic-grade tetramethoxymethyl glycoluril.
In addition, the invention also provides electronic-grade tetramethoxymethyl glycoluril prepared by the preparation method.
The preparation method of the electronic-grade tetramethyloxymethyl glycoluril comprises the steps of mixing AR-grade tetramethyloxymethyl glycoluril and an electronic-grade methanol solvent to form a reaction liquid, adding an electronic-grade catalyst into the reaction liquid, cooling the reaction liquid to room temperature after the reaction is finished, adding an organic base into the reaction liquid to adjust the pH value to be neutral, and then separating and purifying the adjusted reaction liquid to obtain the electronic-grade tetramethyloxymethyl glycoluril. The methanol solution and the catalyst added in the reaction system are both electronic grade reagents, so that the introduction of metal impurities is reduced, and after the reaction is finished, organic alkali is used for replacing the traditional inorganic alkali to adjust the pH value, so that the introduction of the metal impurities is also greatly reduced. Therefore, the tetramethoxymethyl glycoluril prepared by the preparation method has little metal residue and high purity, and can be used as a cross-linking agent in negative photoresist.
Drawings
FIG. 1 is a flow chart of a method for preparing electronic-grade tetramethyloxymethylglycoluril according to an embodiment of the present invention;
FIG. 2 is a chemical reaction formula of an electronic grade tetramethoxymethyl glycoluril provided in an embodiment of the present invention;
FIG. 3 is a nuclear magnetic spectrum of an electronic grade tetramethoxymethyl glycoluril provided in the embodiments of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
As shown in FIG. 1, the embodiment of the invention provides a preparation method of electronic-grade tetramethoxymethyl glycoluril. The method for preparing the electronic-grade tetramethoxymethyl glycoluril comprises the following steps:
step S10, mixing AR-grade tetramethylol glycoluril and an electronic-grade methanol solvent into a reaction solution, and adding an electronic-grade catalyst into the reaction solution;
wherein the mass ratio of the tetramethylolglycoluril to the methanol to the catalyst is 1: 10-25: 0.001 to 0.01.
The AR-grade tetramethylol glycoluril is added into a reaction system to react with an electronic-grade methanol solvent, and an electronic-grade catalyst is used for catalysis, so that the reagent in the whole reaction system has high grade and high purity, and the introduction of metal impurities is reduced.
Through experimental research, the catalyst has good catalytic effect by adopting electronic grade hydrochloric acid as the catalyst. As shown in FIG. 2, the chemical formula of the tetramethoxymethyl glycoluril is shown to be generated by using hydrochloric acid as a catalyst.
Step S20, after the reaction liquid reacts for a preset time at a preset temperature, cooling to room temperature, and adding organic base to adjust the pH value to be neutral;
in this embodiment, the organic base used includes methylamine, ethylamine, tert-butylamine, diisopropylamine, triethylamine, ammonium hydroxide, tetramethylammonium hydroxide, aniline, and the like. The invention adopts organic base to replace the traditional inorganic base, which can greatly reduce the introduction of metal impurities.
And step S30, separating and purifying the adjusted reaction liquid to obtain the electronic-grade tetramethoxymethyl glycoluril.
After the reaction solution after the reaction is adjusted to be neutral by using the organic base, the reaction product tetramethoxymethyl glycoluril obtained in the reaction solution needs to be separated out, and the electronic-grade tetramethoxymethyl glycoluril is obtained through separation and purification of the reaction solution. Performing nuclear magnetic analysis on the separated and purified product, wherein the nuclear magnetic spectrum is shown in figure 3, and the product is identified as tetramethoxymethyl glycoluril by analysis and comparison
In one embodiment, the separation and purification process provided is as follows:
adding activated cation exchange resin into the adjusted reaction solution for ion adsorption;
filtering the residual solution after ion adsorption to obtain filtrate;
and recrystallizing the filtrate to obtain the electronic-grade tetramethoxymethyl glycoluril.
Wherein, the cation exchange resin can be selected from polystyrene cation exchange resin activated by acid and alkali; the adsorption time of the cation exchange resin is 8-36 h; the cooling crystallization time of filtrate recrystallization is 6-24 h, and the cooling temperature is 0-50 ℃; tetrakis (hydroxymethyl) glycoluril: methanol: catalyst: the mass ratio of the cation exchange resin is 1: 10-25: 0.001-0.01: 0.1 to 0.25.
The method adopts a recrystallization mode to separate and purify, can effectively remove metal impurities compared with the traditional method of directly heating and pumping out the solvent, and can effectively avoid the cross-linking phenomenon of the cross-linking agent and improve the purity of the product. In addition, the recrystallization is carried out in a methanol solvent system without adding extra crystallization solvent, and the method is directly carried out in the reaction liquid, thereby saving the cost, optimizing the process and greatly avoiding the introduction of metal impurities.
Further, in order to improve the reaction rate, increase the utilization rate of reactants and improve the yield of reaction products, the reaction conditions of the electronic-grade tetramethyloxymethylglycoluril generated by the reaction of the AR-grade tetramethyloxymethylglycoluril and the electronic-grade methanol solvent are preferably that the reaction is carried out for 3-7 hours at the temperature of 30-80 ℃ by stirring. That is, in step S20, the preset temperature is 30 to 80 ℃, the preset time is 3 to 7 hours, and the reaction condition is stirring.
Wherein the temperature control mode is not limited to the heating modes in electric furnace heating, water bath heating and oil bath heating; the stirring method is not limited to mechanical stirring, magnetic stirring, and other stirring methods.
According to the preparation method of the electronic-grade tetramethoxymethyl glycoluril, the methanol solution and the catalyst which are added into the reaction system are electronic-grade reagents, so that the introduction of metal impurities is reduced, and after the reaction is finished, the organic base is used for replacing the traditional inorganic base to adjust the pH, so that the introduction of the metal impurities is also greatly reduced. Therefore, the tetramethoxymethyl glycoluril prepared by the preparation method has little metal residue and high purity, and can be used as a cross-linking agent in negative photoresist.
The following examples illustrate the preparation of methacrylic resins according to embodiments of the present invention.
Example one
Embodiment 1 provides a preparation method of electronic grade tetramethoxymethyl glycoluril, comprising the following steps:
a. adding 26.2g of AR-grade tetramethylol glycoluril into a single-mouth bottle, and then adding 262g of an electronic-grade methanol solvent; adding 0.131g of electronic grade hydrochloric acid into the solution to serve as a catalyst;
b. heating and stirring the solution at 40 ℃ to react for 8 hours;
c. cooling the reaction liquid to room temperature, and adding triethylamine to adjust the pH value to 7;
d. adding 2.6g of activated cation exchange resin into the neutralization solution for ion adsorption for 24 hours;
e. filtering the solution, removing ion exchange resin, and performing-10 ℃ freezing crystallization on the filtrate for 24 hours;
f. after removing methanol from the mother liquor of the crystals, directly removing trace solvent on the surface of the solid by decompression to obtain 28.9g of white solid, wherein the nuclear magnetic result shows that the product is tetramethoxymethyl glycoluril, and the yield of the tetramethoxymethyl glycoluril is calculated to be 91%.
Example 2
Embodiment 2 provides a preparation method of electronic-grade tetramethoxymethyl glycoluril, comprising the following steps:
a. adding 26.2g of AR-grade tetramethylol glycoluril into a single-mouth bottle, then adding 393g of electronic-grade methanol solvent, and adding 0.26g of electronic-grade hydrochloric acid into the solution to serve as a catalyst;
b. heating and stirring the solution at 50 ℃ to react for 7 hours;
c. cooling the reaction liquid to room temperature, and adding methylamine to adjust the pH value to 7;
d. adding 3.9g of activated cation exchange resin into the neutralization solution for ion adsorption for 12 hours;
e. filtering the solution, removing ion exchange resin, and performing-20 ℃ freezing crystallization on the filtrate for 16 h;
f. after removing methanol from the mother liquor of the crystals, directly removing trace solvent on the surface of the solid by decompression to obtain 28.6g of white solid, wherein the nuclear magnetic result shows that the product is tetramethoxymethyl glycoluril, and the yield of the tetramethoxymethyl glycoluril is calculated to be 90%.
Example 3
Embodiment 3 provides a preparation method of electronic grade tetramethoxymethyl glycoluril, comprising the following steps:
a. adding 26.2g of AR-grade tetramethylol glycoluril into a single-mouth bottle, then adding 520g of electronic-grade methanol solvent, and adding 0.26g of electronic-grade hydrochloric acid into the solution to serve as a catalyst;
b. heating and stirring the solution at 60 ℃ to react for 5 hours;
c. cooling the reaction liquid to room temperature, and adding tetramethylammonium hydroxide to adjust the pH to 7;
d. 6.5g of activated cation exchange resin is added into the neutralization solution for ion adsorption for 18 hours;
e. filtering the solution, removing ion exchange resin, and performing-40 deg.C freezing crystallization on the filtrate for 18 h;
f. after removing methanol from the mother liquor of the crystals, directly removing trace solvent on the surface of the solid by decompression to obtain 27.9g of white solid, wherein the nuclear magnetic result shows that the product is tetramethoxymethyl glycoluril, and the yield of the tetramethoxymethyl glycoluril is calculated to be 88%.
Example 4
a. adding 26.2g of AR-grade tetramethylol glycoluril into a single-mouth bottle, then adding 600g of electronic-grade methanol solvent, and adding 0.26g of electronic-grade hydrochloric acid into the solution to serve as a catalyst;
b. heating and stirring the solution at 70 ℃ to react for 3 h;
c. cooling the reaction liquid to room temperature, and adding tert-butylamine to adjust the pH to 7;
d. 6.5g of activated cation exchange resin is added into the neutralization solution for ion adsorption for 24 hours;
e. filtering the solution, removing ion exchange resin, and performing-50 ℃ freezing crystallization on the filtrate for 24 hours;
f. after removing methanol from the mother liquor of the crystals, the solid was directly decompressed to remove a trace amount of solvent on the surface to obtain 27.6g of white solid, and the nuclear magnetic result showed that the product was tetramethoxymethyl glycoluril, and the yield of the tetramethoxymethyl glycoluril was calculated to be 87%.
Evaluation of Performance
1. The electronic grade tetramethoxymethyl glycoluril cross-linking agent obtained in examples 1 to 4 was subjected to performance tests, the test contents are purity, and the results are shown in table 1 by HPLC (high performance liquid chromatography).
Table 1:
examples | Example 1 | Example 2 | Example 3 | Example 4 |
Purity (wt%) | 99.9 | 99.8 | 99.9 | 99.7 |
2. The electronic grade tetramethoxymethyl glycoluril cross-linking agent obtained in example 2 was subjected to a performance test, wherein the test content is the content of metal impurity ions, and the results are shown in table 2 when measured by ICP-MS (inductively coupled plasma-mass spectrometry), and nd represents no detection.
Table 2:
according to embodiments 1 to 4, the preparation method of the electronic grade tetramethoxymethyl glycoluril provided by the invention is simple to operate, high in production efficiency, easy to obtain reagent raw materials, low in cost, high in product purity, greatly reduced in metal element content in the purified compound, and suitable for application requirements in high-purity materials such as photoresist, and compared with the traditional method, the preparation method is more suitable for large-scale production and is suitable for wide popularization in the industry.
Furthermore, the invention also provides electronic-grade tetramethoxymethyl glycoluril, and the methacrylic resin is prepared by the preparation method of the embodiment. Because the methanol solution and the catalyst added in the reaction system are both electronic grade reagents, the introduction of metal impurities is reduced, and after the reaction is finished, organic alkali is used for replacing the traditional inorganic alkali to adjust the pH value, so that the introduction of the metal impurities is also greatly reduced. Therefore, the tetramethoxymethyl glycoluril prepared by the preparation method has little metal residue and high purity, and can be used as a cross-linking agent in negative photoresist.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A preparation method of electronic-grade tetramethoxymethyl glycoluril is characterized by comprising the following steps:
mixing AR-grade tetramethylolglycoluril and an electronic-grade methanol solvent to obtain a reaction solution, and adding an electronic-grade catalyst into the reaction solution;
after the reaction solution reacts at a preset temperature for a preset time, cooling to room temperature, and adding an organic base to adjust the pH value to be neutral;
and separating and purifying the regulated reaction liquid to obtain the electronic-grade tetramethoxymethyl glycoluril.
2. The method of claim 1, wherein the organic base comprises at least one of methylamine, ethylamine, tert-butylamine, diisopropylamine, triethylamine, ammonium hydroxide, tetramethylammonium hydroxide, and aniline.
3. The method for preparing electronic-grade tetramethoxymethyl glycoluril as claimed in claim 1, wherein the step of separating and purifying the adjusted reaction solution comprises:
adding activated cation exchange resin into the adjusted reaction solution for ion adsorption;
filtering the residual solution after ion adsorption to obtain filtrate;
and recrystallizing the filtrate to obtain the electronic-grade tetramethoxymethyl glycoluril.
4. The method of claim 3, wherein the cation exchange resin is a polystyrene cation exchange resin, and wherein the polystyrene cation exchange resin is activated by an acid or base.
5. The method for preparing electronic-grade tetramethoxymethyl glycoluril according to claim 3, wherein the adsorption time of the cation exchange resin is 8-36 h.
6. The method for preparing the electronic-grade tetramethyloxymethylglycoluril cross-linking agent according to claim 3, wherein the cooling crystallization time for the recrystallization of the filtrate is 6 to 24 hours, and the cooling temperature is 0 to-50 ℃.
7. The method of preparing electronic grade tetramethoxymethyl glycoluril as claimed in any of claims 1 to 6, wherein said electronic grade catalyst is electronic grade hydrochloric acid.
8. The preparation method of the electronic grade tetramethoxymethyl glycoluril as claimed in any of claims 1 to 6, wherein the predetermined temperature is 30-80 ℃, the predetermined time is 3-7 h, and the reaction condition is stirring.
9. The method of preparing electronic grade tetramethoxymethyl glycoluril as claimed in any of claims 1 to 6, wherein said tetramethylolglycoluril: methanol: catalyst: the mass ratio of the cation exchange resin is 1: 10-25: 0.001-0.01: 0.1 to 0.25.
10. An electronic-grade tetramethoxymethyl glycoluril prepared by the method of any one of claims 1 to 9.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011637637.3A CN112778313A (en) | 2020-12-31 | 2020-12-31 | Electronic-grade tetramethoxymethyl glycoluril and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011637637.3A CN112778313A (en) | 2020-12-31 | 2020-12-31 | Electronic-grade tetramethoxymethyl glycoluril and preparation method thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
CN112778313A true CN112778313A (en) | 2021-05-11 |
Family
ID=75755001
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202011637637.3A Pending CN112778313A (en) | 2020-12-31 | 2020-12-31 | Electronic-grade tetramethoxymethyl glycoluril and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN112778313A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114262396A (en) * | 2021-12-24 | 2022-04-01 | 宁波南大光电材料有限公司 | Etching-adjustable glycoluril oligomer and preparation method thereof |
CN114292273A (en) * | 2021-12-30 | 2022-04-08 | 宁波南大光电材料有限公司 | Preparation method of cross-linking agent containing benzene ring |
-
2020
- 2020-12-31 CN CN202011637637.3A patent/CN112778313A/en active Pending
Non-Patent Citations (3)
Title |
---|
刘爱花: "合成四甲氧甲基甘脲工艺条件的研究", 《太原理工大学学报》 * |
吕丽丽: "电子级没食子酸制备过程中若干基础问题研究", 《中国博士学位论文全文数据库 医药卫生科技辑》 * |
赵克健: "《现代药学名词手册》", 31 December 2004 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114262396A (en) * | 2021-12-24 | 2022-04-01 | 宁波南大光电材料有限公司 | Etching-adjustable glycoluril oligomer and preparation method thereof |
CN114292273A (en) * | 2021-12-30 | 2022-04-08 | 宁波南大光电材料有限公司 | Preparation method of cross-linking agent containing benzene ring |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN112778313A (en) | Electronic-grade tetramethoxymethyl glycoluril and preparation method thereof | |
CN108675996B (en) | Preparation method of electronic grade triglycidyl isocyanurate | |
CN1225405C (en) | Magnesium sulfate production method using magnesium oxide and desulfurated waste fluid | |
CN108947987B (en) | High-quality electronic grade triglycidyl isocyanurate | |
CN113045089B (en) | Method for refining and purifying etching waste liquid | |
CN113214266A (en) | Crosslinking agent containing benzene ring and preparation method thereof | |
CN110845704A (en) | Preparation process of high-temperature-resistant glycidylamine epoxy resin | |
CN114989055B (en) | Preparation method of N-acetyl-L-cysteine | |
CN114292293B (en) | Washing process for BDP industrial production | |
CN105693475A (en) | Technology method for utilizing solid acid H2SO4-SiO2 for catalyzing and preparing bisphenol | |
EP3505507A1 (en) | Method for purifying dihydroxynaphthalene | |
CN108863856B (en) | Purification method of analytically pure reagent 5-sulfosalicylic acid | |
CN111606349A (en) | Impurity removal method for gypsum with high impurity ion content | |
CN110256251B (en) | Purification method of high-purity 2-ethyl-2-adamantanol methacrylate | |
CN112194585B (en) | Synthetic method of bromhexine hydrochloride | |
CN112209415B (en) | Process for recovering alcohol water in production of high-purity superfine alumina powder | |
KR20180109380A (en) | Method for producing a mixed salt of ammonium nitrate and calcium nitrate using mixed waste liquid from semiconductor manufacturer | |
CN114573425B (en) | Purification method and application of 1, 1-tri (4-hydroxyphenyl) compound | |
CN104672105A (en) | Method for preparing L-3-(3,4-dimethoxyphenyl)-2-amino-2-methyl propionitrile hydrochloride | |
CN115108951B (en) | P-nitrophenyl-beta-hydroxyethyl thioether and preparation method thereof | |
CN114920658B (en) | Method for purifying choline hydroxide by ion exchange resin | |
CN111978197B (en) | Resource treatment process for oxytetracycline hydrochloride production waste liquid | |
CN111943215A (en) | Preparation method of quartz powder | |
CN113292449B (en) | Refining and purifying method of butanone oxime | |
CN117658775A (en) | Preparation method of ultra-high purity isopropanol |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210511 |