Photoinduced acid generator sulfonate for photoresist and preparation method thereof

Abstract

The invention discloses a process route for synthesizing 4-[4-(1, 1-dimethylethyl) phenyl]-1, 4-oxothiaonium salt and 1-(5, 5, 6, 6-tetrafluorospiro [1, 3-dioxane naphthene-2, 2 '-tricyclo [3.3. 1.13, 7] decane]-5'-yl) 2, 2-difluoro-2-sulfoacetate, cation fragments are provided by bis (4-tert-butylphenyl) iodine trifluoromethanesulfonate, and the cation fragments are provided by bis (4-tert-butylphenyl) iodine trifluoromethanesulfonate. According to the synthetic route, thioxane sulfonate is formed through substitution, then ion exchange is carried out, and finally the obtained intermediate is subjected to ketal to obtain the target photoacid generator product. By optimizing reaction conditions and a process route, the use amount of resin is reduced, side reactions are effectively controlled in the front stage of the process, the purity, stability and yield of the photoacid generator are improved, the metal content and halogen content of the compounds are reduced, and the yield of the photoacid generator is improved. The requirements of modern microelectronic manufacturing on a high-performance photoacid generator are met.

Description

Technical Field

[0001] This invention relates to the field of organic synthesis technology, and in particular to a sulfonate salt of photoacid generator for photoresists and its preparation method. Background Technology

[0002] Photoacid generators are compounds that decompose and ultimately form specific acidic substances under external stimuli (such as light, heat, and radiation). The resulting acidic substances are photo-controllable acids that can cause acid-sensitive substances to decompose or cross-link, making them a key component of high-end semiconductor photoresists. Based on structural characteristics, they can be divided into two main categories: ionic and non-ionic. Among traditional ionic photoacid generators, ononium salts dominate. Ononium salts are diverse, have high acid-generating efficiency, fast photoinitiation rates, good thermal stability, and high acid strength. However, their poor stability and solubility, along with a short absorption wavelength range, limit their applications. Among non-ionic photoacid generators, sulfonates are representative, possessing advantages such as good solubility, low acid-generating toxicity, and a broad absorption spectrum. However, there are relatively few sulfonate acid generators suitable for the visible light wavelength range. Studying the structure-activity relationship between molecular structure and compound type on the acid-generating performance of photoacid generators, and developing novel compounds, has become a research hotspot in the field of photoacid generators in recent years. In addition, traditional methods for preparing photoacid generators often suffer from problems such as complex synthesis routes, low economic efficiency, and poor product stability. New synthesis processes need to be developed to improve the purity and stability of photoacid generators, reduce reaction byproducts, and meet the demand of modern microelectronics manufacturing for high-performance photoacid generators. Summary of the Invention

[0003] The technical problem to be solved: The technical problem to be solved by the present invention is to provide a photoacid-generating sulfonate for photoresist and its preparation method, which produces a product with few impurities, high product yield and low manufacturing cost.

[0004] Technical solution: A method for preparing a sulfonate salt of photoacid-generating agent for photoresist, comprising the following steps: S1. Mix raw material A sodium difluorosulfate, raw material B 5-hydroxyadamantane-2-one and toluene and add sulfuric acid. Heat and stir to carry out esterification reaction. After filtration, add 4-methyl-2-pentanone to the solid and slurry. Filter and dry the solid to obtain intermediate product D1,1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate sodium; S2. The intermediate product D1,1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate sodium salt is exchanged with the starting material S to obtain the intermediate product E4-[4-(1,1-dimethylethyl)phenyl)1,4-oxothiothiamonium salt and 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]5'-yl)2,2-difluoro-2-sulfoacetate salt; S3. The intermediate product E4-[4-(1,1-dimethylethyl)phenyl)1,4-oxothiothiamonium salt, 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]5'-yl)2,2-difluoro-2-sulfoacetate, the starting material C2,2,3,3-tetrafluoro-1,4-butanediol, sulfuric acid, and dichloroethane were mixed and heated to carry out an esterification and ring-closing reaction. The organic phase was washed and concentrated under reduced pressure. Toluene was added to dissolve until clear, and methyl ether was added to crystallize, yielding the photo-induced acid-producing sulfonate. In step S2, the raw material S includes any one of the following: 4-(4-(tert-butyl)phenyl)-1,4-oxalate-4-ammonium salt of trifluoromethanesulfonic acid, bis(4-tert-butylphenyl) iodide hydroxide methanol solution, and 4-(4-tert-butylphenyl)-1,4-oxothiacyclohexane-4-tetrafluoroborate. Preferably, the esterification reaction temperature in step S1 is 110–130°C, the reaction time is 14–18 h, and the molar ratio of raw material A (sodium difluorosulfate), raw material B (5-hydroxyadamantane-2-one), and sulfuric acid is 1:1–1.2:1. Preferably, the preparation method of the raw material trifluoromethanesulfonic acid 4-(4-(tert-butyl)phenyl)-1,4-oxalate-4-ammonium salt and its reaction with the intermediate product D1,1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate sodium salt includes the following steps: S11. Bis(4-tert-butylphenyl)iodotrifluoromethanesulfonate, 1-4-thiaoxane, copper catalyst and dichloroethane are mixed and heated to carry out a substitution reaction. The mass ratio of bis(4-tert-butylphenyl)iodotrifluoromethanesulfonate, 1-4-thiaoxane and copper catalyst is 1:1.1 to 1.5:0.1. After the reaction is completed, the mixture is filtered under reduced pressure and washed with 1-2 wt% citric acid aqueous solution. After separation, the organic layer is washed and concentrated under reduced pressure. A mixed solution of ethyl acetate and methyl tert-ethyl ether is added, the mixture is slurried and dried to obtain 4-(4-(tert-butyl)phenyl)-1,4-oxalate-4-ammonium salt of trifluoromethanesulfonate. S12. Sodium 1,1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate, 4-(4-(tert-butyl)phenyl)-1,4-oxalate-4-ammonium salt of trifluoromethanesulfonate, alkali, water, and dichloromethane are mixed and subjected to an exchange reaction at room temperature. The resulting products are 4-(4-(tert-butyl)phenyl)-1,4-oxalate-4-ammonium salt of trifluoromethanesulfonate and the intermediate D1,1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate. The molar ratio of sodium ethane-1-sulfonate (OH) to base was 1.5–2.5:1:1. The organic phase was separated, washed, and concentrated under reduced pressure. 4-methyl-2-pentanone was added to precipitate a solid. Isopropyl ether was added, the mixture was stirred, filtered, and dried to obtain the intermediate product E4-[4-(1,1-dimethylethyl)phenyl)1,4-oxothiothiamonium salt and 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]5'-yl)2,2-difluoro-2-sulfoacetate. Preferably, the preparation method of the raw material bis(4-tert-butylphenyl)iodide hydroxide methanol solution and the reaction with the intermediate product D1,1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate sodium include the following steps: S21. Mix bis(4-tert-butylphenyl)iodide trifluoromethanesulfonate and resin in methanol solvent at a mass ratio of 1:7-9 and filter. Then add 1-3 times the mass of resin, stir and filter to obtain bis(4-tert-butylphenyl)iodide hydroxide methanol solution. S22. The intermediate product D1,1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate sodium salt was added to a methanol solution of bis(4-tert-butylphenyl)iodide hydroxide, wherein the molar ratio of bis(4-tert-butylphenyl)iodotrifluoromethanesulfonate to the intermediate product D1,1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate sodium salt was 1: 1.5-2, stirred at room temperature and filtered, washed with methanol and concentrated, added dichloromethane to dissolve until clear and washed, concentrated the organic phase under reduced pressure, added 4-methyl-2-pentanone until solid precipitate, added isopropyl ether to slurry, filtered and dried to obtain bis(4-tert-butylphenyl)iodide 1,1-difluoro-2-oxo-2-((1s,3R,5S,7s)-4-oxoadamantane-1-yl)oxoethane-1-sulfonate; S23. A mixture of bis(4-tert-butylphenyl)iodide 1,1-difluoro-2-oxo-2-((1s,3R,5S,7s)-4-oxoadamantane-1-yl)oxoethane-1-sulfonate, 1,4-thiaoxane, a copper catalyst, and dichloroethane is heated to carry out a substitution reaction. The molar ratio was 1:1.1 to 1.5:0.1. The mixture was filtered and the filtrate was washed with 1 to 2 wt% citric acid aqueous solution. The organic phase was washed, separated, concentrated under reduced pressure, and 4-methyl-2-pentanone was added until solid precipitation. Isopropyl ether was added, the mixture was stirred, filtered, and dried to obtain the intermediate product E4-[4-(1,1-dimethylethyl)phenyl)1,4-oxothiothiamonium salt and 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]5'-yl)2,2-difluoro-2-sulfoacetate salt. Preferably, the preparation method of the raw material 4-(4-tert-butylphenyl)-1,4-oxothiacyclohexane-4-tetrafluoroborate and the reaction with the intermediate product D1,1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate sodium salt include the following steps: S31. Triphenylsulfonium chloride and resin in a mass ratio of 1:4 to 6 are stirred in methanol until the reaction is complete. Sodium borate is added and stirred, then filtered and concentrated under reduced pressure. The molar ratio of triphenylsulfonium chloride to sodium borate is 1:1 to 1.3. Ethyl acetate is added to dissolve the solid, methyl tert-ethyl ether is added to precipitate the solid, which is then filtered and dried to obtain bis(4-tert-butylphenyl)iodotetrafluoroborate. S32. Bis(4-tert-butylphenyl)iodotetrafluoroborate, 1-4-thiaoxane, copper catalyst and dichloroethane are mixed and heated to carry out a substitution reaction. The molar ratio of bis(4-tert-butylphenyl)iodotetrafluoroborate, 1-4-thiaoxane and copper catalyst is 1:1.3-1.5:0.1. After the reaction is completed, the mixture is filtered under reduced pressure and washed with 1-2 wt% citric acid aqueous solution. After separation, the organic layer is washed and concentrated under reduced pressure. A mixed solution of ethyl acetate and methyl tert-ethyl ether is added, the mixture is slurried and dried to obtain 4-(4-tert-butylphenyl)-1,4-oxothiacyclohexane-4-tetrafluoroborate. S33. A mixture of 4-(4-tert-butylphenyl)-1,4-oxothiacyclohexane-4-tetrafluoroborate, sodium 1,1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate, alkali, water, and dichloromethane is carried out at room temperature for an exchange reaction. The resulting product is 4-(4-tert-butylphenyl)-1,4-oxothiacyclohexane-4-tetrafluoroborate, and the intermediate D1,1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate. The molar ratio of sodium ethane-1-sulfonate to alkali was 1:1.5 to 2.5:1. The organic phase was separated, washed, and concentrated under reduced pressure. 4-methyl-2-pentanone was added to precipitate a solid. Isopropyl ether was added, the mixture was stirred, filtered, and dried to obtain the intermediate product E4-[4-(1,1-dimethylethyl)phenyl)1,4-oxothiothiamonium salt and 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]5'-yl)2,2-difluoro-2-sulfoacetate. Preferably, the copper catalyst in steps S11, S23 and S32 includes any one of copper acetylacetonate, copper benzoate hydrate, and copper acetate; the substitution reaction temperature in steps S11, S23 and S32 is 100-110°C. Preferably, the alkali mentioned in steps S12 and S33 includes any one or more of triethylamine, sodium bicarbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium tert-butoxide, potassium tert-butoxide, potassium carbonate, sodium carbonate, cesium carbonate, ammonia, a methanol solution of ammonia, and ammonium bicarbonate. Preferably, the esterification ring-closing reaction in step S3 is carried out at a temperature of 100–110 °C for 5–7 h, and the intermediate product E4-[4-(1,1-dimethylethyl)phenyl)1,4-oxothiothiamonium salt, 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]5'-yl)2,2-difluoro-2-sulfoacetate, the raw material C2,2,3,3-tetrafluoro-1,4-butanediol, and sulfuric acid are in a molar ratio of 1:1.5–3:0.03–0.1. Preferably, the photo-induced acid-producing sulfonate is 4-[4-(1,1-dimethylethyl)phenyl]-1,4-oxothiothiamonium salt and 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]-5'-yl)2,2-difluoro-2-sulfonoacetate, with the following structure: Beneficial effects: This invention provides a process for synthesizing 4-[4-(1,1-dimethylethyl)phenyl]-1,4-oxothiothiamonium salt and 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]-5'-yl)2,2-difluoro-2-sulfoacetate salt. The process is stable and easy to operate, the preparation method is simple, and the product yield and purity are high. The current mainstream synthetic route involves bis(4-tert-butylphenyl)iodotrifluoromethanesulfonate and resin exchange. This route first involves ion exchange followed by substitution, and the resulting intermediate is then ketalized to obtain the target photoacid-producing agent. However, this route cannot control the metal ion content during synthesis, resulting in demanding purification methods and high resin usage. Furthermore, the esterification stage introduces other halogen anion impurities, significantly impacting product color and anion content, making process scale-up difficult. The synthetic route provided by this invention first involves substitution to form thiamethoxamate followed by ion exchange, and the resulting intermediate is then ketalized to obtain the target photoacid-producing agent. This optimizes the reaction conditions and process route, avoids the use of large amounts of resin, and effectively controls side reactions in the early stages of the process. This improves the purity, stability, and yield of the photoacid-producing agent, while reducing the metal and halogen content of this type of compound, meeting the demands of modern microelectronics manufacturing for high-performance photoacid-producing agents. Compared with the prior art, the present invention has the following advantages and positive effects: This invention provides a sulfonate-containing photoacid generator, which can be used as a key raw material for photoresists in the field of high-end liquid crystal and chip manufacturing. The product of this invention has low moisture and impurity content, low halogen and metal ion content, high product yield, and low manufacturing cost, enabling large-scale production and application. The overall process of this invention is simple to operate, convenient for post-processing, and environmentally friendly, which is conducive to achieving green production. Attached Figure Description Figure 1 The 1-H NMR spectrum of the final product of Example 2; Figure 2 The 1-F NMR spectrum of the final product of Example 2; Figure 3 The high-performance liquid chromatogram of the final product of Example 2; Figure 4 The 1-H NMR spectrum of the intermediate product of Example 10; Figure 5 The 1-H NMR spectrum of the final product of Example 10; Figure 6 The high-performance liquid chromatogram of the final product of Example 10; Figure 7 The 1-H NMR spectrum of the intermediate product in Example 11; Figure 8 The 1-F NMR spectrum of the intermediate product in Example 11; Figure 9 The 1-H NMR spectrum of the final product of Example 11; Figure 10The high-performance liquid chromatogram of the final product of Example 11; Figure 11 1-H NMR spectrum of the final product of Comparative Example 5; Figure 12 High performance liquid chromatogram of the final product of Comparative Example 5. Detailed Implementation To further understand the present invention, preferred embodiments of the present invention will be described below in conjunction with examples. Specific examples of preferred choices are as follows: Example 1: A method for preparing a sulfonate salt of photoacid-generating agent for photoresist includes the following steps: S1. Mix 50g of raw material A sodium difluorosulfate, 45.3g of raw material B 5-hydroxyadamantane-2-one and toluene, add 24.5g of sulfuric acid, heat to 130℃ and stir for 16h to carry out esterification reaction, filter and add 4-methyl-2-pentanone to the solid to make slurry, filter and dry the solid to obtain 55g of intermediate product D1,1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate sodium; S2. The intermediate product D1, 1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate sodium salt is exchanged with the starting material S: S11. Mix 54.7 g of bis(4-tert-butylphenyl)iodotrifluoromethanesulfonate, 42.9 g of 1-4thiaoxane, 26.1 g of copper acetylacetonate and dichloroethane, heat to 105 °C and stir for 16 h to carry out the substitution reaction. After the reaction is completed, filter under reduced pressure and wash with 1-2 wt% citric acid aqueous solution. After separation, wash the organic layer and concentrate under reduced pressure. Add a mixed solution of ethyl acetate and methyl tert-ethyl ether, slurry and dry to obtain 24.5 g of 4-(4-(tert-butyl)phenyl)-1,4-oxalate-4-ammonium salt of trifluoromethanesulfonate; S12. 55g of intermediate product D1,1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate sodium salt, 24.5g of trifluoromethanesulfonic acid 4-(4-(tert-butyl)phenyl)-1,4-oxalate-4-ammonium salt, and 6.1g of triethylamine were mixed with water and dichloromethane for an exchange reaction. The organic phase was separated, washed, and concentrated under reduced pressure. 4-methyl-2-pentanone was added to precipitate a solid. Isopropyl ether was added to slurry the solid, and the solid was filtered and dried to obtain 30.6g of intermediate product E4-[4-(1,1-dimethylethyl)phenyl)1,4-oxothiothiamonium salt and 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]5'-yl)2,2-difluoro-2-sulfoacetate salt; S3. 30.6 g of intermediate product E4-[4-(1,1-dimethylethyl)phenyl)1,4-oxothiothiamonium salt, 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]5'-yl)2,2-difluoro-2-sulfoacetate, 24.7 g of raw material C2,2,3,3-tetrafluoro-1,4-butanediol, 0.25 g of sulfuric acid and dichloroethane were mixed and heated to 110 °C for esterification and ring-closing reaction for 6 h. The organic phase was washed and concentrated under reduced pressure, dissolved in toluene until clear, and crystallized by adding tertiary methyl ether to obtain 28.1 g of photo-induced acid-producing sulfonate. The photo-induced acid-producing sulfonate is 4-[4-(1,1-dimethylethyl)phenyl]-1,4-oxothiothiamonium salt and 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]-5'-yl)2,2-difluoro-2-sulfonoacetate, with the following structure: Example 2: A method for preparing a sulfonate salt of photoacid-generating agent for photoresist includes the following steps: S1. Mix 50g of raw material A sodium difluorosulfate, 41.5g of raw material B 5-hydroxyadamantane-2-one and toluene, add 24.5g of sulfuric acid, heat to 130℃ and stir for 16h to carry out esterification reaction, filter and add 4-methyl-2-pentanone to the solid to make slurry, filter and dry the solid to obtain 56g of intermediate product D1,1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate sodium; S2. The intermediate product D1, 1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate sodium salt is exchanged with the starting material S: S11. Mix 55.7 g of bis(4-tert-butylphenyl)iodotrifluoromethanesulfonate, 43.7 g of 1-4thiaoxane, 26.6 g of copper acetylacetonate and dichloroethane, heat to 105 °C and stir for 16 h to carry out the substitution reaction. After the reaction is completed, filter under reduced pressure and wash with 1-2 wt% citric acid aqueous solution. After separation, wash the organic layer and concentrate under reduced pressure. Add a mixed solution of ethyl acetate and methyl tert-ethyl ether, slurry and dry to obtain 24.9 g of 4-(4-(tert-butyl)phenyl)-1,4-oxalate-4-ammonium salt of trifluoromethanesulfonate; S12. 56g of intermediate product D1,1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate sodium salt, 24.9g of trifluoromethanesulfonic acid 4-(4-(tert-butyl)phenyl)-1,4-oxalate-4-ammonium salt, and 6.2g of triethylamine were mixed with water and dichloromethane for an exchange reaction. The organic phase was separated, washed, and concentrated under reduced pressure. 4-methyl-2-pentanone was added to precipitate a solid. Isopropyl ether was added to slurry the solid, and the solid was filtered and dried to obtain 31.1g of intermediate product E4-[4-(1,1-dimethylethyl)phenyl)1,4-oxothiothiaonium salt and 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]5'-yl)2,2-difluoro-2-sulfoacetate salt; S3. 31.1 g of intermediate product E4-[4-(1,1-dimethylethyl)phenyl)1,4-oxothiothiamonium salt, 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]5'-yl)2,2-difluoro-2-sulfoacetate, 25.1 g of raw material C2,2,3,3-tetrafluoro-1,4-butanediol, 0.25 g of sulfuric acid and dichloroethane were mixed and heated to 110 °C for esterification and ring-closing reaction for 6 h. The organic phase was washed and concentrated under reduced pressure, dissolved in toluene until clear, and crystallized by adding tertiary methyl ether to obtain 28.6 g of photo-induced acid-producing sulfonate. The photo-induced acid-producing sulfonate is 4-[4-(1,1-dimethylethyl)phenyl]-1,4-oxothiothiamonium salt and 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]-5'-yl)2,2-difluoro-2-sulfonoacetate, with the following structure: Example 3: A method for preparing a sulfonate salt of photoacid-generating agent for photoresist includes the following steps: S1. Mix 50g of raw material A (sodium difluorosulfate), 37.7g of raw material B (5-hydroxyadamantane-2-one), and toluene, add 24.5g of sulfuric acid, heat to 130℃ and stir for 16h to carry out esterification reaction. After filtration, add 4-methyl-2-pentanone to the solid and slurry. Filter and dry the solid to obtain 54.2g of intermediate product D1,1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate. S2. The intermediate product D1, 1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate sodium salt is exchanged with the starting material S: S11. Mix 53.9 g of bis(4-tert-butylphenyl)iodotrifluoromethanesulfonate, 42.3 g of 1-4thiaoxane, 25.8 g of copper acetylacetonate and dichloroethane, heat to 105 °C and stir for 16 h to carry out the substitution reaction. After the reaction is completed, filter under reduced pressure and wash with 1-2 wt% citric acid aqueous solution. After separation, wash the organic layer and concentrate under reduced pressure. Add a mixed solution of ethyl acetate and methyl tert-ethyl ether, slurry and dry to obtain 24.1 g of 4-(4-(tert-butyl)phenyl)-1,4-oxalate-4-ammonium salt of trifluoromethanesulfonate; S12. 54.2 g of intermediate product D1,1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate sodium, 24.1 g of trifluoromethanesulfonic acid 4-(4-(tert-butyl)phenyl)-1,4-oxalate-4-ammonium salt, and 6.0 g of triethylamine were mixed with water and dichloromethane for an exchange reaction. The organic phase was separated, washed, and concentrated under reduced pressure. 4-methyl-2-pentanone was added to precipitate a solid. Isopropyl ether was added, the mixture was stirred, filtered, and dried to obtain 30.1 g of intermediate product E4-[4-(1,1-dimethylethyl)phenyl)1,4-oxothiothiaonium salt and 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]5'-yl)2,2-difluoro-2-sulfoacetate salt; S3. 30.1 g of intermediate product E4-[4-(1,1-dimethylethyl)phenyl)1,4-oxothiothiamonium salt, 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]5'-yl)2,2-difluoro-2-sulfoacetate, 24.3 g of raw material C2,2,3,3-tetrafluoro-1,4-butanediol, 0.25 g of sulfuric acid and dichloroethane were mixed and heated to 110 °C for esterification and ring-closing reaction for 6 h. The organic phase was washed and concentrated under reduced pressure, dissolved in toluene until clear, and crystallized by adding tertiary methyl ether to obtain 27.7 g of photo-induced acid-producing sulfonate. The photo-induced acid-producing sulfonate is 4-[4-(1,1-dimethylethyl)phenyl]-1,4-oxothiothiamonium salt and 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]-5'-yl)2,2-difluoro-2-sulfonoacetate, with the following structure: Example 4: A method for preparing a sulfonate salt of photoacid-generating agent for photoresist includes the following steps: S1. Mix 50g of raw material A sodium difluorosulfate, 41.5g of raw material B 5-hydroxyadamantane-2-one and toluene, add 24.5g of sulfuric acid, heat to 120℃ and stir for 16h to carry out esterification reaction. After filtration, add 4-methyl-2-pentanone to the solid and slurry. Filter and dry the solid to obtain 55.7g of intermediate product D1,1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate sodium; S2. The intermediate product D1, 1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate sodium salt is exchanged with the starting material S: S11. Mix 55.4 g of bis(4-tert-butylphenyl)iodotrifluoromethanesulfonate, 43.5 g of 1-4thiaoxane, 26.5 g of copper acetylacetonate and dichloroethane, heat to 105 °C and stir for 16 h to carry out the substitution reaction. After the reaction is completed, filter under reduced pressure and wash with 1-2 wt% citric acid aqueous solution. After separation, wash the organic layer and concentrate under reduced pressure. Add a mixed solution of ethyl acetate and methyl tert-ethyl ether, slurry and dry to obtain 24.8 g of 4-(4-(tert-butyl)phenyl)-1,4-oxalate-4-ammonium salt of trifluoromethanesulfonate; S12. 55.7 g of intermediate product D1,1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate sodium salt, 24.8 g of trifluoromethanesulfonic acid 4-(4-(tert-butyl)phenyl)-1,4-oxalate-4-ammonium salt, and 6.2 g of triethylamine were mixed with water and dichloromethane for an exchange reaction. The organic phase was separated, washed, and concentrated under reduced pressure. 4-methyl-2-pentanone was added to precipitate a solid. Isopropyl ether was added to slurry the solid, and the solid was filtered and dried to obtain 30.9 g of intermediate product E4-[4-(1,1-dimethylethyl)phenyl)1,4-oxothiothiamonium salt and 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]5'-yl)2,2-difluoro-2-sulfoacetate salt; S3. 30.9 g of intermediate product E4-[4-(1,1-dimethylethyl)phenyl)1,4-oxothiothiamonium salt, 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]5'-yl)2,2-difluoro-2-sulfoacetate, 25.0 g of raw material C2,2,3,3-tetrafluoro-1,4-butanediol, 0.25 g of sulfuric acid and dichloroethane were mixed and heated to 110 °C for esterification and ring-closing reaction for 6 h. The organic phase was washed and concentrated under reduced pressure, dissolved in toluene until clear, and crystallized by adding tertiary methyl ether to obtain 28.5 g of photo-induced acid-producing sulfonate. The photo-induced acid-producing sulfonate is 4-[4-(1,1-dimethylethyl)phenyl]-1,4-oxothiothiamonium salt and 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]-5'-yl)2,2-difluoro-2-sulfonoacetate, with the following structure: Example 5: A method for preparing a sulfonate salt of photoacid-generating agent for photoresist includes the following steps: S1. Mix 50g of raw material A sodium difluorosulfate, 41.5g of raw material B 5-hydroxyadamantane-2-one and toluene, add 24.5g of sulfuric acid, heat to 110℃ and stir for 16h to carry out esterification reaction, filter and add 4-methyl-2-pentanone to the solid to make slurry, filter and dry the solid to obtain 54.1g of intermediate product D1,1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate sodium; S2. The intermediate product D1, 1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate sodium salt is exchanged with the starting material S: S11. Mix 53.8 g of bis(4-tert-butylphenyl)iodine trifluoromethanesulfonate, 42.2 g of 1-4thiaoxane, 25.7 g of copper acetylacetonate and dichloroethane, heat to 105 °C and stir for 16 h to carry out the substitution reaction. After the reaction is completed, filter under reduced pressure and wash with 1-2 wt% citric acid aqueous solution. After separation, wash the organic layer and concentrate under reduced pressure. Add a mixed solution of ethyl acetate and methyl tert-ethyl ether, slurry and dry to obtain 24.1 g of 4-(4-(tert-butyl)phenyl)-1,4-oxalate-4-ammonium salt of trifluoromethanesulfonate; S12. 54.1 g of intermediate product D1,1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate sodium salt, 24.1 g of trifluoromethanesulfonic acid 4-(4-(tert-butyl)phenyl)-1,4-oxalate-4-ammonium salt, and 6.0 g of triethylamine were mixed with water and dichloromethane for an exchange reaction. The organic phase was separated, washed, and concentrated under reduced pressure. 4-methyl-2-pentanone was added to precipitate a solid. Isopropyl ether was added to slurry the solid, and the solid was filtered and dried to obtain 30.1 g of intermediate product E4-[4-(1,1-dimethylethyl)phenyl)1,4-oxothiothiaonium salt and 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]5'-yl)2,2-difluoro-2-sulfoacetate salt; S3. 30.1 g of intermediate product E4-[4-(1,1-dimethylethyl)phenyl)1,4-oxothiothiamonium salt, 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]5'-yl)2,2-difluoro-2-sulfoacetate, 24.2 g of raw material C2,2,3,3-tetrafluoro-1,4-butanediol, 0.24 g of sulfuric acid and dichloroethane were mixed and heated to 110 °C for esterification and ring-closing reaction for 6 h. The organic phase was washed and concentrated under reduced pressure, dissolved in toluene until clear, and crystallized by adding tertiary methyl ether to obtain 27.6 g of photo-induced acid-producing sulfonate. The photo-induced acid-producing sulfonate is 4-[4-(1,1-dimethylethyl)phenyl]-1,4-oxothiothiamonium salt and 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]-5'-yl)2,2-difluoro-2-sulfonoacetate, with the following structure: Example 6: A method for preparing a sulfonate salt of photoacid-generating agent for photoresist includes the following steps: S1. Mix 50g of raw material A sodium difluorosulfate, 41.5g of raw material B 5-hydroxyadamantane-2-one and toluene, add 24.5g of sulfuric acid, heat to 130℃ and stir for 16h to carry out esterification reaction, filter and add 4-methyl-2-pentanone to the solid to make slurry, filter and dry the solid to obtain 56g of intermediate product D1,1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate sodium; S2. The intermediate product D1, 1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate sodium salt is exchanged with the starting material S: S11. Mix 55.7 g of bis(4-tert-butylphenyl)iodotrifluoromethanesulfonate, 43.7 g of 1-4thiaoxane, 26.6 g of copper acetylacetonate and dichloroethane, heat to 105 °C and stir for 16 h to carry out the substitution reaction. After the reaction is completed, filter under reduced pressure and wash with 1-2 wt% citric acid aqueous solution. After separation, wash the organic layer and concentrate under reduced pressure. Add a mixed solution of ethyl acetate and methyl tert-ethyl ether, slurry and dry to obtain 24.9 g of 4-(4-(tert-butyl)phenyl)-1,4-oxalate-4-ammonium salt of trifluoromethanesulfonate; S12. 56g of intermediate product D1,1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate sodium salt, 24.9g of trifluoromethanesulfonic acid 4-(4-(tert-butyl)phenyl)-1,4-oxalate-4-ammonium salt, and 6.2g of triethylamine were mixed with water and dichloromethane for an exchange reaction. The organic phase was separated, washed, and concentrated under reduced pressure. 4-methyl-2-pentanone was added to precipitate a solid. Isopropyl ether was added to slurry the solid, and the solid was filtered and dried to obtain 31.1g of intermediate product E4-[4-(1,1-dimethylethyl)phenyl)1,4-oxothiothiaonium salt and 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]5'-yl)2,2-difluoro-2-sulfoacetate salt; S3. 31.1 g of intermediate product E4-[4-(1,1-dimethylethyl)phenyl)1,4-oxothiothiamonium salt, 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]5'-yl)2,2-difluoro-2-sulfoacetate, 18.2 g of raw material C2,2,3,3-tetrafluoro-1,4-butanediol, 0.25 g of sulfuric acid and dichloroethane were mixed and heated to 110 °C for esterification and ring-closing reaction for 6 h. The organic phase was washed and concentrated under reduced pressure, dissolved in toluene until clear, and crystallized by adding tertiary methyl ether to obtain 28.1 g of photo-induced acid-producing sulfonate. The photo-induced acid-producing sulfonate is 4-[4-(1,1-dimethylethyl)phenyl]-1,4-oxothiothiamonium salt and 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]-5'-yl)2,2-difluoro-2-sulfonoacetate, with the following structure: Example 7: A method for preparing a sulfonate salt of photoacid-generating agent for photoresist includes the following steps: S1. Mix 50g of raw material A sodium difluorosulfate, 41.5g of raw material B 5-hydroxyadamantane-2-one and toluene, add 24.5g of sulfuric acid, heat to 130℃ and stir for 16h to carry out esterification reaction, filter and add 4-methyl-2-pentanone to the solid to make slurry, filter and dry the solid to obtain 56g of intermediate product D1,1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate sodium; S2. The intermediate product D1, 1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate sodium salt is exchanged with the starting material S: S11. Mix 55.7 g of bis(4-tert-butylphenyl)iodotrifluoromethanesulfonate, 43.7 g of 1-4thiaoxane, 26.6 g of copper acetylacetonate and dichloroethane, heat to 105 °C and stir for 16 h to carry out the substitution reaction. After the reaction is completed, filter under reduced pressure and wash with 1-2 wt% citric acid aqueous solution. After separation, wash the organic layer and concentrate under reduced pressure. Add a mixed solution of ethyl acetate and methyl tert-ethyl ether, slurry and dry to obtain 24.9 g of 4-(4-(tert-butyl)phenyl)-1,4-oxalate-4-ammonium salt of trifluoromethanesulfonate; S12. 56g of intermediate product D1,1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate sodium salt, 24.9g of trifluoromethanesulfonic acid 4-(4-(tert-butyl)phenyl)-1,4-oxalate-4-ammonium salt, and 6.2g of triethylamine were mixed with water and dichloromethane for an exchange reaction. The organic phase was separated, washed, and concentrated under reduced pressure. 4-methyl-2-pentanone was added to precipitate a solid. Isopropyl ether was added to slurry the solid, and the solid was filtered and dried to obtain 31.1g of intermediate product E4-[4-(1,1-dimethylethyl)phenyl)1,4-oxothiothiaonium salt and 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]5'-yl)2,2-difluoro-2-sulfoacetate salt; S3. 31.1 g of intermediate product E4-[4-(1,1-dimethylethyl)phenyl)1,4-oxothiothiamonium salt, 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]5'-yl)2,2-difluoro-2-sulfoacetate, 23.4 g of raw material C2,2,3,3-tetrafluoro-1,4-butanediol, 0.25 g of sulfuric acid and dichloroethane were mixed and heated to 110 °C for esterification and ring-closing reaction for 6 h. The organic phase was washed and concentrated under reduced pressure, dissolved in toluene until clear, and crystallized by adding tertiary methyl ether to obtain 27.7 g of photo-induced acid-producing sulfonate. The photo-induced acid-producing sulfonate is 4-[4-(1,1-dimethylethyl)phenyl]-1,4-oxothiothiamonium salt and 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]-5'-yl)2,2-difluoro-2-sulfonoacetate, with the following structure: Example 8: A method for preparing a sulfonate salt of photoacid-generating agent for photoresist includes the following steps: S1. Mix 50g of raw material A sodium difluorosulfate, 41.5g of raw material B 5-hydroxyadamantane-2-one and toluene, add 24.5g of sulfuric acid, heat to 130℃ and stir for 16h to carry out esterification reaction, filter and add 4-methyl-2-pentanone to the solid to make slurry, filter and dry the solid to obtain 56g of intermediate product D1,1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate sodium; S2. The intermediate product D1, 1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate sodium salt is exchanged with the starting material S: S11. Mix 55.7 g of bis(4-tert-butylphenyl)iodotrifluoromethanesulfonate, 43.7 g of 1-4thiaoxane, 26.6 g of copper acetylacetonate and dichloroethane, heat to 105 °C and stir for 16 h to carry out the substitution reaction. After the reaction is completed, filter under reduced pressure and wash with 1-2 wt% citric acid aqueous solution. After separation, wash the organic layer and concentrate under reduced pressure. Add a mixed solution of ethyl acetate and methyl tert-ethyl ether, slurry and dry to obtain 24.9 g of 4-(4-(tert-butyl)phenyl)-1,4-oxalate-4-ammonium salt of trifluoromethanesulfonate; S12. 56g of intermediate product D1,1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate sodium salt, 24.9g of trifluoromethanesulfonic acid 4-(4-(tert-butyl)phenyl)-1,4-oxalate-4-ammonium salt, and 6.2g of triethylamine were mixed with water and dichloromethane for an exchange reaction. The organic phase was separated, washed, and concentrated under reduced pressure. 4-methyl-2-pentanone was added to precipitate a solid. Isopropyl ether was added to slurry the solid, and the solid was filtered and dried to obtain 31.1g of intermediate product E4-[4-(1,1-dimethylethyl)phenyl)1,4-oxothiothiaonium salt and 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]5'-yl)2,2-difluoro-2-sulfoacetate salt; S3. 31.1 g of intermediate product E4-[4-(1,1-dimethylethyl)phenyl)1,4-oxothiothiamonium salt, 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]5'-yl)2,2-difluoro-2-sulfoacetate, 25.1 g of raw material C2,2,3,3-tetrafluoro-1,4-butanediol, 0.25 g of sulfuric acid and dichloroethane were mixed and heated to 105 °C for esterification and ring-closing reaction for 6 h. The organic phase was washed and concentrated under reduced pressure, dissolved in toluene until clear, and crystallized by adding tertiary methyl ether to obtain 28.3 g of photo-induced acid-producing sulfonate. The photo-induced acid-producing sulfonate is 4-[4-(1,1-dimethylethyl)phenyl]-1,4-oxothiothiamonium salt and 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]-5'-yl)2,2-difluoro-2-sulfonoacetate, with the following structure: Example 9: A method for preparing a sulfonate salt of photoacid-generating agent for photoresist includes the following steps: S1. Mix 50g of raw material A sodium difluorosulfate, 41.5g of raw material B 5-hydroxyadamantane-2-one and toluene, add 24.5g of sulfuric acid, heat to 130℃ and stir for 16h to carry out esterification reaction, filter and add 4-methyl-2-pentanone to the solid to make slurry, filter and dry the solid to obtain 56g of intermediate product D1,1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate sodium; S2. The intermediate product D1, 1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate sodium salt is exchanged with the starting material S: S11. Mix 55.7 g of bis(4-tert-butylphenyl)iodotrifluoromethanesulfonate, 43.7 g of 1-4thiaoxane, 26.6 g of copper acetylacetonate and dichloroethane, heat to 105 °C and stir for 16 h to carry out the substitution reaction. After the reaction is completed, filter under reduced pressure and wash with 1-2 wt% citric acid aqueous solution. After separation, wash the organic layer and concentrate under reduced pressure. Add a mixed solution of ethyl acetate and methyl tert-ethyl ether, slurry and dry to obtain 24.9 g of 4-(4-(tert-butyl)phenyl)-1,4-oxalate-4-ammonium salt of trifluoromethanesulfonate; S12. 56g of intermediate product D1,1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate sodium salt, 24.9g of trifluoromethanesulfonic acid 4-(4-(tert-butyl)phenyl)-1,4-oxalate-4-ammonium salt, and 6.2g of triethylamine were mixed with water and dichloromethane for an exchange reaction. The organic phase was separated, washed, and concentrated under reduced pressure. 4-methyl-2-pentanone was added to precipitate a solid. Isopropyl ether was added to slurry the solid, and the solid was filtered and dried to obtain 31.1g of intermediate product E4-[4-(1,1-dimethylethyl)phenyl)1,4-oxothiothiaonium salt and 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]5'-yl)2,2-difluoro-2-sulfoacetate salt; S3. 31.1 g of intermediate product E4-[4-(1,1-dimethylethyl)phenyl)1,4-oxothiothiamonium salt, 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]5'-yl)2,2-difluoro-2-sulfoacetate, 25.1 g of raw material C2,2,3,3-tetrafluoro-1,4-butanediol, 0.25 g of sulfuric acid and dichloroethane were mixed and heated to 100 °C for esterification and ring-closing reaction for 6 h. The organic phase was washed and concentrated under reduced pressure, dissolved in toluene until clear, and crystallized by adding tertiary methyl ether to obtain 27.6 g of photo-induced acid-producing sulfonate. The photo-induced acid-producing sulfonate is 4-[4-(1,1-dimethylethyl)phenyl]-1,4-oxothiothiamonium salt and 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]-5'-yl)2,2-difluoro-2-sulfonoacetate, with the following structure: Example 10: A method for preparing a sulfonate salt of photoacid-generating agent for photoresist includes the following steps: S1. Mix 49.6g of raw material A sodium difluorosulfate, 41.2g of raw material B 5-hydroxyadamantane-2-one and toluene, add 24.3g of sulfuric acid, heat to 130℃ and stir for 16h to carry out esterification reaction, filter and add 4-methyl-2-pentanone to the solid to make slurry, filter and dry the solid to obtain 55.6g of intermediate product D1,1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate sodium; S2. The intermediate product D1, 1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate sodium salt is exchanged with the starting material S: S21. 54.4 g of bis(4-tert-butylphenyl)iodide trifluoromethanesulfonate and 435 g of resin were stirred and filtered in methanol solvent. Then, 108.8 g of resin was added, stirred, and filtered again to obtain a methanol solution of bis(4-tert-butylphenyl)iodide hydroxide. S22. 55.6 g of the intermediate product D1,1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate was added to the methanol solvent containing bis(4-tert-butylphenyl)iodide trifluoromethanesulfonate. In a methanol solution of bis(4-tert-butylphenyl)iodide hydroxide, the mixture was stirred at room temperature and filtered. After washing with methanol, the solution was concentrated, dissolved in dichloromethane until clear, and washed. The organic phase was concentrated under reduced pressure, and 4-methyl-2-pentanone was added until a solid precipitated. Isopropyl ether was added, the mixture was stirred, filtered, and dried to obtain 43.5 g of bis(4-tert-butylphenyl)iodide 1,1-difluoro-2-oxo-2-((1s,3R,5S,7s)-4-oxoadamantane-1-yl)oxoethane-1-sulfonate. S23. Mix 43.5 g of bis(4-tert-butylphenyl)iodide 1,1-difluoro-2-oxo-2-((1s,3R,5S,7s)-4-oxoadamantane-1-yl)oxoethane-1-sulfonate, 8.9 g of 1,4-thiaoxane, and 1.6 g of copper acetylacetonate with dichloroethane, heat to 110 °C and stir for 16 h to carry out the substitution reaction, filter and wash with 1-2 wt% citric acid aqueous solution. The filtrate was washed with the organic phase, separated, concentrated under reduced pressure, and 4-methyl-2-pentanone was added until solid precipitate. Isopropyl ether was added, the mixture was stirred, filtered, and dried to obtain 20g of intermediate product E4-[4-(1,1-dimethylethyl)phenyl)1,4-oxothiothiatonium salt and 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]5'-yl)2,2-difluoro-2-sulfoacetate salt; S3. 20g of intermediate product E4-[4-(1,1-dimethylethyl)phenyl)1,4-oxothiothiamonium salt, 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]5'-yl)2,2-difluoro-2-sulfoacetate, 16.2g of raw material C2,2,3,3-tetrafluoro-1,4-butanediol, 1.54g of sulfuric acid and dichloroethane were mixed and heated to 110℃ for esterification and ring-closing reaction for 6h. The organic phase was washed and concentrated under reduced pressure, dissolved in toluene until clear, and crystallized by adding tertiary methyl ether to obtain 17.8g of photo-induced acid-producing sulfonate. The photo-induced acid-producing sulfonate is 4-[4-(1,1-dimethylethyl)phenyl]-1,4-oxothiothiamonium salt and 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]-5'-yl)2,2-difluoro-2-sulfonoacetate, with the following structure: Example 11: A method for preparing a sulfonate salt of photoacid-generating agent for photoresist includes the following steps: S1. Mix 39.3g of raw material A sodium difluorosulfate, 32.6g of raw material B 5-hydroxyadamantane-2-one and toluene, add 19.2g of sulfuric acid, heat to 130℃ and stir for 16h to carry out esterification reaction, filter and add 4-methyl-2-pentanone to the solid to make slurry, filter and dry the solid to obtain 44.6g of intermediate product D1,1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate sodium; S2. The intermediate product D1, 1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate sodium salt is exchanged with the starting material S: S31. 300.8g of triphenylsulfonium chloride and 1910g of resin were stirred in methanol until the reaction was complete. 85.3g of sodium borate was added and stirred. The mixture was then filtered, concentrated under reduced pressure, dissolved in ethyl acetate, and precipitated as a solid by adding methyl tert-butyl ether. The solid was filtered and dried to obtain 42.1g of bis(4-tert-butylphenyl)iodotetrafluoroborate. S32. 42.1 g of bis(4-tert-butylphenyl)iodotetrafluoroborate, 24.1 g of 1-4thiaoxane, 0.67 g of copper acetylacetonate and dichloroethane were mixed and heated to 105 °C and stirred for 16 h to carry out a substitution reaction. After the reaction was completed, the mixture was filtered under reduced pressure and washed with 1-2 wt% citric acid aqueous solution. After separation, the organic layer was washed and concentrated under reduced pressure. A mixed solution of ethyl acetate and methyl tert-ethyl ether was added, the mixture was stirred and dried to obtain 16 g of 4-(4-tert-butylphenyl)-1,4-oxothiacyclohexane-4-tetrafluoroborate. S33. 16g of 4-(4-tert-butylphenyl)-1,4-oxothiacyclohexane-4-tetrafluoroborate, 44g of intermediate product D1,1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate, and 4g of triethylamine were mixed with water and dichloromethane and subjected to an exchange reaction. The organic phase was separated, washed, and concentrated under reduced pressure. 4-methyl-2-pentanone was added to precipitate a solid. Isopropyl ether was added to slurry the solid and filtered and dried to obtain 20g of intermediate product E4-[4-(1,1-dimethylethyl)phenyl)1,4-oxothiacyclohexane salt and 1-(5,5,6,6-tetrafluorospiro[1,3-dioxacyclohexane-2,2'-adamantane]5'-yl)2,2-difluoro-2-sulfoacetate salt; S3. 20g of intermediate product E4-[4-(1,1-dimethylethyl)phenyl)1,4-oxothiothiamonium salt, 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]5'-yl)2,2-difluoro-2-sulfoacetate, 16.2g of raw material C2,2,3,3-tetrafluoro-1,4-butanediol, 1.54g of sulfuric acid and dichloroethane were mixed and heated to 110℃ for esterification and ring-closing reaction for 6h. The organic phase was washed and concentrated under reduced pressure, dissolved in toluene until clear, and crystallized by adding tertiary methyl ether to obtain 18.6g of photo-induced acid-producing sulfonate. The photo-induced acid-producing sulfonate is 4-[4-(1,1-dimethylethyl)phenyl]-1,4-oxothiothiamonium salt and 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]-5'-yl)2,2-difluoro-2-sulfonoacetate, with the following structure: To further illustrate the technical effects of the present invention, a comparative example is also provided, as follows: Comparative Example 1: A method for preparing a sulfonate salt of photoacid-generating agent for photoresist includes the following steps: S1. Mix 50g of raw material A sodium difluorosulfate, 56.6g of raw material B 5-hydroxyadamantane-2-one and toluene, add 24.5g of sulfuric acid, heat to 130℃ and stir for 16h to carry out esterification reaction, filter and add 4-methyl-2-pentanone to the solid to make slurry, filter and dry the solid to obtain 55g of intermediate product D1,1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate sodium; S2. The intermediate product D1, 1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate sodium salt is exchanged with the starting material S: S11. Mix 54.7 g of bis(4-tert-butylphenyl)iodotrifluoromethanesulfonate, 42.9 g of 1-4thiaoxane, 26.1 g of copper acetylacetonate and dichloroethane, heat to 105 °C and stir for 16 h to carry out the substitution reaction. After the reaction is completed, filter under reduced pressure and wash with 1-2 wt% citric acid aqueous solution. After separation, wash the organic layer and concentrate under reduced pressure. Add a mixed solution of ethyl acetate and methyl tert-ethyl ether, slurry and dry to obtain 24.5 g of 4-(4-(tert-butyl)phenyl)-1,4-oxalate-4-ammonium salt of trifluoromethanesulfonate; S12. 55g of intermediate product D1,1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate sodium salt, 24.5g of trifluoromethanesulfonic acid 4-(4-(tert-butyl)phenyl)-1,4-oxalate-4-ammonium salt, and 6.1g of triethylamine were mixed with water and dichloromethane for an exchange reaction. The organic phase was separated, washed, and concentrated under reduced pressure. 4-methyl-2-pentanone was added to precipitate a solid. Isopropyl ether was added to slurry the solid, and the solid was filtered and dried to obtain 30.6g of intermediate product E4-[4-(1,1-dimethylethyl)phenyl)1,4-oxothiothiamonium salt and 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]5'-yl)2,2-difluoro-2-sulfoacetate salt; S3. 30.6 g of intermediate product E4-[4-(1,1-dimethylethyl)phenyl)1,4-oxothiothiamonium salt, 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]5'-yl)2,2-difluoro-2-sulfoacetate, 24.7 g of raw material C2,2,3,3-tetrafluoro-1,4-butanediol, 0.25 g of sulfuric acid and dichloroethane were mixed and heated to 110 °C for esterification and ring-closing reaction for 6 h. The organic phase was washed and concentrated under reduced pressure, dissolved in toluene until clear, and crystallized by adding tertiary methyl ether to obtain 28.1 g of photo-induced acid-producing sulfonate. The photo-induced acid-producing sulfonate is 4-[4-(1,1-dimethylethyl)phenyl]-1,4-oxothiothiamonium salt and 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]-5'-yl)2,2-difluoro-2-sulfonoacetate, with the following structure: Comparative Example 2: A method for preparing a sulfonate salt of photoacid-generating agent for photoresist includes the following steps: S1. Mix 50g of raw material A sodium difluorosulfate, 41.5g of raw material B 5-hydroxyadamantane-2-one and toluene, add 24.5g of sulfuric acid, heat to 90℃ and stir for 16h to carry out esterification reaction, filter and add 4-methyl-2-pentanone to the solid to make slurry, filter and dry the solid to obtain 38g of intermediate product D1,1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate sodium; S2. The intermediate product D1, 1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate sodium salt is exchanged with the starting material S: S11. Mix 37.8 g of bis(4-tert-butylphenyl)iodotrifluoromethanesulfonate, 29.6 g of 1-4thiaoxane, 18.0 g of copper acetylacetonate and dichloroethane, heat to 105 °C and stir for 16 h to carry out the substitution reaction. After the reaction is completed, filter under reduced pressure and wash with 1-2 wt% citric acid aqueous solution. After separation, wash the organic layer and concentrate under reduced pressure. Add a mixed solution of ethyl acetate and methyl tert-ethyl ether, slurry and dry to obtain 16.9 g of 4-(4-(tert-butyl)phenyl)-1,4-oxalate-4-ammonium salt of trifluoromethanesulfonate; S12. 38g of intermediate product D1,1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate sodium salt, 16.9g of trifluoromethanesulfonic acid 4-(4-(tert-butyl)phenyl)-1,4-oxalate-4-ammonium salt, and 4.2g of triethylamine were mixed with water and dichloromethane for an exchange reaction. The organic phase was separated, washed, and concentrated under reduced pressure. 4-methyl-2-pentanone was added to precipitate a solid. Isopropyl ether was added to slurry the solid, and the solid was filtered and dried to obtain 21.1g of intermediate product E4-[4-(1,1-dimethylethyl)phenyl)1,4-oxothiothiaonium salt and 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]5'-yl)2,2-difluoro-2-sulfoacetate salt; S3. 21.1 g of intermediate product E4-[4-(1,1-dimethylethyl)phenyl)1,4-oxothiothiamonium salt, 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]5'-yl)2,2-difluoro-2-sulfoacetate, 17.0 g of raw material C2,2,3,3-tetrafluoro-1,4-butanediol, 0.17 g of sulfuric acid and dichloroethane were mixed and heated to 110 °C for esterification and ring-closing reaction for 6 h. The organic phase was washed and concentrated under reduced pressure, dissolved in toluene until clear, and crystallized by adding tertiary methyl ether to obtain 19.4 g of photo-induced acid-producing sulfonate. The photo-induced acid-producing sulfonate is 4-[4-(1,1-dimethylethyl)phenyl]-1,4-oxothiothiamonium salt and 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]-5'-yl)2,2-difluoro-2-sulfonoacetate, with the following structure: Comparative Example 3: A method for preparing a sulfonate salt of photoacid-generating agent for photoresist includes the following steps: S1. Mix 50g of raw material A sodium difluorosulfate, 41.5g of raw material B 5-hydroxyadamantane-2-one and toluene, add 24.5g of sulfuric acid, heat to 130℃ and stir for 16h to carry out esterification reaction, filter and add 4-methyl-2-pentanone to the solid to make slurry, filter and dry the solid to obtain 56g of intermediate product D1,1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate sodium; S2. The intermediate product D1, 1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate sodium salt is exchanged with the starting material S: S11. Mix 55.7 g of bis(4-tert-butylphenyl)iodotrifluoromethanesulfonate, 43.7 g of 1-4thiaoxane, 26.6 g of copper acetylacetonate and dichloroethane, heat to 105 °C and stir for 16 h to carry out the substitution reaction. After the reaction is completed, filter under reduced pressure and wash with 1-2 wt% citric acid aqueous solution. After separation, wash the organic layer and concentrate under reduced pressure. Add a mixed solution of ethyl acetate and methyl tert-ethyl ether, slurry and dry to obtain 24.9 g of 4-(4-(tert-butyl)phenyl)-1,4-oxalate-4-ammonium salt of trifluoromethanesulfonate; S12. 56g of intermediate product D1,1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate sodium salt, 24.9g of trifluoromethanesulfonic acid 4-(4-(tert-butyl)phenyl)-1,4-oxalate-4-ammonium salt, and 6.2g of triethylamine were mixed with water and dichloromethane for an exchange reaction. The organic phase was separated, washed, and concentrated under reduced pressure. 4-methyl-2-pentanone was added to precipitate a solid. Isopropyl ether was added to slurry the solid, and the solid was filtered and dried to obtain 31.1g of intermediate product E4-[4-(1,1-dimethylethyl)phenyl)1,4-oxothiothiaonium salt and 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]5'-yl)2,2-difluoro-2-sulfoacetate salt; S3. 31.1 g of intermediate product E4-[4-(1,1-dimethylethyl)phenyl)1,4-oxothiothiamonium salt, 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]5'-yl)2,2-difluoro-2-sulfoacetate, 8.96 g of raw material C2,2,3,3-tetrafluoro-1,4-butanediol, 0.25 g of sulfuric acid and dichloroethane were mixed and heated to 110 °C for esterification and ring-closing reaction for 6 h. The organic phase was washed and concentrated under reduced pressure, dissolved in toluene until clear, and crystallized by adding tertiary methyl ether to obtain 10.0 g of photo-induced acid-producing sulfonate. The photo-induced acid-producing sulfonate is 4-[4-(1,1-dimethylethyl)phenyl]-1,4-oxothiothiamonium salt and 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]-5'-yl)2,2-difluoro-2-sulfonoacetate, with the following structure: Comparative Example 4: A method for preparing a sulfonate salt of photoacid-generating agent for photoresist includes the following steps: S1. Mix 50g of raw material A sodium difluorosulfate, 41.5g of raw material B 5-hydroxyadamantane-2-one and toluene, add 24.5g of sulfuric acid, heat to 130℃ and stir for 16h to carry out esterification reaction, filter and add 4-methyl-2-pentanone to the solid to make slurry, filter and dry the solid to obtain 56g of intermediate product D1,1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate sodium; S2. The intermediate product D1, 1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate sodium salt is exchanged with the starting material S: S11. Mix 55.7 g of bis(4-tert-butylphenyl)iodotrifluoromethanesulfonate, 43.7 g of 1-4thiaoxane, 26.6 g of copper acetylacetonate and dichloroethane, heat to 105 °C and stir for 16 h to carry out the substitution reaction. After the reaction is completed, filter under reduced pressure and wash with 1-2 wt% citric acid aqueous solution. After separation, wash the organic layer and concentrate under reduced pressure. Add a mixed solution of ethyl acetate and methyl tert-ethyl ether, slurry and dry to obtain 24.9 g of 4-(4-(tert-butyl)phenyl)-1,4-oxalate-4-ammonium salt of trifluoromethanesulfonate; S12. 56g of intermediate product D1,1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate sodium salt, 24.9g of trifluoromethanesulfonic acid 4-(4-(tert-butyl)phenyl)-1,4-oxalate-4-ammonium salt, and 6.2g of triethylamine were mixed with water and dichloromethane for an exchange reaction. The organic phase was separated, washed, and concentrated under reduced pressure. 4-methyl-2-pentanone was added to precipitate a solid. Isopropyl ether was added to slurry the solid, and the solid was filtered and dried to obtain 31.1g of intermediate product E4-[4-(1,1-dimethylethyl)phenyl)1,4-oxothiothiaonium salt and 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]5'-yl)2,2-difluoro-2-sulfoacetate salt; S3. 31.1 g of intermediate product E4-[4-(1,1-dimethylethyl)phenyl)1,4-oxothiothiamonium salt, 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]5'-yl)2,2-difluoro-2-sulfoacetate, 25.1 g of raw material C2,2,3,3-tetrafluoro-1,4-butanediol, 0.25 g of sulfuric acid and dichloroethane were mixed and heated to 90 °C for esterification and ring-closing reaction for 6 h. The organic phase was washed and concentrated under reduced pressure, dissolved in toluene until clear, and crystallized by adding tertiary methyl ether to obtain 14.6 g of photo-induced acid-producing sulfonate. The photo-induced acid-producing sulfonate is 4-[4-(1,1-dimethylethyl)phenyl]-1,4-oxothiothiamonium salt and 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]-5'-yl)2,2-difluoro-2-sulfonoacetate, with the following structure: Comparative Example 5: A method for preparing a sulfonate salt of photoacid-generating agent for photoresist includes the following steps: S1. 11.26 g of bis(4-tert-butylphenyl)iodine chloride, 10 g of intermediate product D1,1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate, 50 g of chloroform and 25 g of water were mixed and stirred for 15 h. The mixture was separated, the chloroform layer was washed with water and concentrated, 50 g of methyl ether was added and stirred for 30 min, and then filtered to obtain 11.75 g of bis(4-tert-butylphenyl)iodide 1,1-difluoro-2-oxo-2-((1s,3R,5S,7s)-4-oxoadamantane-1-yl)oxyethane-1-sulfonate. S2. 11.71 g of bis(4-tert-butylphenyl)iodide 1,1-difluoro-2-oxo-2-((1s,3R,5S,7s)-4-oxoadamantane-1-yl)oxoethane-1-sulfonate, 1.70 g of 1-4-thiaoxane, and 46.84 g of chlorobenzene were mixed and stirred for 30 min. 0.12 g of copper benzoate was added, and the mixture was heated to 100 °C and stirred for min. The mixture was then concentrated and the organic layer was washed with water. 50 g of tert-butyl methyl ether was added, stirred, and filtered to obtain 6.84 g of intermediate product E4-[4-(1,1-dimethylethyl)phenyl)1,4-oxothiamonium salt and 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]5'-yl)2,2-difluoro-2-sulfoacetate. S3. 6.84 g of intermediate product E4-[4-(1,1-dimethylethyl)phenyl)1,4-oxothiothiamonium salt, 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]5'-yl)2,2-difluoro-2-sulfoacetate, 5.94 g of raw material C2,2,3,3-tetrafluoro-1,4-butanediol, 0.23 g of sulfuric acid and dichloroethane were mixed and heated to 58 °C for esterification and ring-closing reaction for 16 h. The mixture was washed and concentrated under reduced pressure, dissolved in toluene until clear, and then crystallized with methyl ether to obtain 4.87 g of photo-induced acid-producing sulfonate. The photo-induced acid-producing sulfonate is 4-[4-(1,1-dimethylethyl)phenyl]-1,4-oxothiothiamonium salt and 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]-5'-yl)2,2-difluoro-2-sulfonoacetate, with the following structure: The purity of each example and comparative example was tested and the yield was calculated. The results are shown in Tables 1 to 5. Table 1. Effect of different raw material molar ratios on product yield and purity. name Raw material A: Raw material B Yield / % purity / % Example 1 1：1.2 29.52 99.82 Example 2 1：1.1 30.03 99.80 Example 3 1：1 29.06 99.76 Comparative Example 1 1：1.5 29.52 97.55 Table 2. Effect of different esterification reaction temperatures in step S1 on product yield and purity. name Reaction temperature / ℃ Yield / % purity / % Example 2 130 30.03 99.80 Example 4 120 29.88 99.67 Example 5 110 29.03 99.85 Comparative Example 2 90 20.36 95.46 Table 3. Effect of different intermediate product molar ratios on product yield and purity. Table 4. Effect of different esterification ring-closing reaction temperatures in step S3 on product yield and purity. name Reaction temperature / ℃ Yield / % purity / % Example 2 110 30.03 99.80 Example 8 105 29.75 99.95 Example 9 100 28.96 99.77 Comparative Example 4 90 15.33 99.12 Table 5. Effects of different reaction routes on product yield and purity. In summary, the product prepared by this invention has low impurity content and high purity. Compared with traditional processes, it has a significantly higher yield and lower manufacturing cost, and is expected to achieve large-scale production and application.

Claims

1. A method for preparing a sulfonate salt of photoacid-generating agent for photoresist, characterized in that, Includes the following steps: S1. Sodium difluorosulfate acetate, 5-hydroxyadamantane-2-one and toluene were mixed and sulfuric acid was added. The mixture was heated and stirred to carry out the esterification reaction. After filtration, 4-methyl-2-pentanone was added to the solid and slurryed. The solid was then filtered and dried to obtain sodium 1,1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate. S2. Sodium 1,1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate is exchanged with raw material S to obtain 4-[4-(1,1-dimethylethyl)phenyl)1,4-oxothiothiamonium salt and 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]5'-yl)2,2-difluoro-2-sulfoacetate salt; S3. 4-[4-(1,1-dimethylethyl)phenyl)1,4-oxothiothiamonium salt was mixed with 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]5'-yl)2,2-difluoro-2-sulfoacetate, 2,2,3,3-tetrafluoro-1,4-butanediol, sulfuric acid, and dichloroethane. The mixture was heated to carry out an esterification and ring-closing reaction. The organic phase was washed and concentrated under reduced pressure. Toluene was added to dissolve the mixture until it became clear. Tertiary methyl ether was added to induce crystallization, yielding the photo-induced acid-producing sulfonate. In step S2, the raw material S includes any one of the following: 4-(4-(tert-butyl)phenyl)-1,4-oxalate-4-ammonium salt of trifluoromethanesulfonic acid, bis(4-tert-butylphenyl) iodide hydroxide methanol solution, and 4-(4-tert-butylphenyl)-1,4-oxothiacyclohexane-4-tetrafluoroborate.

2. The method for preparing photoacid-generating sulfonate salt for photoresist according to claim 1, characterized in that: The esterification reaction in step S1 is carried out at a temperature of 110–130°C for 14–18 h, and the molar ratio of sodium difluorosulfate, 5-hydroxyadamantane-2-one, and sulfuric acid is 1:1 to 1.2:

1.

3. The method for preparing photoacid-generating sulfonate salt for photoresist according to claim 1, characterized in that: The specific method for generating 4-[4-(1,1-dimethylethyl)phenyl)1,4-oxothiothiamonium salt and 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]5'-yl)2,2-difluoro-2-sulfonoacetate salt in step S2 is as follows: When the raw material S is 4-(4-(tert-butyl)phenyl)-1,4-oxalate-4-ammonium salt of trifluoromethanesulfonic acid, the reaction steps are as follows: Sodium 1,1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate, 4-(4-(tert-butyl)phenyl)-1,4-oxalate-4-ammonium salt of trifluoromethanesulfonate, alkali, water, and dichloromethane were mixed and subjected to an exchange reaction at room temperature. The reaction produced 4-(4-(tert-butyl)phenyl)-1,4-oxalate-4-ammonium salt of trifluoromethanesulfonate and 1,1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate... The molar ratio of sodium ethane-1-sulfonate to alkali was 1.5–2.5:1:

1. The organic phase was separated, washed, and concentrated under reduced pressure. 4-methyl-2-pentanone was added to precipitate a solid. Isopropyl ether was added, the mixture was stirred, filtered, and dried to obtain 4-[4-(1,1-dimethylethyl)phenyl)1,4-oxothiothiamonium salt and 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]5'-yl)2,2-difluoro-2-sulfoacetate salt.

4. The method for preparing photoacid-generating sulfonate salt for photoresist according to claim 1, characterized in that: The specific method for generating 4-[4-(1,1-dimethylethyl)phenyl)1,4-oxothiothiamonium salt and 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]5'-yl)2,2-difluoro-2-sulfonoacetate salt in step S2 is as follows: When the raw material S is a methanol solution of bis(4-tert-butylphenyl)iodide hydroxide, the reaction steps are as follows: S21. Sodium 1,1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate was added to a methanol solution of bis(4-tert-butylphenyl)iodide hydroxide, with a molar ratio of bis(4-tert-butylphenyl)iodide trifluoromethanesulfonate to sodium 1,1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate of 1:1.5-2. The mixture was stirred at room temperature and filtered. After washing with methanol, the mixture was concentrated, dissolved in dichloromethane until clear, and washed. The organic phase was concentrated under reduced pressure, and 4-methyl-2-pentanone was added until a solid precipitated. Isopropyl ether was added, the mixture was stirred, filtered, and dried to obtain bis(4-tert-butylphenyl)iodide 1,1-difluoro-2-oxo-2-((1s,3R,5S,7s)-4-oxoadamantane-1-yl)oxyethane-1-sulfonate. S22. A substitution reaction is carried out by mixing bis(4-tert-butylphenyl)iodide 1,1-difluoro-2-oxo-2-((1s,3R,5S,7s)-4-oxoadamantane-1-yl)oxoethane-1-sulfonate, 1,4-thiaoxane, and a copper catalyst with dichloroethane and heating. The molar ratio of the reagents was 1:1.1 to 1.5:0.

1. The mixture was filtered and the filtrate was washed with 1 to 2 wt% citric acid aqueous solution. The organic phase was washed, separated, concentrated under reduced pressure, and 4-methyl-2-pentanone was added until solid precipitate. Isopropyl ether was added, the mixture was stirred, filtered, and dried to obtain 4-[4-(1,1-dimethylethyl)phenyl)1,4-oxothiothiamonium salt and 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]5'-yl)2,2-difluoro-2-sulfoacetate salt.

5. The method for preparing photoacid-generating sulfonate salt for photoresist according to claim 1, characterized in that: The specific method for generating 4-[4-(1,1-dimethylethyl)phenyl)1,4-oxothiothiamonium salt and 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]5'-yl)2,2-difluoro-2-sulfonoacetate salt in step S2 is as follows: When the starting material S is 4-(4-tert-butylphenyl)-1,4-oxothiacyclohexane-4-tetrafluoroborate, the reaction steps are as follows: Sodium 1,1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate, alkali, water, and dichloromethane were mixed and subjected to an exchange reaction at room temperature. The resulting mixtures were: 4-(4-tert-butylphenyl)-1,4-oxothiacyclohexane-4-tetrafluoroborate, 1,1-difluoro-2-oxo-2-((4-oxoadamantane-1-yl)oxy)ethane-1-sulfonate. The molar ratio of sodium ethane-1-sulfonate to base was 1:1.5 to 2.5:

1. The organic phase was separated, washed, and concentrated under reduced pressure. 4-methyl-2-pentanone was added to precipitate a solid. Isopropyl ether was added, the mixture was stirred, filtered, and dried to obtain 4-[4-(1,1-dimethylethyl)phenyl)1,4-oxothiothiamonium salt and 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]5'-yl)2,2-difluoro-2-sulfoacetate salt.

6. The method for preparing photoacid-generating sulfonate salt for photoresist according to claim 4, characterized in that: The copper catalyst includes any one of copper acetylacetonate, copper benzoate hydrate, and copper acetate; the substitution reaction temperature is 100–110°C.

7. The method for preparing photoacid-generating sulfonate salts for photoresists according to claims 3 and 5, characterized in that: The alkali includes any one or more of triethylamine, sodium bicarbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium tert-butoxide, potassium tert-butoxide, potassium carbonate, sodium carbonate, cesium carbonate, ammonia, a methanol solution of ammonia, and ammonium bicarbonate.

8. The method for preparing photoacid-generating sulfonate salt for photoresist according to claim 1, characterized in that: The esterification ring-closing reaction in step S3 is carried out at a temperature of 100–110 °C for 5–7 h. The molar ratio of 4-[4-(1,1-dimethylethyl)phenyl)1,4-oxothiothiamonium salt to 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]5'-yl)2,2-difluoro-2-sulfoacetate, 2,2,3,3-tetrafluoro-1,4-butanediol, and sulfuric acid is 1:1.5–3:0.03–0.

1.

9. The photoacid-generating sulfonate obtained by the preparation method of the photoacid-generating sulfonate for photoresist according to claims 1 to 8.

10. The photo-induced acid-producing sulfonate according to claim 9, characterized in that: The photo-induced acid-producing sulfonate is 4-[4-(1,1-dimethylethyl)phenyl]-1,4-oxothiothiamonium salt and 1-(5,5,6,6-tetrafluorospiro[1,3-dioxane-2,2'-adamantane]-5'-yl)2,2-difluoro-2-sulfonoacetate, with the following structure:

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