Photoacid generator

Abstract

The invention discloses a photo-acid generator containing an aromatic trifluoromethyl oxime sulfonate structure and a preparation method of the photo-acid generator. Meanwhile, the invention discloses a preparation method of the photoacid generator containing the aromatic trifluoromethyl oxime sulfonate structure. The method comprises the following steps: under the protection of inert gas, dissolving a trifluoroacetophenone compound in an organic solvent, adding excessive sodium acetate and hydroxylamine hydrochloride, reacting at room temperature, and detecting that the reaction is complete by TLC (Thin Layer Chromatography); and stopping the reaction. And carrying out suction filtration, concentrating the filtrate, and purifying to obtain a trifluoromethyl hydroxime product. Under the protection of inert gas, dissolving the trifluoromethyl hydroxime product obtained in the step (1) in an organic solvent, adding alkali and excessive sulfonyl chloride compound, reacting at room temperature, and detecting that the reaction is complete by TLC (Thin Layer Chromatography). And stopping the reaction. And carrying out suction filtration, concentrating the filtrate, and purifying to obtain the photoacid generator containing the aromatic trifluoromethoxime sulfonate structure. The invention also provides application of the compound as a photoacid generator.

Description

Technical Field

[0001] The invention relates to a photoacid generator containing an aromatic trifluoromethoxime sulfonate structure and a preparation method and application thereof, belonging to the field of cationic photoinitiators. Background Art

[0002] Photoreaction is a rapid chemical process triggered by light, and it plays an important role in the synthesis and cross-linking of polymers. Photopolymerization technology is a green and environmentally friendly technology with the "5E" characteristics of high efficiency, high quality, environmental protection, energy saving, and controllability. It has been widely used in functional coatings, inks, adhesives, photoresists, medical treatment, and 3D printing. Photoinitiator is one of the key ingredients in photopolymerization and photocuring formulas. Depending on the active intermediates produced by the photoinitiator, photoinitiators can be divided into three categories: free radical photoinitiators, photoacid generators, and photobase generators. Among them, photoacid generators (PAGs) are photosensitive substances that react or dissociate under light to produce one or more acidic compounds to initiate polymerization reactions. They will form strong acids with high quantum yields at the excitation wavelength. Photoacid generators as photoinitiators for initiating cationic polymerization have the following characteristics: 1. They are insensitive to oxygen, and there is almost no oxygen inhibition during the polymerization process; 2. There are many types of monomers (epoxy resins, vinyl ethers and alkylene oxides), which make the final polymer have excellent adhesion, mechanical strength and chemical corrosion resistance; 3. Due to the existence of dark reactions, cationic polymerization is guaranteed to have high curing efficiency. Currently, common photoacid generators can be divided into two types: ionic and non-ionic. Although onium salt ionic photoacid generators can produce super strong proton acids under light, thereby initiating cationic polymerization, most ionic photoacid generators have poor solubility in some cationic monomers and oligomers, which limits their application in polymeric materials. In addition, some cationic polymerization formulas containing onium salt ionic photoacid generators are not suitable for the application of colorless and transparent materials. Therefore, in order to broaden the application scope of photoacid generators in industrial production, non-ionic photoacid generators have been developed and received widespread attention.

[0003] The most studied nonionic photoacid generators include aryl sulfonates, iminosulfonates and oxime sulfonates. Among oxime sulfonates, due to the high active cleavage characteristics of the NO bond in the oxime ester, oxime sulfonate photoacid generators are prone to NO bond homolysis under light to produce sulfonyloxy free radicals, which then combine with hydrogen donors to form sulfonic acid to initiate cationic polymerization. The development of photoacid generators from early ionic compounds to recent nonionic compounds is to overcome the solubility, complex functionalization process and absorption wavelength regulation of ionic photoacid generators in the photocuring process. In addition, the development of new nonionic photoacid generators also faces the problem of low monomer polymerization efficiency, which affects their wide application in polymer initiation and surface coating. Therefore, the design of new nonionic photoacid generators generally improves their polymerization effect by changing anions, chromophores or designing two-photon absorption systems, thereby expanding their application range for vinyl ether and epoxide resin materials. Summary of the invention

[0004] The purpose of the present invention is to overcome a series of problems in photocurable materials caused by the low polymerization efficiency of monomers in the photocurable system of the common non-ionic photoacid generator in the prior art, and to provide a non-ionic photoacid generator containing an aromatic trifluoromethoxysulfonate structure and a preparation method and application thereof. The photoinitiator of the present invention exhibits strong absorption in the ultraviolet region and has a high polymerization initiation ability for vinyl ether and epoxide resins.

[0005] The purpose of the present invention is achieved through the following solutions: A photoacid generator containing an aromatic trifluoromethoxysulfonate structure has the following structural formula.

[0006]

[0007] in: R 1 Including but not limited to one of the following groups: ; R 2 is trifluoromethyl or p-tolyl; Where R 3 , R 4 and R 5 It can be one of the following groups: ; R 6 is oxygen or sulfur; R 7 and R 8 including but not limited to hydrogen, methyl, ethyl, butyl, phenyl, 2-ethylhexyl, allyl, ethoxycarbonylmethyl or carboxymethyl; The preparation method of the above-mentioned photoacid generator containing an aromatic trifluoromethoxime sulfonate structure uses a trifluoroaryl acetone compound and sulfonyl chloride as raw materials and adopts the synthesis route shown in the following formula.

[0008]

[0009] The preparation method comprises the following steps: (1) Dissolve a trifluoroaryl acetone compound in an organic solvent, add an excess of sodium acetate and hydroxylamine hydrochloride, and react until the trifluoroaryl acetone compound reacts completely. Filter by suction, concentrate the filtrate, and purify to obtain a trifluoromethyl hydroxime product.

[0010] (2) Under the protection of an inert gas, the trifluoromethyl hydroxime product obtained in step (1) is dissolved in an organic solvent, and a base and an excess of a sulfonyl chloride compound are added to react until the trifluoromethyl hydroxime product is completely reacted. The filtrate is filtered and concentrated, and after purification, a photoacid generator containing an aromatic trifluoromethoxysulfonate structure is obtained.

[0011] The trifluoroaryl acetone compounds include but are not limited to: .

[0012] Where R 3 , R 4 and R 5 is one of the following groups: ; R 6 is oxygen or sulfur; R 7 and R 8 These include, but are not limited to, hydrogen, methyl, ethyl, butyl, phenyl, 2-ethylhexyl, allyl, ethoxycarbonylmethyl, or carboxymethyl.

[0013] The sulfonyl chloride compound is: R 2 SO2Cl, where R 2 Including but not limited to trifluoromethyl or p-tolyl.

[0014] The solvent includes but is not limited to ethanol, methanol, acetone, tetrahydrofuran, acetonitrile, N, N-dimethylformamide or N, N-dimethylacetamide; the base includes but is not limited to sodium hydroxide (NaOH), potassium hydroxide (KOH), pyridine, triethylamine ((C2H5)3N), piperidine or pyrrolidine.

[0015] In the preparation method, the reaction in each step is carried out at room temperature.

[0016] The aromatic trifluoromethoxime-containing sulfonate structure can be used to initiate curing of prepolymers containing one or more of epoxy, acrylate, styrene, and vinyl ether cationic photopolymerization systems.

[0017] Compared with traditional photoacid generators, this type of photoacid generator containing an aromatic trifluoromethoxysulfonate structure not only exhibits better solubility in organic solvents and resins, but also exhibits higher polymerization efficiency in photocuring systems, thereby broadening its application range in cationic photocuring systems.

[0018] The advantages and beneficial effects of the present invention are: The photoinitiation efficiency is high. The photopolymerization kinetics study shows that the photoacid generator containing the aromatic trifluoromethoxime sulfonate structure of the present invention can efficiently initiate the polymerization of free radical monomers under the irradiation of ultraviolet LED light. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 This is the FT-IR spectrum of the target product containing an aromatic trifluoromethoxime sulfonate structure prepared in Example 1.

[0020] Figure 2 The target product containing the aromatic trifluoromethoxysulfonate structure prepared in Example 1 1 H-NMR spectrum.

[0021] Figure 3 The target product containing the aromatic trifluoromethoxysulfonate structure prepared in Example 1 13 C-NMR spectrum.

[0022] Figure 4 This is the UV-vis spectrum of the target product containing an aromatic trifluoromethoxime sulfonate structure prepared in Example 1.

[0023] Figure 5 This is the kinetic curve of the mixed system of HDDA and EPOX initiated by the target product containing an aromatic trifluoromethoxime sulfonate structure prepared in Example 1. DETAILED DESCRIPTION

[0024] The features and advantages of the present invention can be further understood through the following detailed description in conjunction with the accompanying drawings. The embodiments provided are only illustrative of the method of the present invention and do not limit the rest of the content disclosed by the present invention in any way.

[0025] Example 1. Photoacid generator Preparation (1) 3.41 g (10 mmol) (4-diphenylamino)phenyl trifluoromethyl ethyl ketone and 40 mL anhydrous ethanol were added to a 100 mL single-necked bottle. After stirring and mixing at 25 °C in an argon atmosphere, 1.22 g (15 mmol) sodium acetate and 2.12 g (30 mmol) hydroxylamine hydrochloride were added. The mixture was reacted at 25 °C for 3 h in an argon atmosphere. The reaction was complete when detected by TLC. The reaction system was filtered, diluted with an appropriate amount of ethyl acetate, washed with water three times, and the organic phase was concentrated to obtain 3.12 g trifluoromethyl hydroxime product.

[0026] (2) 0.71 g (2 mmol) of trifluoromethyl hydroxime product and 20 mL of tetrahydrofuran were added to a 50 mL single-necked bottle. After stirring at 25 °C in an argon atmosphere until completely dissolved, 0.33 g (3 mmol) of triethylamine and 0.42 g (2.5 mmol) of trifluoromethylsulfonyl chloride were added. The reaction was carried out at 25 °C in an argon atmosphere for 2 h. The reaction was complete when detected by TLC. The reaction system was filtered, diluted with an appropriate amount of ethyl acetate, washed with water three times, and the organic phase was concentrated to obtain 0.69 g of the target compound 1.

[0027] Figure 1-Figure 3 The FT-IR, 1 H and 13 C NMR confirmed the structure of the target compound 1.

[0028] Figure 1 The FT-IR spectrum of -1 The absorption peak can be attributed to the characteristic absorption peak of CH stretching vibration on the benzene ring skeleton in its molecular structure; 1747 cm -1 The absorption peaks at 1600, 1564, and 1520 cm-1 can be attributed to the C=N stretching vibration peaks of the oxime ester in its molecular structure; -1 The C=C stretching vibration characteristic absorption peak of the benzene ring skeleton is at 1266 cm -1 The peak at 1182 cm is the characteristic peak of the S=O asymmetric stretching vibration of the sulfonate bond in the molecular structure; -1 The center is the characteristic peak of CF stretching vibration of trifluoromethyl in the molecular structure.

[0029] Depend on Figure 2 It can be seen that the chemical shift at 7.8 ppm is the proton peak of the benzene ring skeleton close to the trifluoromethyl ethyl ketone side, the range of 7.1-7.4 ppm is the proton peak of the benzene ring skeleton on the diphenylamino group, and the peak at 6.9 ppm is the proton peak of the benzene ring skeleton close to the diphenylamino side.

[0030] Figure 3It can be seen that the chemical shift at 154.1 ppm is the carbon peak of C=N in the trifluoromethanesulfonic acid oxime ester structure, 145.5 ppm is the carbon peak of -CH-N- in the triethylamine structure, 132.1, 129.9, 126.7 and 125.8 ppm are the carbon peaks on the benzene ring in the triethylamine structure, and 118.1 ppm is the carbon peak of -CF in the trifluoromethyl structure. These results indicate that the target compound 1 has been successfully prepared.

[0031] from Figure 4 It can be seen from the UV-vis spectrum that the maximum absorption wavelength of the target compound 1 is at 351 nm, its maximum absorption wavelength is in the ultraviolet light region, and the effective absorption range covers 325-375 nm.

[0032] Figure 5 The kinetic curve of the mixed system of HDDA and EPOX was given: the change of the absorption intensity of a characteristic peak under illumination was recorded by using real-time infrared with a high-speed recorder. The mixed system of HDDA and EPOX was used as the polymerization monomer, and a certain amount of target compound 1 ([PI] = 2×10 -5 mol / g) / HDDA+EPOX sample solution was added dropwise to the middle of the potassium bromide salt sheet to form a uniform liquid film. After irradiation with LED ultraviolet light for 15 min, the changes in the absorption peak areas of carbon-carbon double bonds and epoxy bonds were recorded by infrared spectrometer to obtain the conversion rate of the corresponding monomer.

[0033] Example 2. Photoacid generator Preparation (1) Add 3.44 g (10 mmol) (2-ethyl-4-dimethylamino-6-cyclohexylamino)phenyl trifluoromethyl ethyl ketone and 40 mL anhydrous ethanol to a 100 mL single-necked bottle. Stir at 17 °C in an argon atmosphere until completely dissolved. Then add 1.2 g (15 mmol) sodium acetate and 2.1 g (30 mmol) hydroxylamine hydrochloride. React at 17 °C in an argon atmosphere for 3 h. TLC indicates that the reaction is complete. Filter the reaction system, dilute with an appropriate amount of ethyl acetate, wash with water three times, and concentrate the organic phase to obtain 3.24 g trifluoromethyl hydroxime product.

[0034] (2) 0.36 g (1 mmol) of trifluoromethyl hydroxime product and 20 mL of tetrahydrofuran were added to a 50 mL single-necked bottle. After stirring at 17 °C in an argon atmosphere until completely dissolved, 0.15 g (1.5 mmol) of triethylamine and 0.17 g (1 mmol) of trifluoromethylsulfonyl chloride were added. The reaction was carried out at 17 °C in an argon atmosphere for 1 h. The reaction was complete after TLC detection. The reaction system was filtered, diluted with an appropriate amount of ethyl acetate, washed with water three times, and the organic phase was concentrated to obtain 0.31 g of the target compound 2.

[0035] The kinetic application test of the vinyl ether DVE-3 and epoxy EPOX mixed system was initiated by compound 2: the change of the absorption intensity of a characteristic peak under illumination was recorded by real-time infrared with a high-speed recorder. The DVE-3 and EPOX mixed system was used as the polymerization monomer, and the target compound 2 ([PI] = 2×10 -5 mol / g) / (DVE-3+EPOX) sample solution was added dropwise to the middle of the potassium bromide salt sheet to form a uniform liquid film. After irradiation with LED ultraviolet light for 15 min, the changes in the absorption peak areas of carbon-carbon double bonds and epoxy bonds were recorded by infrared spectrometer. The conversion rates of monomers DVE-3 and EPOX were detected to be 91% and 68% respectively.

[0036] Example 3. Photoacid generator Preparation (1) Add 3.88 g (10 mmol) (2-methoxy-4-amino-6-morpholinyl)phenyl trifluoromethyl ethyl ketone and 40 mL anhydrous methanol to a 100 mL single-necked bottle. Stir at 18 °C in an argon atmosphere until completely dissolved. Then add 1.2 g (15 mmol) sodium acetate and 2.1 g (30 mmol) hydroxylamine hydrochloride. React at 18 °C in an argon atmosphere for 3 h. TLC indicates that the reaction is complete. Filter the reaction system, dilute with an appropriate amount of ethyl acetate, wash with water three times, and concentrate the organic phase to obtain 3.31 g trifluoromethyl hydroxime product.

[0037] (2) 0.41 g (1 mmol) of trifluoromethyl hydroxime product and 20 mL of tetrahydrofuran were added to a 50 mL single-necked bottle. After stirring at 18 °C in an argon atmosphere until completely dissolved, 0.15 g (1.5 mmol) of triethylamine and 0.17 g (1 mmol) of trifluoromethylsulfonyl chloride were added. The reaction was carried out at 18 °C in an argon atmosphere for 1 h. The reaction was complete when detected by TLC. The reaction system was filtered, diluted with an appropriate amount of ethyl acetate, washed with water three times, and the organic phase was concentrated to obtain 0.35 g of the target compound 3.

[0038] Example 4. Photoacid generator Preparation (1) Add 3.58 g (10 mmol) (2-hydroxy-4-(ethyl-n-butyl)amino-6-cyclopentylamino)phenyl trifluoromethyl ethyl ketone and 40 mL anhydrous methanol to a 100 mL single-necked bottle. Stir at 19 °C in an argon atmosphere until completely dissolved. Then add 1.2 g (15 mmol) sodium acetate and 2.1 g (30 mmol) hydroxylamine hydrochloride. React at 19 °C in an argon atmosphere for 3 h. TLC indicates that the reaction is complete. Filter the reaction system, dilute with an appropriate amount of ethyl acetate, wash with water three times, and concentrate the organic phase to obtain 3.27 g trifluoromethyl hydroxime product.

[0039] (2) 0.37 g (1 mmol) of trifluoromethyl hydroxime product and 20 mL of acetone were added to a 50 mL single-necked bottle. After stirring at 19 °C in an argon atmosphere until completely dissolved, 0.11 g (1.5 mmol) of tetrahydropyrrole and 0.17 g (1 mmol) of trifluoromethylsulfonyl chloride were added. The reaction was carried out at 19 °C in an argon atmosphere for 1 h. The reaction was complete when detected by TLC. The reaction system was filtered, diluted with an appropriate amount of ethyl acetate, washed with water three times, and the organic phase was concentrated to obtain 0.29 g of the target compound 4.

[0040] Example 5. Photoacid generator Preparation (1) Add 5.59 g (10 mmol) (2-butoxy-4-di(2-ethyl)hexylamino-6-ethoxycarbonylmethoxy)phenyl trifluoromethyl ethyl ketone and 40 mL acetone to a 100 mL single-necked bottle. Stir at 20 °C in an argon atmosphere until the mixture is completely dissolved. Then add 1.2 g (15 mmol) sodium acetate and 2.1 g (30 mmol) hydroxylamine hydrochloride. The mixture is reacted at 20 °C in an argon atmosphere for 3 h. The reaction is complete when detected by TLC. Filter the reaction system, dilute with an appropriate amount of ethyl acetate, wash with water three times, and concentrate the organic phase to obtain 4.87 g trifluoromethyl hydroxime product.

[0041] (2) 0.58 g (1 mmol) of trifluoromethyl hydroxime product and 20 mL of acetone were added to a 50 mL single-necked bottle. After stirring at 20 °C in an argon atmosphere until completely dissolved, 0.11 g (1.5 mmol) of tetrahydropyrrole and 0.17 g (1 mmol) of trifluoromethylsulfonyl chloride were added. The reaction was carried out at 21 °C in an argon atmosphere for 1 h. The reaction was complete when detected by TLC. The reaction system was filtered, diluted with an appropriate amount of ethyl acetate, washed with water three times, and the organic phase was concentrated to obtain 0.51 g of the target compound 5.

[0042] The kinetic application test of the mixed system of vinyl ether BVE and epoxy ERL-4221 was initiated by using compound 5: the change of the absorption intensity of a characteristic peak under illumination was recorded by using real-time infrared with a high-speed recorder. The mixed system of BVE and ERL-4221 was used as the polymerization monomer, and the target compound 5 ([PI] = 2×10 -5 mol / g) / (BVE+ERL-4221) sample solution was added dropwise to the middle of the potassium bromide salt sheet to form a uniform liquid film. After irradiation with LED ultraviolet light for 15 min, the changes in the absorption peak areas of carbon-carbon double bonds and epoxy bonds were recorded by infrared spectrometer. The conversion rates of monomers BVE and ERL-4221 were 72% and 61% respectively.

[0043] Example 6. Photoacid generator Preparation (1) Add 4.03 g (10 mmol) of (2-(2-ethyl)hexyloxy-4-(diethoxycarbonylmethyl)amino)phenyltrifluoromethylethanone and 40 mL of tetrahydrofuran to a 100 mL single-necked bottle. Stir at 22 °C in an argon atmosphere until the mixture is completely dissolved. Then add 1.2 g (15 mmol) of sodium acetate and 2.1 g (30 mmol) of hydroxylamine hydrochloride. The mixture is reacted at 22 °C in an argon atmosphere for 5 h. The reaction is complete when detected by TLC. Filter the reaction system, dilute with an appropriate amount of ethyl acetate, wash with water three times, and concentrate the organic phase to obtain 3.31 g of trifluoromethylhydroxime product.

[0044] (2) 0.42 g (1 mmol) of trifluoromethyl hydroxime product and 20 mL of acetonitrile were added to a 50 mL single-necked bottle. After stirring at 22 °C in an argon atmosphere until completely dissolved, 0.11 g (1.5 mmol) of tetrahydropyrrole and 0.17 g (1 mmol) of trifluoromethylsulfonyl chloride were added. The reaction was carried out at 22 °C in an argon atmosphere for 2 h. The reaction was complete when detected by TLC. The reaction system was filtered, diluted with an appropriate amount of ethyl acetate, washed with water three times, and the organic phase was concentrated to obtain 0.32 g of the target compound 6.

[0045] The kinetic application test of the mixed system of styrene DVB and epoxy E51 was initiated by using compound 6: the change of the absorption intensity of a characteristic peak under illumination was recorded by using real-time infrared with a high-speed recorder. The mixed system of DVB and E51 was used as the polymerization monomer, and the target compound 6 ([PI] = 2×10 -5 mol / g) / (DVB+E51) sample solution was added dropwise to the middle of the potassium bromide salt sheet to form a uniform liquid film. After irradiation with LED ultraviolet light for 15 min, the changes in the absorption peak areas of carbon-carbon double bonds and epoxy bonds were recorded by infrared spectrometer. The conversion rates of monomers DVB and E51 were detected to be 84% and 64% respectively.

[0046] Example 7. Photoacid generator Preparation (1) Add 1.64 g (10 mmol) furan-2-trifluoromethyl ethyl ketone and 40 mL tetrahydrofuran to a 100 mL single-necked bottle, stir at 23 °C in an argon atmosphere until completely dissolved, then add 1.2 g (15 mmol) sodium acetate and 2.1 g (30 mmol) hydroxylamine hydrochloride, react at 23 °C in an argon atmosphere for 2 h, and TLC indicates that the reaction is complete. Filter the reaction system, dilute with an appropriate amount of ethyl acetate, wash with water three times, and concentrate the organic phase to obtain 1.48 g trifluoromethyl hydroxime product.

[0047] (2) 0.18 g (1 mmol) of trifluoromethyl hydroxime product and 20 mL of acetonitrile were added to a 50 mL single-necked bottle. After stirring at 23 °C in an argon atmosphere until completely dissolved, 0.06 g (1.5 mmol) of sodium hydroxide and 0.17 g (1 mmol) of trifluoromethylsulfonyl chloride were added. The reaction was carried out at 23 °C in an argon atmosphere for 1 h. The reaction was complete when detected by TLC. The reaction system was filtered, diluted with an appropriate amount of ethyl acetate, washed with water three times, and the organic phase was concentrated to obtain 0.12 g of the target compound 7.

[0048] Compound 7 was used to initiate the kinetic application test of the mixed system of acrylate HDDA and epoxy ERL-4221: a real-time infrared and high-speed recorder were used to record the change of the absorption intensity of a characteristic peak under illumination. The mixed system of HDDA and ERL-4221 was used as the polymerization monomer, and the target compound 7 ([PI] = 2×10 -5 mol / g) / (HDDA+ERL-4221) sample solution was added dropwise to the middle of the potassium bromide salt sheet to form a uniform liquid film. After irradiation with LED ultraviolet light for 15 min, the changes in the absorption peak areas of carbon-carbon double bonds and epoxy bonds were recorded by infrared spectrometer. The conversion rates of monomers HDDA and ERL-4221 were 85% and 72% respectively.

[0049] Example 8. Photoacid generator Preparation (1) Add 1.95 g (10 mmol) 5-hydroxythiophene-2-trifluoromethyl ethyl ketone and 40 mL acetonitrile to a 100 mL single-necked bottle, stir at 24 °C in an argon atmosphere until completely dissolved, then add 1.2 g (15 mmol) sodium acetate and 2.1 g (30 mmol) hydroxylamine hydrochloride, react at 24 °C in an argon atmosphere for 2 h, and TLC indicates that the reaction is complete. Filter the reaction system, dilute with an appropriate amount of ethyl acetate, wash with water three times, and concentrate the organic phase to obtain 1.78 g trifluoromethyl hydroxime product.

[0050] (2) 0.22 g (1 mmol) of trifluoromethyl hydroxime product and 20 mL of N, N-dimethylformamide were added to a 50 mL single-necked bottle. After stirring at 24 °C in an argon atmosphere until completely dissolved, 0.09 g (1.5 mmol) of piperidine and 0.21 g (1 mmol) of p-toluenesulfonyl chloride were added. The reaction was carried out at 24 °C in an argon atmosphere for 1 h. The reaction was complete when detected by TLC. The reaction system was filtered, diluted with an appropriate amount of ethyl acetate, washed with water three times, and the organic phase was concentrated to obtain 0.29 g of the target compound 8.

[0051] Example 9. Photoacid generator Preparation (1) Add 1.94 g (10 mmol) 5-methoxyfuran-3-trifluoromethyl ethyl ketone and 40 mL acetonitrile to a 100 mL single-necked bottle, stir at 25 °C in an argon atmosphere until completely dissolved, then add 1.2 g (15 mmol) sodium acetate and 2.1 g (30 mmol) hydroxylamine hydrochloride, react at 25 °C in an argon atmosphere for 4 h, and complete the reaction by TLC. Filter the reaction system, dilute with an appropriate amount of ethyl acetate, wash with water three times, and concentrate the organic phase to obtain 1.87 g trifluoromethyl hydroxime product.

[0052] (2) 0.21 g (1 mmol) of trifluoromethylhydroxamate and 20 mL of N, N-dimethylformamide were added to a 50 mL single-necked bottle. After stirring at 25 °C in an argon atmosphere until the mixture was completely dissolved, 0.09 g (1.5 mmol) of piperidine and 0.21 g (1 mmol) of p-toluenesulfonyl chloride were added. The mixture was reacted at 25 °C in an argon atmosphere for 1 h. The reaction was complete after TLC. The reaction system was filtered, diluted with an appropriate amount of ethyl acetate, washed with water three times, and the organic phase was concentrated to obtain 0.27 g of the target compound 9.

[0053] Example 10. Photoacid generator Preparation (1) Add 2.24 g (10 mmol) 5-ethoxythiophene-3-trifluoromethyl ethyl ketone and 40 mL acetonitrile to a 100 mL single-necked bottle, stir at 26 °C in an argon atmosphere until completely dissolved, then add 1.2 g (15 mmol) sodium acetate and 2.1 g (30 mmol) hydroxylamine hydrochloride, react at 26 °C in an argon atmosphere for 4 h, and complete the reaction by TLC. Filter the reaction system, dilute with an appropriate amount of ethyl acetate, wash with water three times, and concentrate the organic phase to obtain 1.96 g trifluoromethyl hydroxime product.

[0054] (2) 0.24 g (1 mmol) of trifluoromethylhydroxime product and 20 mL of N, N-dimethylacetamide were added to a 50 mL single-necked bottle. After stirring at 26 °C in an argon atmosphere until completely dissolved, 0.15 g (1.5 mmol) of triethylamine and 0.21 g (1 mmol) of p-toluenesulfonyl chloride were added. The reaction was carried out at 26 °C in an argon atmosphere for 1 h. The reaction was complete when detected by TLC. The reaction system was filtered, diluted with an appropriate amount of ethyl acetate, washed with water three times, and the organic phase was concentrated to obtain 0.34 g of the target compound 10.

[0055] Example 11. Photoacid generator Preparation (1) Add 2.14 g (10 mmol) of benzofuran-2-trifluoromethyl ethyl ketone and 40 mL of N,N-dimethylformamide to a 100 mL single-necked bottle, stir at 27 °C in an argon atmosphere until completely dissolved, then add 1.2 g (15 mmol) of sodium acetate and 2.1 g (30 mmol) of hydroxylamine hydrochloride, react at 27 °C in an argon atmosphere for 2 h, and complete the reaction by TLC. Filter the reaction system, dilute with an appropriate amount of ethyl acetate, wash with water three times, and concentrate the organic phase to obtain 1.86 g of trifluoromethyl hydroxime product.

[0056] (2) 0.23 g (1 mmol) of trifluoromethylhydroxime product and 20 mL of N, N-dimethylacetamide were added to a 50 mL single-necked bottle. After stirring at 27 °C in an argon atmosphere until completely dissolved, 0.11 g (1.5 mmol) of potassium hydroxide and 0.21 g (1 mmol) of p-toluenesulfonyl chloride were added. The reaction was carried out at 27 °C in an argon atmosphere for 1 h. The reaction was complete when detected by TLC. The reaction system was filtered, diluted with an appropriate amount of ethyl acetate, washed with water three times, and the organic phase was concentrated to obtain 0.31 g of the target compound 11.

[0057] The kinetic application test of the mixed system of acrylate TMPTA and epoxy E51 was initiated by using compound 11: the change of the absorption intensity of a characteristic peak under light was recorded by using real-time infrared with a high-speed recorder. The mixed system of TMPTA and E51 was used as the polymerization monomer, and the target compound 11 ([PI] = 2×10 -5 mol / g) / (TMPTA+E51) sample solution was added dropwise to the middle of the potassium bromide salt sheet to form a uniform liquid film. After irradiation with LED ultraviolet light for 15 min, the changes in the absorption peak areas of carbon-carbon double bonds and epoxy bonds were recorded by infrared spectrometer. The conversion rates of monomers TMPTA and E51 were detected to be 65% and 53% respectively.

[0058] Example 12. Photoacid generator Preparation (1) Add 2.3 g (10 mmol) of benzothiophene-2-trifluoromethyl ethyl ketone and 40 mL of N,N-dimethylformamide to a 100 mL single-necked bottle, stir at 28 °C in an argon atmosphere until completely dissolved, then add 1.2 g (15 mmol) of sodium acetate and 2.1 g (30 mmol) of hydroxylamine hydrochloride, react at 28 °C in an argon atmosphere for 2 h, and complete the reaction by TLC. Filter the reaction system, dilute with an appropriate amount of ethyl acetate, wash with water three times, and concentrate the organic phase to obtain 2.05 g of trifluoromethyl hydroxime product.

[0059] (2) 0.25 g (1 mmol) of trifluoromethyl hydroxime product and 20 mL of tetrahydrofuran were added to a 50 mL single-necked bottle. After stirring at 28 °C in an argon atmosphere until completely dissolved, 0.15 g (1.5 mmol) of triethylamine and 0.21 g (1 mmol) of p-toluenesulfonyl chloride were added. The reaction was carried out at 28 °C in an argon atmosphere for 1 h. The reaction was complete when detected by TLC. The reaction system was filtered, diluted with an appropriate amount of ethyl acetate, washed with water three times, and the organic phase was concentrated to obtain 0.35 g of the target compound 12.

[0060] The kinetic application test of the mixed system of vinyl ether CHVE and epoxy EPOX was initiated by using compound 12: the change of the absorption intensity of a characteristic peak under illumination was recorded by using real-time infrared with a high-speed recorder. The mixed system of CHVE and EPOX was used as the polymerization monomer, and the target compound 12 ([PI] = 2×10 -5 mol / g) / (CHVE+EPOX) sample solution was added dropwise to the middle of the potassium bromide salt sheet to form a uniform liquid film. After irradiation with LED ultraviolet light for 15 min, the changes in the absorption peak areas of carbon-carbon double bonds and epoxy bonds were recorded by infrared spectrometer. The conversion rates of monomers CHVE and EPOX were 75% and 68% respectively.

[0061] Example 13. Photoacid generator Preparation (1) Add 2.14 g (10 mmol) of benzofuran-3-trifluoromethyl ethyl ketone and 40 mL of N, N-dimethylformamide to a 100 mL single-necked bottle, stir at 29 °C in an argon atmosphere until completely dissolved, then add 1.2 g (15 mmol) of sodium acetate and 2.1 g (30 mmol) of hydroxylamine hydrochloride, react at 29 °C in an argon atmosphere for 1 h, and complete the reaction by TLC. Filter the reaction system, dilute with an appropriate amount of ethyl acetate, wash with water three times, and concentrate the organic phase to obtain 1.94 g of trifluoromethyl hydroxime product.

[0062] (2) 0.23 g (1 mmol) of trifluoromethyl hydroxime product and 20 mL of tetrahydrofuran were added to a 50 mL single-necked bottle. After stirring at 29 °C in an argon atmosphere until completely dissolved, 0.13 g (1.5 mmol) of pyridine and 0.21 g (1 mmol) of p-toluenesulfonyl chloride were added. The reaction was carried out at 29 °C in an argon atmosphere for 1 h. The reaction was complete when detected by TLC. The reaction system was filtered, diluted with an appropriate amount of ethyl acetate, washed with water three times, and the organic phase was concentrated to obtain 0.33 g of the target compound 13.

[0063] The kinetic application test of the vinyl ether CHVE and epoxy DGED mixed system was initiated by compound 13: the change of the absorption intensity of a characteristic peak under illumination was recorded by real-time infrared with a high-speed recorder. The CHVE and DGED mixed system was used as the polymerization monomer, and the target compound 13 ([PI] = 2×10 -5 mol / g) / (CHVE+DGED) sample solution was added dropwise to the middle of the potassium bromide salt sheet to form a uniform liquid film. After irradiation with LED ultraviolet light for 15 min, the changes in the absorption peak areas of carbon-carbon double bonds and epoxy bonds were recorded by infrared spectrometer. The conversion rates of monomers CHVE and DGED were 88% and 71% respectively.

[0064] Example 14. Photoacid generator Preparation (1) Add 2.3 g (10 mmol) benzothiophene-3-trifluoromethyl ethyl ketone and 40 mL N,N-dimethylformamide to a 100 mL single-necked bottle, stir at 30 °C in an argon atmosphere until completely dissolved, then add 1.2 g (15 mmol) sodium acetate and 2.1 g (30 mmol) hydroxylamine hydrochloride, react at 30 °C in an argon atmosphere for 2 h, and complete the reaction by TLC. Filter the reaction system, dilute with an appropriate amount of ethyl acetate, wash with water three times, and concentrate the organic phase to obtain 1.94 g trifluoromethyl hydroxime product.

[0065] (2) 0.25 g (1 mmol) of trifluoromethylhydroxamate and 20 mL of N, N-dimethylacetamide were added to a 50 mL single-necked bottle. The mixture was stirred at 30 °C in an argon atmosphere until completely dissolved. Then, 0.13 g (1.5 mmol) of pyridine and 0.21 g (1 mmol) of p-toluenesulfonyl chloride were added. The mixture was reacted at 30 °C in an argon atmosphere for 3 h. The reaction was complete when detected by TLC. The reaction system was filtered, diluted with an appropriate amount of ethyl acetate, washed with water three times, and the organic phase was concentrated to obtain 0.31 g of the target compound 14.

[0066] The kinetic application test of the mixed system of acrylate TPGDA and epoxy DGED was initiated by using compound 14: a real-time infrared and high-speed recorder were used to record the change of the absorption intensity of a certain characteristic peak under illumination. The mixed system of TPGDA and DGED was used as the polymerization monomer, and the target compound 14 ([PI] = 2×10 -5 mol / g) / (TPGDA+DGED) sample solution was added dropwise to the middle of the potassium bromide salt sheet to form a uniform liquid film. After irradiation with LED ultraviolet light for 15 min, the changes in the absorption peak areas of carbon-carbon double bonds and epoxy bonds were recorded by infrared spectrometer. The conversion rates of monomers TPGDA and DGED were 90% and 68% respectively.

[0067] The photoacid generators prepared in the above embodiments can efficiently initiate polymerization of epoxy and double bond monomers under irradiation of ultraviolet LED light.

Claims

1. A photoacid generator containing an aromatic trifluoromethoxysulfonate structure, characterized in that: The photoacid generator structural formula is as follows: , R2 is trifluoromethyl or p-tolyl, wherein: R1 is selected from , where R 3 , R 4 and R 5 Selected from , , , , Any one of the following, and not all of the following , , , , Any one of R 7 and R 8 Selected from hydrogen, methyl, ethyl, butyl, phenyl, 2-ethylhexyl, allyl, or carboxymethyl.

2. The photoacid generator containing an aromatic trifluoromethoxime sulfonate structure according to claim 1, characterized in that: The photoacid generator structural formula is as follows: , R2 is trifluoromethyl or p-tolyl, wherein: R1 is selected from , R 3 For H. ; R 6 is oxygen or sulfur; R 7 Selected from hydrogen.

3. The photoacid generator containing an aromatic trifluoromethoxime sulfonate structure according to claim 1, characterized in that: The photoacid generator structural formula is as follows: , R2 is trifluoromethyl or p-tolyl, wherein: R1 is selected from , R 3 for ; R 6 is oxygen or sulfur; R 7 Selected from: methyl, or ethyl.

4. The photoacid generator containing an aromatic trifluoromethoxime sulfonate structure according to claim 1, characterized in that: The photoacid generator structural formula is as follows: , R2 is trifluoromethyl or p-tolyl, wherein: R1 is selected from , R 6 for oxygen; Or, R1 is selected from , R 6 Oxygen or sulfur.

5. A method for preparing a photoacid generator as claimed in any one of claims 1 to 4, characterized in that: The preparation method comprises the following steps: (1) Under the protection of inert gas, a trifluoroaryl acetone compound is dissolved in an organic solvent, and an excess of sodium acetate and hydroxylamine hydrochloride are added to react at room temperature. When the reaction is complete as detected by TLC, the reaction is stopped, filtered, and the filtrate is concentrated. After purification, a trifluoromethyl hydroxime product is obtained; (2) Under the protection of inert gas, the trifluoromethyl hydroxime product obtained in step (1) is dissolved in an organic solvent, a base and an excess of a sulfonyl chloride compound are added, and the reaction is carried out at room temperature. When the reaction is complete by TLC detection, the reaction is stopped, filtered, and the filtrate is concentrated. After purification, a photoacid generator containing an aromatic trifluoromethoxysulfonate structure is obtained.

6. The method for preparing a photoacid generator according to claim 5, characterized in that: The trifluoroaryl acetone compound is any one of the following compounds: ; When When R 3 , R 4 and R 5 Selected from , , , , Any one of the following, and not all of the following , , , , Any one of R 7 and R 8 is selected from hydrogen, methyl, ethyl, butyl, phenyl, 2-ethylhexyl, allyl, or carboxymethyl; When When R 3 For H. ; R 6 is oxygen or sulfur; R 7 Selected from hydrogen; When When R 3 for ; R 6 is oxygen or sulfur; R 7 Selected from: methyl or ethyl; When When R 6 for oxygen; When When R 6 Oxygen or sulfur.

7. The method for preparing a photoacid generator according to claim 6, characterized in that: The sulfonyl chloride compound is trifluoromethylsulfonyl chloride or p-toluenesulfonyl chloride.

8. The method for preparing a photoacid generator according to claim 6, characterized in that: The solvent includes ethanol, methanol, acetone, tetrahydrofuran, acetonitrile, N, N-dimethylformamide or N, N-dimethylacetamide.

9. The method for preparing a photoacid generator according to claim 6, characterized in that: The base includes sodium hydroxide, potassium hydroxide, pyridine, triethylamine, piperidine or tetrahydropyrrole.

10. The photoacid generator according to any one of claims 1 to 4 or the photoacid generator prepared by the method according to any one of claims 5 to 9 is used as a photoacid generator in a prepolymer containing two or more of epoxy, acrylate, styrene, and vinyl ether cationic photopolymerization systems.

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