Preparation method of high-purity electronic-grade photoacid generator derived from 2-adamantanoic acid-trifluoropropane sulfonic acid

Abstract

The invention provides a preparation method of a high-purity electronic-grade photoacid generator derived from 2-adamantanoic acid-trifluoropropane sulfonic acid, and the synthetic route is as follows: firstly preparing 3, 3, 3-trifluoro-2-hydroxy-1-propane sulfonate, then reacting with an adamantyl derivative, and finally performing ion exchange and purification with a cationic fragment. The product is M, 2-adamantanoic acid-trifluoropropane sulfonate, and M is a triaryl sulfonium salt, a diaryl iodonium salt and a derivative of the triaryl sulfonium salt and the diaryl iodonium salt. The invention has the advantages of high stability, good solubility, simple preparation method, no introduction of halogen ions in the preparation process, high product yield and purity, low metal ion content, convenient post-treatment and environmental friendliness, and the product as a photoresist-level core main material has wide application in the fields of semiconductor photoresists, other imaging systems, photocureable coatings and the like, and has wide application prospects. The market scale is continuously expanded, and the material is an indispensable key material in semiconductor manufacturing and other related fields.

Description

Technical Field

[0001] The invention relates to the technical field of organic synthesis, and in particular to a high-purity electronic-grade photoacid generator derived from 2-adamantanyl acid-trifluoropropane sulfonic acid. Background Art

[0002] Photoacid generators are key components of high-end semiconductor photoresists and have an important impact on the yield, quality, and processing accuracy of photoresists and photolithography products. Photoacid generators mainly include onium salt acid generators and sulfonate acid generators. Onium salt acid generators have been used for a long time, with mature processes, high acid production efficiency, fast photoinitiation rate, good thermal stability, and high acid strength, which helps to promote chemical reactions in photoresists. However, they have poor solubility, complex synthesis steps, and low product purity, which limits their application scope. Sulfonate acid generators appeared relatively late, have good solubility in solvents and resin systems, are easy to cut and process, and have low toxicity of photolysis products. They have developed rapidly in the field of photochemistry, but there are few sulfonate acid generators suitable for the visible light wavelength range. Therefore, the development of high-performance and high-purity photoacid generators has become an important topic in the field of microelectronics technology.

[0003] In addition, the traditional preparation methods of photoacid generators often have problems such as low purity, many side reactions, and poor stability. Metal ions and anions are easily introduced during the preparation process, which cannot meet the high-precision requirements of modern microelectronics manufacturing. In order to improve the purity and stability of photoacid generators and reduce the preparation cost, it is necessary to develop a new preparation method to improve the purity and stability of photoacid generators, reduce the metal content and halogen content of such compounds, and meet the needs of modern microelectronics manufacturing for high-performance photoacid generators. Summary of the invention

[0004] The object of the present invention is to provide a method for preparing a high-purity electronic-grade photoacid generator derived from 2-adamantanyl acid-trifluoropropane sulfonic acid.

[0005] Technical solution: A method for preparing a high-purity electronic-grade photoacid generator derived from 2-adamantanyl acid-trifluoropropane sulfonic acid, comprising the following steps: S1. 1,1,1-trifluoro-2,3-propylene oxide, a sulfonating agent and sodium hydroxide are added to an aqueous solution, the temperature is maintained and stirred to open the epoxy ring, and after the reaction is completed, the reaction is cooled to room temperature and dried to obtain sodium 3,3,3-trifluoro-2-hydroxy-1-propane sulfonate; S2. The sodium 3,3,3-trifluoro-2-hydroxy-1-propane sulfonate prepared in S1 is dissolved in solvent A, and an adamantyl derivative, an acid binding agent and a catalyst are added, and the mixture is stirred at a constant temperature until the reaction is complete, washed and dried, tertiary methyl ether is added to pulp and filtered to obtain sodium 2-adamantanyl acid-trifluoropropane sulfonate; S3. The 2-adamantanyl acid - sodium trifluoropropane sulfonate and M salt chloride prepared in S2 were added to solvent A, stirred at room temperature until the reaction was complete, washed with water, concentrated and dried, methyl tert-ether was added to pulp and filtered to obtain a crude product M, 2-adamantanyl acid - trifluoropropane sulfonate; S4. The crude product M, 2-adamantanic acid - trifluoropropane sulfonate was dissolved in solvent A, R210 resin was added and stirred, diatomaceous earth was added for adsorption and filtration, R210 resin was added again and stirred, then filtered and dried, isopropyl ether was added for crystallization to obtain high purity M, 2-adamantanic acid - trifluoropropane sulfonate; The solvent A in steps S2, S3 and S4 comprises any one of dichloromethane, ethyl acetate and diethyl ether.

[0006] Preferably, the high-purity electronic-grade photoacid generator derived from 2-adamantanyl acid-trifluoropropane sulfonic acid has the following general structural formula I: (I) Wherein, M is triarylsulfonium salt, diaryliodonium salt and derivatives thereof.

[0007] Preferably, the sulfonating agent in step S1 includes any one or more of sodium bisulfite, sodium dithionite, sodium sulfite, and sodium thiosulfate.

[0008] Preferably, in step S1, the molar ratio of 1,1,1-trifluoro-2,3-propylene oxide, sulfonating agent and sodium hydroxide is 1:1-1.5:0.2-0.4, and the reaction temperature is 40-50°C.

[0009] Preferably, the adamantyl derivative in step S2 includes any one of adamantane acid chloride and adamantane carboxylic acid, the acid binding agent includes any one or more of triethylamine, trimethylamine, dimethylamine, ethanolamine, and isopropylamine, and the catalyst includes any one or more of 4-dimethylaminopyridine, pyridine, 4,4'-bipyridine, and aminopyridine.

[0010] Preferably, in step S2, the molar ratio of the solvent, the acid binding agent, the catalyst, the adamantane esterification raw material and the 3,3,3-trifluoro-2-hydroxypropane sulfonate is 10-20:1-1.5:0.3-0.5:1-3:1, and the reaction temperature is 25-30°C.

[0011] Preferably, in step S3, the molar ratio of 2-adamantanyl acid-trifluoropropane sulfonate sodium to M salt chloride is 1:0.6-0.8.

[0012] Preferably, in step S4, the mass ratio of the solvent, the R210 resin and the crude product M, 2-adamantanyl acid-trifluoropropane sulfonate is 10-20:8-12:1.

[0013] Beneficial effects: Compared with the prior art, the present invention has the following characteristics: The invention provides a high-purity electronic-grade photoacid generator derived from 2-adamantanic acid-trifluoropropane sulfonic acid. The compound has good stability, a simple preparation method, a high product yield, high purity, no introduction of halogen ions, and a low metal ion content. The prepared product is used as a DUV photoresist-grade core main material and is widely used in the fields of semiconductor photoresists, other imaging systems, photocurable coatings, and the like.

[0014] As a key raw material for semiconductor photoresists, photoacid generators have high industrial value, so there are high requirements for their thermal stability, solubility, and the difficulty of the synthesis process. Adamantane is a symmetrical, highly stable cage hydrocarbon, and its basic carbon skeleton is similar to a lattice unit of diamond. Introducing the adamantane skeleton structure into the main chain or side chain of the polymer can significantly improve the thermal oxygen stability, chemical stability, and optical stability of the polymer, and improve its mechanical, dielectric and other properties, thereby obtaining a series of liquid crystal display materials, semiconductor photoresist materials, holographic photosensitive materials, membrane separation materials, smart plastics, corneal contact lenses and drug carriers with special functions. Introducing the adamantane structure into sulfonate compounds to prepare adamantane ester sulfonate compounds, as a new type of photoacid generator raw material, has the advantages of good stability, high solubility, high light transmittance, and high photosensitivity, so it shows great application potential in the preparation of high-purity electronic-grade photoacid generators.

[0015] At present, the synthesis route of the photoacid generator whose anion fragment is 2-adamantanic acid-trifluoropropane sulfonic acid is to first prepare 3,3,3-trifluoro-2-hydroxy-1-propane sulfonate and then perform ion exchange on the cationic fragment, and finally obtain the intermediate through esterification to obtain the target photoacid generator product. This route cannot control the content of metal ions in the synthesis stage, and the purification method is relatively harsh. At the same time, other halogen anion impurities will be introduced in the esterification stage, which will have a greater impact on the product color and anion content, and the process is difficult to scale up. The present invention proposes a method for preparing a high-purity electronic-grade photoacid generator derived from 2-adamantanic acid-trifluoropropane sulfonic acid. Compared with the traditional method, this method optimizes the reaction conditions and process route, effectively controls the occurrence of side reactions in the front stage of the process, improves the purity and stability of the photoacid generator, reduces the metal content and halogen content of this type of compound, and meets the demand for high-performance photoacid generators in modern microelectronics manufacturing.

[0016] Compared with the prior art, the present invention has the following advantages and positive effects: The invention provides a novel photoacid generator containing 2-adamantanyl acid-trifluoropropane sulfonate, which can be used as a key raw material for photoresist in the field of high-end liquid crystal and chip manufacturing.

[0017] The product of the invention has low moisture and impurity contents, low halogen ion and metal ion contents, high product yield, low manufacturing cost, and can realize large-scale production and application.

[0018] The overall process technology route of the present invention is simple to operate, convenient for post-processing, and environmentally friendly, which is conducive to achieving green production. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 The invention is a preparation step of a photoacid generator 2-adamantanyl acid-trifluoropropane sulfonate compound; Figure 2 is the NMR spectrum of triphenylsulfonium, 2-adamantananoic acid-trifluoropropane sulfonate prepared in Example 1; Figure 3 HPLC spectrum of triphenylsulfonium 2-adamantanyl acid-trifluoropropane sulfonate prepared in Example 1; Figure 4 LC-MS spectrum of triphenylsulfonium 2-adamantanyl acid-trifluoropropane sulfonate prepared in Example 1; Figure 5 This is a table showing the metal content of triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate prepared in Example 1; Figure 6 This is the NMR spectrum of monofluorotriphenylsulfonium, 2-adamantananoic acid-trifluoropropane sulfonate of Example 3; Figure 7 This is the NMR spectrum of Example 4 monofluoro-di(tert-butyl)triphenylsulfonium, 2-adamantananoic acid-trifluoropropane sulfonate. DETAILED DESCRIPTION The present invention will be further described below in conjunction with embodiments, which are explanations of the present invention and are not limited to the following embodiments: Example 1

[0019] A method for preparing a high-purity electronic-grade photoacid generator derived from 2-adamantanyl acid-trifluoropropane sulfonic acid comprises the following steps: S1. Add 1,1,1-trifluoro-2,3-propylene oxide, sodium bisulfite and sodium hydroxide into an aqueous solution, wherein the molar ratio of 1,1,1-trifluoro-2,3-propylene oxide, sodium bisulfite and sodium hydroxide is 1:1:0.2, and stir to open the epoxy ring while maintaining a constant temperature of 40°C. After the reaction is completed, cool to room temperature and dry to obtain sodium 3,3,3-trifluoro-2-hydroxy-1-propane sulfonate; S2. The sodium 3,3,3-trifluoro-2-hydroxy-1-propane sulfonate prepared in S1 is dissolved in dichloromethane, and adamantane acid chloride, triethylamine and 4-dimethylaminopyridine are added, the molar ratio of dichloromethane, triethylamine, 4-dimethylaminopyridine, adamantane acid chloride and 3,3,3-trifluoro-2-hydroxypropane sulfonate is 15:1:0.3:2:1, stirred at 30°C until the reaction is complete, washed and dried, tertiary methyl ether is added to pulp, filtered and dried, to obtain 2-adamantananoic acid-trifluoropropane sulfonate sodium; S3. Add the 2-adamantanyl acid-trifluoropropane sulfonate sodium and triphenylsulfonium chloride prepared in S2 to dichloromethane, wherein the molar ratio of 2-adamantanyl acid-trifluoropropane sulfonate sodium to triphenylsulfonium chloride is 1:0.8, stir at room temperature until the reaction is complete, wash with water, concentrate and dry, add tertiary methyl ether to pulp, filter and dry, and obtain crude triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate; S4. The crude triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate is dissolved in dichloromethane, R210 resin is added and stirred, diatomaceous earth is added for adsorption and filtration, R210 resin is added again and stirred, and then filtered and dried, the mass ratio of dichloromethane, R210 resin and crude triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate is 15:10:1, isopropyl ether is added for crystallization, and high-purity triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate is obtained; The general structural formula I of the high-purity electronic-grade photoacid generator derived from 2-adamantanyl acid-trifluoropropane sulfonic acid is shown below: (I) Wherein, M is triphenylsulfonium salt. Example 2

[0020] A method for preparing a high-purity electronic-grade photoacid generator derived from 2-adamantanyl acid-trifluoropropane sulfonic acid comprises the following steps: S1. Add 1,1,1-trifluoro-2,3-propylene oxide, sodium bisulfite and sodium hydroxide into an aqueous solution, wherein the molar ratio of 1,1,1-trifluoro-2,3-propylene oxide, sodium bisulfite and sodium hydroxide is 1:1:0.2, and stir to open the epoxy ring while maintaining a constant temperature of 40°C. After the reaction is completed, cool to room temperature and dry to obtain sodium 3,3,3-trifluoro-2-hydroxy-1-propane sulfonate; S2. The sodium 3,3,3-trifluoro-2-hydroxy-1-propane sulfonate prepared in S1 is dissolved in dichloromethane, and adamantane acid chloride, triethylamine and 4-dimethylaminopyridine are added, the molar ratio of dichloromethane, triethylamine, 4-dimethylaminopyridine, adamantane acid chloride and 3,3,3-trifluoro-2-hydroxypropane sulfonate is 15:1:0.3:2:1, stirred at 25°C until the reaction is complete, washed and dried, tertiary methyl ether is added to pulp, filtered and dried, to obtain 2-adamantananoic acid-trifluoropropane sulfonate sodium; S3. Add the 2-adamantanyl acid-trifluoropropane sulfonate sodium and triphenylsulfonium chloride prepared in S2 to dichloromethane, wherein the molar ratio of 2-adamantanyl acid-trifluoropropane sulfonate sodium to triphenylsulfonium chloride is 1:0.8, stir at room temperature until the reaction is complete, wash with water, concentrate and dry, add tertiary methyl ether to pulp, filter and dry, and obtain crude triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate; S4. The crude triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate is dissolved in dichloromethane, R210 resin is added and stirred, diatomaceous earth is added for adsorption and filtration, R210 resin is added again and stirred, and then filtered and dried, the mass ratio of dichloromethane, R210 resin and crude triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate is 15:10:1, isopropyl ether is added for crystallization, and high-purity triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate is obtained; The general structural formula I of the high-purity electronic-grade photoacid generator derived from 2-adamantanyl acid-trifluoropropane sulfonic acid is shown below: (I) Wherein, M is triphenylsulfonium salt. Example 3

[0021] A method for preparing a high-purity electronic-grade photoacid generator derived from 2-adamantanyl acid-trifluoropropane sulfonic acid comprises the following steps: S1. Add 1,1,1-trifluoro-2,3-propylene oxide, sodium bisulfite and sodium hydroxide into an aqueous solution, wherein the molar ratio of 1,1,1-trifluoro-2,3-propylene oxide, sodium bisulfite and sodium hydroxide is 1:1:0.2, and stir to open the epoxy ring while maintaining a constant temperature of 40°C. After the reaction is completed, cool to room temperature and dry to obtain sodium 3,3,3-trifluoro-2-hydroxy-1-propane sulfonate; S2. The sodium 3,3,3-trifluoro-2-hydroxy-1-propane sulfonate prepared in S1 is dissolved in dichloromethane, and adamantane acid chloride, triethylamine and 4-dimethylaminopyridine are added, the molar ratio of dichloromethane, triethylamine, 4-dimethylaminopyridine, adamantane acid chloride and 3,3,3-trifluoro-2-hydroxypropane sulfonate is 15:1:0.3:2:1, stirred at 30°C until the reaction is complete, washed and dried, tertiary methyl ether is added to pulp, filtered and dried, to obtain 2-adamantananoic acid-trifluoropropane sulfonate sodium; S3. Add 2-adamantanyl acid-trifluoropropane sulfonate sodium and monofluoro triphenylsulfonium chloride prepared in S2 to dichloromethane, wherein the molar ratio of 2-adamantanyl acid-trifluoropropane sulfonate sodium to monofluoro triphenylsulfonium chloride is 1:0.8, stir at room temperature until the reaction is complete, wash with water, concentrate and dry, add tertiary methyl ether to pulp, filter and dry, and obtain a crude product of monofluoro triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate; S4. Dissolve the crude monofluorotriphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate in dichloromethane, add R210 resin and stir, add diatomaceous earth for adsorption and filtration, add R210 resin again and stir, then filter and dry, the mass ratio of dichloromethane, R210 resin and crude monofluorotriphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate is 15:10:1, add isopropyl ether for crystallization, and obtain high-purity monofluorotriphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate; The general structural formula I of the high-purity electronic-grade photoacid generator derived from 2-adamantanyl acid-trifluoropropane sulfonic acid is shown below: (I) Wherein, M is monofluorotriphenylsulfonium salt. Example 4

[0022] A method for preparing a high-purity electronic-grade photoacid generator derived from 2-adamantanyl acid-trifluoropropane sulfonic acid comprises the following steps: S1. Add 1,1,1-trifluoro-2,3-propylene oxide, sodium bisulfite and sodium hydroxide into an aqueous solution, wherein the molar ratio of 1,1,1-trifluoro-2,3-propylene oxide, sodium bisulfite and sodium hydroxide is 1:1:0.2, and stir to open the epoxy ring while maintaining a constant temperature of 40°C. After the reaction is completed, cool to room temperature and dry to obtain sodium 3,3,3-trifluoro-2-hydroxy-1-propane sulfonate; S2. The sodium 3,3,3-trifluoro-2-hydroxy-1-propane sulfonate prepared in S1 is dissolved in dichloromethane, and adamantane acid chloride, triethylamine and 4-dimethylaminopyridine are added, the molar ratio of dichloromethane, triethylamine, 4-dimethylaminopyridine, adamantane acid chloride and 3,3,3-trifluoro-2-hydroxypropane sulfonate is 15:1:0.3:2:1, stirred at 30°C until the reaction is complete, washed and dried, tertiary methyl ether is added to pulp, filtered and dried, to obtain 2-adamantananoic acid-trifluoropropane sulfonate sodium; S3. Add 2-adamantanyl acid-trifluoropropane sulfonate sodium and monofluoro-di(tert-butyl)triphenylsulfonium chloride prepared in S2 to dichloromethane, wherein the molar ratio of 2-adamantanyl acid-trifluoropropane sulfonate sodium and monofluoro-di(tert-butyl)triphenylsulfonium chloride is 1:0.8, stir at room temperature until the reaction is complete, wash with water, concentrate and dry, add methyl tert-ether to pulp, filter and dry, and obtain crude monofluoro-di(tert-butyl)triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate; S4. Dissolve the crude monofluorotriphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate in dichloromethane, add R210 resin and stir, add diatomaceous earth for adsorption and filtration, add R210 resin again and stir, then filter and dry, the mass ratio of dichloromethane, R210 resin and crude monofluoro-di(tert-butyl)triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate is 15:10:1, add isopropyl ether for crystallization, and obtain high-purity monofluoro-di(tert-butyl)triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate; The general structural formula I of the high-purity electronic-grade photoacid generator derived from 2-adamantanyl acid-trifluoropropane sulfonic acid is shown below: (I) Wherein, M is monofluoro-di(tert-butyl)triphenylsulfonium salt; Example 5

[0023] A method for preparing a high-purity electronic-grade photoacid generator derived from 2-adamantanyl acid-trifluoropropane sulfonic acid, comprising the following steps: S1. adding 1,1,1-trifluoro-2,3-propylene oxide, sodium bisulfite and sodium hydroxide into an aqueous solution, wherein the molar ratio of 1,1,1-trifluoro-2,3-propylene oxide, sodium bisulfite and sodium hydroxide is 1:1:0.2, maintaining a constant temperature of 40°C and stirring to open the epoxy ring, cooling to room temperature after the reaction is completed and drying to obtain sodium 3,3,3-trifluoro-2-hydroxy-1-propane sulfonate; S2. The sodium 3,3,3-trifluoro-2-hydroxy-1-propane sulfonate prepared in S1 is dissolved in dichloromethane, and adamantane acid chloride, triethylamine and 4-dimethylaminopyridine are added, the molar ratio of dichloromethane, triethylamine, 4-dimethylaminopyridine, adamantane acid chloride and 3,3,3-trifluoro-2-hydroxypropane sulfonate is 15:1:0.3:2:1, stirred at 30°C until the reaction is complete, washed and dried, tertiary methyl ether is added to pulp, filtered and dried, to obtain 2-adamantananoic acid-trifluoropropane sulfonate sodium; S3. Add the 2-adamantanyl acid-trifluoropropane sulfonate sodium and diphenyliodonium chloride prepared in S2 to dichloromethane, wherein the molar ratio of 2-adamantanyl acid-trifluoropropane sulfonate to diphenyliodonium chloride is 1:0.8, stir at room temperature until the reaction is complete, wash with water, concentrate and dry, add tert-methyl ether to pulp, filter and dry, and obtain crude diphenyliodonium, 2-adamantanyl acid-trifluoropropane sulfonate; S4. Dissolve the crude diphenyliodonium, 2-adamantanyl acid-trifluoropropane sulfonate in dichloromethane, add R210 resin and stir, add diatomaceous earth for adsorption and filtration, add R210 resin again and stir, then filter and dry, the mass ratio of dichloromethane, R210 resin and crude diphenyliodonium, 2-adamantanyl acid-trifluoropropane sulfonate is 15:10:1, add isopropyl ether for crystallization, and obtain high-purity diphenyliodonium, 2-adamantanyl acid-trifluoropropane sulfonate; The general structural formula I of the high-purity electronic-grade photoacid generator derived from 2-adamantanyl acid-trifluoropropane sulfonic acid is shown below: (I) Wherein, M is diphenyliodonium salt.

[0024] Table 1 Product yields of different products name product Yield / % Example 1 Triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate 90 Example 3 Triphenylsulfonium fluoride, 2-adamantanyl acid-trifluoropropane sulfonate 83 Example 4 Monofluoro-di(tert-butyl)triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate 80 Example 5 Diphenyliodonium, 2-adamantanyl acid-trifluoropropane sulfonate 85 Example 6

[0025] A method for preparing a high-purity electronic-grade photoacid generator derived from 2-adamantanyl acid-trifluoropropane sulfonic acid comprises the following steps: S1. Add 1,1,1-trifluoro-2,3-propylene oxide, sodium bisulfite and sodium hydroxide into an aqueous solution, wherein the molar ratio of 1,1,1-trifluoro-2,3-propylene oxide, sodium bisulfite and sodium hydroxide is 1:1:0.2, and stir to open the epoxy ring while maintaining a constant temperature of 40°C. After the reaction is completed, cool to room temperature and dry to obtain sodium 3,3,3-trifluoro-2-hydroxy-1-propane sulfonate; S2. The sodium 3,3,3-trifluoro-2-hydroxy-1-propane sulfonate prepared in S1 is dissolved in ethyl acetate, and adamantane acid chloride, triethylamine and 4-dimethylaminopyridine are added, the molar ratio of ethyl acetate, triethylamine, 4-dimethylaminopyridine, adamantane acid chloride and 3,3,3-trifluoro-2-hydroxypropane sulfonate is 15:1:0.3:2:1, stirred at 30°C until the reaction is complete, washed and dried, tertiary methyl ether is added to pulp, filtered and dried, and 2-adamantananoic acid-trifluoropropane sulfonate sodium is obtained; S3. Add the 2-adamantanyl acid-trifluoropropane sulfonate sodium and triphenylsulfonium chloride prepared in S2 to ethyl acetate, wherein the molar ratio of 2-adamantanyl acid-trifluoropropane sulfonate sodium to triphenylsulfonium chloride is 1:0.8, stir at room temperature until the reaction is complete, wash with water, concentrate and dry, add tertiary methyl ether to pulp, filter and dry, and obtain crude triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate; S4. The crude triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate is dissolved in ethyl acetate, R210 resin is added and stirred, diatomaceous earth is added for adsorption and filtration, R210 resin is added again and stirred, and then filtered and dried, the mass ratio of ethyl acetate, R210 resin and crude triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate is 15:10:1, isopropyl ether is added for crystallization, and high-purity triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate is obtained; The general structural formula I of the high-purity electronic-grade photoacid generator derived from 2-adamantanyl acid-trifluoropropane sulfonic acid is shown below: (I) Wherein, M is triphenylsulfonium salt. Example 7

[0026] A method for preparing a high-purity electronic-grade photoacid generator derived from 2-adamantanyl acid-trifluoropropane sulfonic acid comprises the following steps: S1. Add 1,1,1-trifluoro-2,3-propylene oxide, sodium bisulfite and sodium hydroxide into an aqueous solution, wherein the molar ratio of 1,1,1-trifluoro-2,3-propylene oxide, sodium bisulfite and sodium hydroxide is 1:1:0.2, and stir to open the epoxy ring while maintaining a constant temperature of 40°C. After the reaction is completed, cool to room temperature and dry to obtain sodium 3,3,3-trifluoro-2-hydroxy-1-propane sulfonate; S2. The sodium 3,3,3-trifluoro-2-hydroxy-1-propane sulfonate prepared in S1 is dissolved in ether, and adamantane acid chloride, triethylamine and 4-dimethylaminopyridine are added, the molar ratio of ether, triethylamine, 4-dimethylaminopyridine, adamantane acid chloride and 3,3,3-trifluoro-2-hydroxypropane sulfonate is 15:1:0.3:2:1, stirred at 30°C until the reaction is complete, washed and dried, tertiary methyl ether is added to pulp, filtered and dried, and 2-adamantananoic acid-trifluoropropane sulfonate sodium is obtained; S3. Add the 2-adamantanyl acid-trifluoropropane sulfonate sodium and triphenylsulfonium chloride prepared in S2 to diethyl ether, wherein the molar ratio of 2-adamantanyl acid-trifluoropropane sulfonate sodium to triphenylsulfonium chloride is 1:0.8, stir at room temperature until the reaction is complete, wash with water, concentrate and dry, add tertiary methyl ether to pulp, filter and dry, and obtain crude triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate; S4. The crude triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate is dissolved in ether, R210 resin is added and stirred, diatomaceous earth is added for adsorption and filtration, R210 resin is added again and stirred, and then filtered and dried, the mass ratio of ether, R210 resin and crude triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate is 15:10:1, isopropyl ether is added for crystallization, and high-purity triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate is obtained; The general structural formula I of the high-purity electronic-grade photoacid generator derived from 2-adamantanyl acid-trifluoropropane sulfonic acid is shown below: (I) Wherein, M is triphenylsulfonium salt. Example 8

[0027] A method for preparing a high-purity electronic-grade photoacid generator derived from 2-adamantanyl acid-trifluoropropane sulfonic acid comprises the following steps: S1. Add 1,1,1-trifluoro-2,3-propylene oxide, sodium bisulfite and sodium hydroxide into an aqueous solution, wherein the molar ratio of 1,1,1-trifluoro-2,3-propylene oxide, sodium bisulfite and sodium hydroxide is 1:1:0.2, and stir to open the epoxy ring while maintaining a constant temperature of 40°C. After the reaction is completed, cool to room temperature and dry to obtain sodium 3,3,3-trifluoro-2-hydroxy-1-propane sulfonate; S2. The sodium 3,3,3-trifluoro-2-hydroxy-1-propane sulfonate prepared in S1 is dissolved in dichloromethane, and adamantane acid chloride, triethylamine and 4-dimethylaminopyridine are added, the molar ratio of dichloromethane, triethylamine, 4-dimethylaminopyridine, adamantane acid chloride and 3,3,3-trifluoro-2-hydroxypropane sulfonate is 15:1.1:0.3:2:1, stirred at 30°C until the reaction is complete, washed and dried, tertiary methyl ether is added to pulp, filtered and dried, to obtain 2-adamantananoic acid-trifluoropropane sulfonate sodium; S3. Add the 2-adamantanyl acid-trifluoropropane sulfonate sodium and triphenylsulfonium chloride prepared in S2 to dichloromethane, wherein the molar ratio of 2-adamantanyl acid-trifluoropropane sulfonate sodium to triphenylsulfonium chloride is 1:0.8, stir at room temperature until the reaction is complete, wash with water, concentrate and dry, add tertiary methyl ether to pulp, filter and dry, and obtain crude triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate; S4. The crude triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate is dissolved in dichloromethane, R210 resin is added and stirred, diatomaceous earth is added for adsorption and filtration, R210 resin is added again and stirred, and then filtered and dried, the mass ratio of dichloromethane, R210 resin and crude triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate is 15:10:1, isopropyl ether is added for crystallization, and high-purity triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate is obtained; The general structural formula I of the high-purity electronic-grade photoacid generator derived from 2-adamantanyl acid-trifluoropropane sulfonic acid is shown below: (I) Wherein, M is triphenylsulfonium salt.

[0028] Example 9 A method for preparing a high-purity electronic-grade photoacid generator derived from 2-adamantanyl acid-trifluoropropane sulfonic acid comprises the following steps: S1. Add 1,1,1-trifluoro-2,3-propylene oxide, sodium bisulfite and sodium hydroxide into an aqueous solution, wherein the molar ratio of 1,1,1-trifluoro-2,3-propylene oxide, sodium bisulfite and sodium hydroxide is 1:1:0.2, and stir to open the epoxy ring while maintaining a constant temperature of 40°C. After the reaction is completed, cool to room temperature and dry to obtain sodium 3,3,3-trifluoro-2-hydroxy-1-propane sulfonate; S2. The sodium 3,3,3-trifluoro-2-hydroxy-1-propane sulfonate prepared in S1 is dissolved in dichloromethane, and adamantane acid chloride, triethylamine and 4-dimethylaminopyridine are added, the molar ratio of dichloromethane, triethylamine, 4-dimethylaminopyridine, adamantane acid chloride and 3,3,3-trifluoro-2-hydroxypropane sulfonate is 15:1.3:0.3:2:1, stirred at 30°C until the reaction is complete, washed and dried, tertiary methyl ether is added to pulp, filtered and dried, to obtain 2-adamantananoic acid-trifluoropropane sulfonate sodium; S3. Add the 2-adamantanyl acid-trifluoropropane sulfonate sodium and triphenylsulfonium chloride prepared in S2 to dichloromethane, wherein the molar ratio of 2-adamantanyl acid-trifluoropropane sulfonate sodium to triphenylsulfonium chloride is 1:0.8, stir at room temperature until the reaction is complete, wash with water, concentrate and dry, add tertiary methyl ether to pulp, filter and dry, and obtain crude triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate; S4. The crude triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate is dissolved in dichloromethane, R210 resin is added and stirred, diatomaceous earth is added for adsorption and filtration, R210 resin is added again and stirred, and then filtered and dried, the mass ratio of dichloromethane, R210 resin and crude triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate is 15:10:1, isopropyl ether is added for crystallization, and high-purity triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate is obtained; The general structural formula I of the high-purity electronic-grade photoacid generator derived from 2-adamantanyl acid-trifluoropropane sulfonic acid is shown below: (I) Wherein, M is triphenylsulfonium salt.

[0029] Embodiment 10: A method for preparing a high-purity electronic-grade photoacid generator derived from 2-adamantanyl acid-trifluoropropane sulfonic acid comprises the following steps: S1. Add 1,1,1-trifluoro-2,3-propylene oxide, sodium bisulfite and sodium hydroxide into an aqueous solution, wherein the molar ratio of 1,1,1-trifluoro-2,3-propylene oxide, sodium bisulfite and sodium hydroxide is 1:1:0.2, and stir to open the epoxy ring while maintaining a constant temperature of 40°C. After the reaction is completed, cool to room temperature and dry to obtain sodium 3,3,3-trifluoro-2-hydroxy-1-propane sulfonate; S2. The sodium 3,3,3-trifluoro-2-hydroxy-1-propane sulfonate prepared in S1 is dissolved in dichloromethane, and adamantane acid chloride, triethylamine and 4-dimethylaminopyridine are added, the molar ratio of dichloromethane, triethylamine, 4-dimethylaminopyridine, adamantane acid chloride and 3,3,3-trifluoro-2-hydroxypropane sulfonate is 15:1.5:0.3:2:1, stirred at 30°C until the reaction is complete, washed and dried, tertiary methyl ether is added to pulp, filtered and dried, and 2-adamantananoic acid-trifluoropropane sulfonate sodium is obtained; S3. Add the 2-adamantanyl acid-trifluoropropane sulfonate sodium and triphenylsulfonium chloride prepared in S2 to dichloromethane, wherein the molar ratio of 2-adamantanyl acid-trifluoropropane sulfonate sodium to triphenylsulfonium chloride is 1:0.8, stir at room temperature until the reaction is complete, wash with water, concentrate and dry, add tertiary methyl ether to pulp, filter and dry, and obtain crude triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate; S4. The crude triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate is dissolved in dichloromethane, R210 resin is added and stirred, diatomaceous earth is added for adsorption and filtration, R210 resin is added again and stirred, and then filtered and dried, the mass ratio of dichloromethane, R210 resin and crude triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate is 15:10:1, isopropyl ether is added for crystallization, and high-purity triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate is obtained; The general structural formula I of the high-purity electronic-grade photoacid generator derived from 2-adamantanyl acid-trifluoropropane sulfonic acid is shown below: (I) Wherein, M is triphenylsulfonium salt.

[0030] Embodiment 11: A method for preparing a high-purity electronic-grade photoacid generator derived from 2-adamantanyl acid-trifluoropropane sulfonic acid, comprising the following steps: S1. adding 1,1,1-trifluoro-2,3-propylene oxide, sodium bisulfite and sodium hydroxide into an aqueous solution, wherein the molar ratio of 1,1,1-trifluoro-2,3-propylene oxide, sodium bisulfite and sodium hydroxide is 1:1:0.2, maintaining a constant temperature of 40°C and stirring to open the epoxy ring, cooling to room temperature after the reaction is completed and drying to obtain sodium 3,3,3-trifluoro-2-hydroxy-1-propane sulfonate; S2. The sodium 3,3,3-trifluoro-2-hydroxy-1-propane sulfonate prepared in S1 is dissolved in dichloromethane, and adamantane acid chloride, triethylamine and 4-dimethylaminopyridine are added, the molar ratio of dichloromethane, triethylamine, 4-dimethylaminopyridine, adamantane acid chloride and 3,3,3-trifluoro-2-hydroxypropane sulfonate is 15:1:0.4:2:1, stirred at 30°C until the reaction is complete, washed and dried, tertiary methyl ether is added to pulp, filtered and dried, and 2-adamantananoic acid-trifluoropropane sulfonate sodium is obtained; S3. Add the 2-adamantanyl acid-trifluoropropane sulfonate sodium and triphenylsulfonium chloride prepared in S2 to dichloromethane, wherein the molar ratio of 2-adamantanyl acid-trifluoropropane sulfonate sodium to triphenylsulfonium chloride is 1:0.8, stir at room temperature until the reaction is complete, wash with water, concentrate and dry, add tertiary methyl ether to pulp, filter and dry, and obtain crude triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate; S4. The crude triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate is dissolved in dichloromethane, R210 resin is added and stirred, diatomaceous earth is added for adsorption and filtration, R210 resin is added again and stirred, and then filtered and dried, the mass ratio of dichloromethane, R210 resin and crude triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate is 15:10:1, isopropyl ether is added for crystallization, and high-purity triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate is obtained; The general structural formula I of the high-purity electronic-grade photoacid generator derived from 2-adamantanyl acid-trifluoropropane sulfonic acid is shown below: (I) Wherein, M is triphenylsulfonium salt.

[0031] Embodiment 12: A method for preparing a high-purity electronic-grade photoacid generator derived from 2-adamantanyl acid-trifluoropropane sulfonic acid comprises the following steps: S1. Add 1,1,1-trifluoro-2,3-propylene oxide, sodium bisulfite and sodium hydroxide into an aqueous solution, wherein the molar ratio of 1,1,1-trifluoro-2,3-propylene oxide, sodium bisulfite and sodium hydroxide is 1:1:0.2, and stir to open the epoxy ring while maintaining a constant temperature of 40°C. After the reaction is completed, cool to room temperature and dry to obtain sodium 3,3,3-trifluoro-2-hydroxy-1-propane sulfonate; S2. The sodium 3,3,3-trifluoro-2-hydroxy-1-propane sulfonate prepared in S1 is dissolved in dichloromethane, and adamantane acid chloride, triethylamine and 4-dimethylaminopyridine are added, the molar ratio of dichloromethane, triethylamine, 4-dimethylaminopyridine, adamantane acid chloride and 3,3,3-trifluoro-2-hydroxypropane sulfonate is 15:1:0.5:2:1, stirred at 30°C until the reaction is complete, washed and dried, tertiary methyl ether is added to pulp, filtered and dried, to obtain 2-adamantananoic acid-trifluoropropane sodium sulfonate; S3. Add the 2-adamantanyl acid-trifluoropropane sulfonate sodium and triphenylsulfonium chloride prepared in S2 to dichloromethane, wherein the molar ratio of 2-adamantanyl acid-trifluoropropane sulfonate sodium to triphenylsulfonium chloride is 1:0.8, stir at room temperature until the reaction is complete, wash with water, concentrate and dry, add tertiary methyl ether to pulp, filter and dry, and obtain crude triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate; S4. The crude triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate is dissolved in dichloromethane, R210 resin is added and stirred, diatomaceous earth is added for adsorption and filtration, R210 resin is added again and stirred, and then filtered and dried, the mass ratio of dichloromethane, R210 resin and crude triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate is 15:10:1, isopropyl ether is added for crystallization, and high-purity triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate is obtained; The general structural formula I of the high-purity electronic-grade photoacid generator derived from 2-adamantanyl acid-trifluoropropane sulfonic acid is shown below: (I) Wherein, M is triphenylsulfonium salt.

[0032] Comparative Example 1: A method for preparing a high-purity electronic-grade photoacid generator derived from 2-adamantanyl acid-trifluoropropane sulfonic acid comprises the following steps: S1. Add 1,1,1-trifluoro-2,3-propylene oxide, sodium bisulfite and sodium hydroxide into an aqueous solution, wherein the molar ratio of 1,1,1-trifluoro-2,3-propylene oxide, sodium bisulfite and sodium hydroxide is 1:1:0.2, and stir to open the epoxy ring while maintaining a constant temperature of 40°C. After the reaction is completed, cool to room temperature and dry to obtain sodium 3,3,3-trifluoro-2-hydroxy-1-propane sulfonate; S2. The sodium 3,3,3-trifluoro-2-hydroxy-1-propane sulfonate prepared in S1 is dissolved in dichloromethane, and adamantane carboxylic acid, triethylamine and 4-dimethylaminopyridine are added, the molar ratio of dichloromethane, triethylamine, 4-dimethylaminopyridine, adamantane carboxylic acid and 3,3,3-trifluoro-2-hydroxypropane sulfonate is 15:1:0.3:2:1, stirred at 30°C until the reaction is complete, washed and dried, tertiary methyl ether is added to pulp, filtered and dried, to obtain sodium 2-adamantananoic acid-trifluoropropane sulfonate; S3. Add the 2-adamantanyl acid-trifluoropropane sulfonate sodium and triphenylsulfonium chloride prepared in S2 to dichloromethane, wherein the molar ratio of 2-adamantanyl acid-trifluoropropane sulfonate sodium to triphenylsulfonium chloride is 1:0.8, stir at room temperature until the reaction is complete, wash with water, concentrate and dry, add tertiary methyl ether to pulp, filter and dry, and obtain crude triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate; S4. The crude triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate is dissolved in dichloromethane, R210 resin is added and stirred, diatomaceous earth is added for adsorption and filtration, R210 resin is added again and stirred, and then filtered and dried, the mass ratio of dichloromethane, R210 resin and crude M, 2-adamantanyl acid-trifluoropropane sulfonate is 15:10:1, isopropyl ether is added for crystallization, and high-purity triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate is obtained; The general structural formula I of the high-purity electronic-grade photoacid generator derived from 2-adamantanyl acid-trifluoropropane sulfonic acid is shown below: (I) Wherein, M is triphenylsulfonium salt.

[0033] Table 2 Effect of different raw materials used in esterification reaction on product yield name Esterification raw materials Yield / % Example 1 Adamantane acid chloride 90 Comparative Example 1 Adamantane carboxylic acid 65 Comparative Example 2: A method for preparing a high-purity electronic-grade photoacid generator derived from 2-adamantanyl acid-trifluoropropane sulfonic acid comprises the following steps: S1. Add 1,1,1-trifluoro-2,3-propylene oxide, sodium bisulfite and sodium hydroxide into an aqueous solution, wherein the molar ratio of 1,1,1-trifluoro-2,3-propylene oxide, sodium bisulfite and sodium hydroxide is 1:1:0.2, and stir to open the epoxy ring while maintaining a constant temperature of 40°C. After the reaction is completed, cool to room temperature and dry to obtain sodium 3,3,3-trifluoro-2-hydroxy-1-propane sulfonate; S2. The sodium 3,3,3-trifluoro-2-hydroxy-1-propane sulfonate prepared in S1 is dissolved in dichloromethane, and adamantane acid chloride, triethylamine and 4-dimethylaminopyridine are added, the molar ratio of dichloromethane, triethylamine, 4-dimethylaminopyridine, adamantane acid chloride and 3,3,3-trifluoro-2-hydroxypropane sulfonate is 15:1:0.3:2:1, stirred at 20°C until the reaction is complete, washed and dried, tertiary methyl ether is added to pulp, filtered and dried, to obtain 2-adamantananoic acid-trifluoropropane sulfonate sodium; S3. Add the 2-adamantanyl acid-trifluoropropane sulfonate sodium and triphenylsulfonium chloride prepared in S2 to dichloromethane, wherein the molar ratio of 2-adamantanyl acid-trifluoropropane sulfonate sodium to triphenylsulfonium chloride is 1:0.8, stir at room temperature until the reaction is complete, wash with water, concentrate and dry, add tertiary methyl ether to pulp, filter and dry, and obtain crude triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate; S4. The crude triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate is dissolved in dichloromethane, R210 resin is added and stirred, diatomaceous earth is added for adsorption and filtration, R210 resin is added again and stirred, and then filtered and dried, the mass ratio of dichloromethane, R210 resin and crude triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate is 15:10:1, isopropyl ether is added for crystallization, and high-purity triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate is obtained; The general structural formula I of the high-purity electronic-grade photoacid generator derived from 2-adamantanyl acid-trifluoropropane sulfonic acid is shown below: (I) Wherein, M is triphenylsulfonium salt.

[0034] Comparative Example 3: A method for preparing a high-purity electronic-grade photoacid generator derived from 2-adamantanyl acid-trifluoropropane sulfonic acid comprises the following steps: S1. Add 1,1,1-trifluoro-2,3-propylene oxide, sodium bisulfite and sodium hydroxide into an aqueous solution, wherein the molar ratio of 1,1,1-trifluoro-2,3-propylene oxide, sodium bisulfite and sodium hydroxide is 1:1:0.2, and stir to open the epoxy ring while maintaining a constant temperature of 40°C. After the reaction is completed, cool to room temperature and dry to obtain sodium 3,3,3-trifluoro-2-hydroxy-1-propane sulfonate; S2. The sodium 3,3,3-trifluoro-2-hydroxy-1-propane sulfonate prepared in S1 is dissolved in dichloromethane, and adamantane acid chloride, triethylamine and 4-dimethylaminopyridine are added, the molar ratio of dichloromethane, triethylamine, 4-dimethylaminopyridine, adamantane acid chloride and 3,3,3-trifluoro-2-hydroxypropane sulfonate is 15:1:0.3:2:1, stirred at 40°C until the reaction is complete, washed and dried, tertiary methyl ether is added to pulp, filtered and dried, to obtain 2-adamantananoic acid-trifluoropropane sulfonate sodium; S3. Add the 2-adamantanyl acid-trifluoropropane sulfonate sodium and triphenylsulfonium chloride prepared in S2 to dichloromethane, wherein the molar ratio of 2-adamantanyl acid-trifluoropropane sulfonate sodium to triphenylsulfonium chloride is 1:0.8, stir at room temperature until the reaction is complete, wash with water, concentrate and dry, add tertiary methyl ether to pulp, filter and dry, and obtain crude triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate; S4. The crude triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate is dissolved in dichloromethane, R210 resin is added and stirred, diatomaceous earth is added for adsorption and filtration, R210 resin is added again and stirred, and then filtered and dried, the mass ratio of dichloromethane, R210 resin and crude triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate is 15:10:1, isopropyl ether is added for crystallization, and high-purity triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate is obtained; The general structural formula I of the high-purity electronic-grade photoacid generator derived from 2-adamantanyl acid-trifluoropropane sulfonic acid is shown below: (I) Wherein, M is triphenylsulfonium salt.

[0035] Table 3 Effect of different esterification reaction temperatures on product yield name Reaction temperature / °C Yield / % Example 1 30 90 Example 2 25 85 Comparative Example 2 20 72 Comparative Example 3 40 60 Comparative Example 4: A method for preparing a high-purity electronic-grade photoacid generator derived from 2-adamantanyl acid-trifluoropropane sulfonic acid comprises the following steps: S1. Add 2-bromo-3,3,3-trifluoropropan-1-ol and sodium bisulfite to an aqueous solution, the molar ratio of 2-bromo-3,3,3-trifluoropropan-1-ol to sodium bisulfite is 1:2, continuously introduce nitrogen, stir at 85°C until the reaction is complete, cool to room temperature and dry to obtain sodium 3,3,3-trifluoro-2-hydroxy-1-propane sulfonate; S2. The sodium 3,3,3-trifluoro-2-hydroxy-1-propane sulfonate prepared in S1 is dissolved in dichloromethane, and adamantane acid chloride, triethylamine and 4-dimethylaminopyridine are added, the molar ratio of dichloromethane, triethylamine, 4-dimethylaminopyridine, adamantane acid chloride and 3,3,3-trifluoro-2-hydroxypropane sulfonate is 15:1:0.3:2:1, stirred at 30°C until the reaction is complete, washed and dried, tertiary methyl ether is added to pulp, filtered and dried, to obtain 2-adamantananoic acid-trifluoropropane sulfonate sodium; S3. Add the 2-adamantanyl acid-trifluoropropane sulfonate sodium and triphenylsulfonium chloride prepared in S2 to dichloromethane, wherein the molar ratio of 2-adamantanyl acid-trifluoropropane sulfonate sodium to triphenylsulfonium chloride is 1:0.8, stir at room temperature until the reaction is complete, wash with water, concentrate and dry, add tertiary methyl ether to pulp, filter and dry, and obtain crude triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate; S4. The crude triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate is dissolved in dichloromethane, R210 resin is added and stirred, diatomaceous earth is added for adsorption and filtration, R210 resin is added again and stirred, and then filtered and dried, the mass ratio of dichloromethane, R210 resin and crude triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate is 15:10:1, isopropyl ether is added for crystallization, and high-purity triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate is obtained; The general structural formula I of the high-purity electronic-grade photoacid generator derived from 2-adamantanyl acid-trifluoropropane sulfonic acid is shown below: (I) Wherein, M is triphenylsulfonium salt.

[0036] Table 4 Effect of different synthetic routes of sodium 3,3,3-trifluoro-2-hydroxy-1-propane sulfonate on product yield

[0037] Comparative Example 5: A method for preparing a high-purity electronic-grade photoacid generator derived from 2-adamantanyl acid-trifluoropropane sulfonic acid comprises the following steps: S1. Add 1,1,1-trifluoro-2,3-propylene oxide, sodium bisulfite and sodium hydroxide into an aqueous solution, wherein the molar ratio of 1,1,1-trifluoro-2,3-propylene oxide, sodium bisulfite and sodium hydroxide is 1:1:0.2, and stir to open the epoxy ring while maintaining a constant temperature of 40°C. After the reaction is completed, cool to room temperature and dry to obtain sodium 3,3,3-trifluoro-2-hydroxy-1-propane sulfonate; S2. The sodium 3,3,3-trifluoro-2-hydroxy-1-propane sulfonate prepared in S1 is dissolved in xylene, and adamantane acid chloride, triethylamine and 4-dimethylaminopyridine are added, the molar ratio of xylene, triethylamine, 4-dimethylaminopyridine, adamantane acid chloride and 3,3,3-trifluoro-2-hydroxypropane sulfonate is 15:1:0.3:2:1, stirred at 30°C until the reaction is complete, washed and dried, tertiary methyl ether is added to pulp, filtered and dried, and 2-adamantananoic acid-trifluoropropane sulfonate sodium is obtained; S3. Add the 2-adamantanyl acid-trifluoropropane sulfonate sodium and triphenylsulfonium chloride prepared in S2 to xylene, wherein the molar ratio of 2-adamantanyl acid-trifluoropropane sulfonate sodium to triphenylsulfonium chloride is 1:0.8, stir at room temperature until the reaction is complete, wash with water, concentrate and dry, add tertiary methyl ether to pulp, filter and dry, and obtain crude triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate; S4. The crude triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate is dissolved in xylene, R210 resin is added and stirred, diatomaceous earth is added for adsorption and filtration, R210 resin is added again and stirred, and then filtered and dried, the mass ratio of xylene, R210 resin and crude triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate is 15:10:1, isopropyl ether is added for crystallization, and high-purity triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate is obtained; The general structural formula I of the high-purity electronic-grade photoacid generator derived from 2-adamantanyl acid-trifluoropropane sulfonic acid is shown below: (I) Wherein, M is triphenylsulfonium salt.

[0038] Table 5 Effect of different solvents on product yield name Solvents Yield / % Example 1 Dichloromethane 90 Example 6 Ethyl acetate 82 Example 7 Ether 80 Comparative Example 5 Xylene 65 Comparative Example 6: A method for preparing a high-purity electronic-grade photoacid generator derived from 2-adamantanyl acid-trifluoropropane sulfonic acid comprises the following steps: S1. Add 1,1,1-trifluoro-2,3-propylene oxide, sodium bisulfite and sodium hydroxide into an aqueous solution, wherein the molar ratio of 1,1,1-trifluoro-2,3-propylene oxide, sodium bisulfite and sodium hydroxide is 1:1:0.2, and stir to open the epoxy ring while maintaining a constant temperature of 40°C. After the reaction is completed, cool to room temperature and dry to obtain sodium 3,3,3-trifluoro-2-hydroxy-1-propane sulfonate; S2. The sodium 3,3,3-trifluoro-2-hydroxy-1-propane sulfonate prepared in S1 is dissolved in dichloromethane, and adamantane acid chloride, triethylamine and 4-dimethylaminopyridine are added, the molar ratio of dichloromethane, triethylamine, 4-dimethylaminopyridine, adamantane acid chloride and 3,3,3-trifluoro-2-hydroxypropane sulfonate is 15:2:1:2:1, stirred at 30°C until the reaction is complete, washed and dried, tertiary methyl ether is added to pulp, filtered and dried, to obtain 2-adamantananoic acid-trifluoropropane sulfonate sodium; S3. Add the 2-adamantanyl acid-trifluoropropane sulfonate sodium and triphenylsulfonium chloride prepared in S2 to dichloromethane, wherein the molar ratio of 2-adamantanyl acid-trifluoropropane sulfonate sodium to triphenylsulfonium chloride is 1:0.8, stir at room temperature until the reaction is complete, wash with water, concentrate and dry, add tertiary methyl ether to pulp, filter and dry, and obtain crude triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate; S4. The crude triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate is dissolved in dichloromethane, R210 resin is added and stirred, diatomaceous earth is added for adsorption and filtration, R210 resin is added again and stirred, and then filtered and dried, the mass ratio of dichloromethane, R210 resin and crude triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate is 15:10:1, isopropyl ether is added for crystallization, and high-purity triphenylsulfonium, 2-adamantanyl acid-trifluoropropane sulfonate is obtained; The general structural formula I of the high-purity electronic-grade photoacid generator derived from 2-adamantanyl acid-trifluoropropane sulfonic acid is shown below: (I) Wherein, M is triphenylsulfonium salt.

[0039] Table 6 Effect of different molar ratios of acid-binding agent, catalyst and reactant on product yield in esterification reaction name The molar ratio of solvent, acid binding agent, catalyst, esterification raw material and reactant Yield / % Example 1 15：1：0.3：2：1 90 Example 8 15：1.1：0.3：2：1 88 Example 9 15：1.3：0.3：2：1 85 Example 10 15：1.5：0.3：2：1 82 Embodiment 11 15：1：0.4：2：1 87 Example 12 15：1：0.5：2：1 85 Comparative Example 6 15：2：1：2：1 70 The above is only a preferred embodiment of the present invention and does not limit the present invention in any form. Any technician familiar with the art can make many possible changes and modifications to the technical solution of the present invention by using the above disclosed methods and technical contents without departing from the spirit and technical solution of the present invention, or modify it into an equivalent embodiment of equivalent changes. Therefore, any simple modification, equivalent replacement, equivalent change and modification made to the above embodiments according to the technical essence of the present invention without departing from the content of the technical solution of the present invention still falls within the scope of protection of the technical solution of the present invention.

Claims

1. A method for preparing a high-purity electronic-grade photoacid generator derived from 2-adamantanyl acid-trifluoropropane sulfonic acid, characterized in that: The following steps are involved: S1. 1,1,1-trifluoro-2,3-propylene oxide, a sulfonating agent and sodium hydroxide are added to an aqueous solution, the temperature is maintained and stirred to open the epoxy ring, and after the reaction is completed, the reaction is cooled to room temperature and dried to obtain sodium 3,3,3-trifluoro-2-hydroxy-1-propane sulfonate; S2. The sodium 3,3,3-trifluoro-2-hydroxy-1-propane sulfonate prepared in S1 is dissolved in solvent A, and an adamantyl derivative, an acid binding agent and a catalyst are added, and the mixture is stirred at a constant temperature until the reaction is complete, washed and dried, tertiary methyl ether is added to pulp and filtered to obtain sodium 2-adamantanyl acid-trifluoropropane sulfonate; S3. The 2-adamantanyl acid - sodium trifluoropropane sulfonate and M salt chloride prepared in S2 were added to solvent A, stirred at room temperature until the reaction was complete, washed with water, concentrated and dried, methyl tert-ether was added to pulp and filtered to obtain a crude product M, 2-adamantanyl acid - trifluoropropane sulfonate; S4. The crude product M, 2-adamantanic acid - trifluoropropane sulfonate was dissolved in solvent A, R210 resin was added and stirred, diatomaceous earth was added for adsorption and filtration, R210 resin was added again and stirred, then filtered and dried, isopropyl ether was added for crystallization to obtain high purity M, 2-adamantanic acid - trifluoropropane sulfonate; The solvent A in steps S2, S3 and S4 comprises any one of dichloromethane, ethyl acetate and diethyl ether.

2. The method for preparing the high-purity electronic-grade photoacid generator derived from 2-adamantanyl acid-trifluoropropane sulfonic acid according to claim 1, characterized in that: The general structural formula I of the high-purity electronic-grade photoacid generator derived from 2-adamantanyl acid-trifluoropropane sulfonic acid is shown below: （Ⅰ） Wherein, M is triarylsulfonium salt, diaryliodonium salt and derivatives thereof.

3. The method for preparing the high-purity electronic-grade photoacid generator derived from 2-adamantanyl acid-trifluoropropane sulfonic acid according to claim 1, characterized in that: The sulfonating agent in step S1 includes any one or more of sodium bisulfite, sodium dithionite, sodium sulfite, and sodium thiosulfate.

4. The method for preparing the high-purity electronic-grade photoacid generator derived from 2-adamantanyl acid-trifluoropropane sulfonic acid according to claim 1, characterized in that: In step S1, the molar ratio of 1,1,1-trifluoro-2,3-propylene oxide, sulfonating agent and sodium hydroxide is 1:1-1.5:0.2-0.4, and the reaction temperature is 40-50°C.

5. The method for preparing the high-purity electronic-grade photoacid generator derived from 2-adamantanyl acid-trifluoropropane sulfonic acid according to claim 1, characterized in that: In step S2, the adamantyl derivative includes any one of adamantane chloride and adamantane carboxylic acid, the acid binding agent includes any one or more of triethylamine, trimethylamine, dimethylamine, ethanolamine, and isopropylamine, and the catalyst includes any one or more of 4-dimethylaminopyridine, pyridine, 4,4'-bipyridine, and aminopyridine.

6. The method for preparing the high-purity electronic-grade photoacid generator derived from 2-adamantanyl acid-trifluoropropane sulfonic acid according to claim 1, characterized in that: In step S2, the molar ratio of the solvent, the acid binding agent, the catalyst, the adamantane esterification raw material and the 3,3,3-trifluoro-2-hydroxypropane sulfonate is 10-20:1-1.5:0.3-0.5:1-3:1, and the reaction temperature is 25-30°C.

7. The method for preparing the high-purity electronic-grade photoacid generator derived from 2-adamantanyl acid-trifluoropropane sulfonic acid according to claim 1, characterized in that: In step S3, the molar ratio of 2-adamantanyl acid-trifluoropropane sulfonate sodium to M salt chloride is 1:0.6-0.

8.

8. The method for preparing the high-purity electronic-grade photoacid generator derived from 2-adamantanyl acid-trifluoropropane sulfonic acid according to claim 1, characterized in that: In the step S4, the mass ratio of the solvent, the R210 resin and the crude product M, 2-adamantanyl acid-trifluoropropane sulfonate is 10-20:8-12:1.

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