Synthesis method of photoinitiator diazonaphthoquinone sulfonate

Abstract

The method comprises the following steps: taking diazonaphthol sulfonyl chloride and a phenolic hydroxyl compound as raw materials, taking aminated polystyrene porous microspheres as an acid-binding agent, and carrying out heat preservation reaction in a polar solvent to obtain a first product; 2, filtering the first product obtained in the step 1, and recovering to obtain aminated polystyrene porous microsphere hydrochloride; carrying out post-treatment on the aminated polystyrene porous microsphere hydrochloride in the step 2 to obtain a crude product diazo naphthoquinone sulfonate; and 3, pulping and washing the crude product diazonaphthoquinone sulfonate in the step 3 with a solvent, filtering, and drying to obtain the product diazonaphthoquinone sulfonate. The synthesis method disclosed by the invention is simple to operate, low in cost, very suitable for industrialization and capable of being widely popularized and used.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, and in particular to a method for synthesizing the photoinitiator diazonoquinone sulfonate. Background Technology

[0002] Diazonaphthoquinone sulfonate photoinitiators are mainly used in argon ion laser scanning curing, holographic laser imaging, polyimide photocuring, PCB inks, PCB resists, solder resists, and photocurable dental materials. They are also widely used in UV coatings, UV inks, UV adhesives, photoresists, photopolymer printing plates, and photocurable composite materials. They possess advantages such as strong resistance to dry etching, good heat resistance, and easy adhesive removal, making them widely applicable in microelectronics, micromechanics, and printing fields.

[0003] Diazonaphthoquinone sulfonate photoinitiators typically have the following structures:

[0004]

[0005] in

[0006] Or H.

[0007] The number of diazo groups in each diazonaphthoquinone sulfonate photoinitiator molecule directly affects the photoinitiator's performance. Currently, most diazonaphthoquinone sulfonate photoinitiators are prepared by esterification reactions of 2,1-diazonaphthoquinone-5-sulfonyl chloride (abbreviated as 215 sulfonyl chloride) or 2,1-diazonaphthoquinone-4-sulfonyl chloride (abbreviated as 214 sulfonyl chloride) with polyphenolic hydroxy compounds (such as trihydroxybenzophenone, tetrahydroxybenzophenone, TrisP-PA (trade name, manufactured by Honshu Chemical Industry), pyrogallol A, etc.). The content of monoester, diester, trimer, and tetraester in the esterification product directly determines the number of diazo groups, thus affecting the photoinitiator's performance. Currently, to ensure the esterification rate, alkaline acid-absorbing agents are added to this esterification reaction. For example, CN119859113A uses metal ion bases such as potassium hydroxide or sodium hydroxide as acid-absorbing agents. This introduces metal elements into the reaction, increasing the purification difficulty for obtaining diazonaphthoquinone sulfonate photoinitiators with low metal element content. Dongwoo Fine Chemicals Co., Ltd. of South Korea reported in CN118108621A the use of small organic molecule amines such as triethylamine as acid-absorbing agents. In this case, amine hydrochlorides are generated and mixed into the diazonaphthoquinone sulfonate, making them difficult to separate. Repeated and large-volume acid washing is required, resulting in cumbersome operation and difficulty in obtaining high-purity diazonaphthoquinone sulfonate photoinitiators with low metal element content. Patents such as CN104974107A and CN101717361 may also encounter the same problem. Summary of the Invention

[0008] The purpose of this invention is to provide a method for synthesizing the photoinitiator diazonoquinone sulfonate, thereby solving one or more of the problems in the prior art.

[0009] The present invention provides a method for synthesizing the photoinitiator diazonoquinone sulfonate, comprising the following steps:

[0010] Step 1: Using diazonaphthol sulfonyl chloride and phenolic hydroxyl compounds as raw materials, and amino-modified polystyrene porous microspheres as acid-absorbing agents, the reaction is carried out in a polar solvent at a constant temperature to obtain the first product;

[0011] Step 2: Filter the first product obtained in Step 1 to recover the amino-modified polystyrene porous microsphere hydrochloride.

[0012] Step 3: Post-process the amino-modified polystyrene porous microsphere hydrochloride obtained in Step 2 to obtain crude diazonoquinone sulfonate;

[0013] Step 4: The crude diazonoquinone sulfonate from Step 3 is pulped, washed, filtered, and dried to obtain the product diazonoquinone sulfonate.

[0014] Among them, the raw materials can be obtained by a simple metal element removal step to obtain electronic grade raw materials, and the polar solvent is commercially available electronic grade, so that low metal content electronic grade photoresist diazonium naphthalene sulfonate photoinitiator can be easily obtained.

[0015] In some embodiments, the phenolic hydroxyl compound in step one is a monohydroxy substituted phenol, a polyhydroxy substituted phenol, or a compound having a phenolic hydroxyl structure.

[0016] In some embodiments, the molar ratio of the phenolic hydroxyl compound and the diazonopyranosulfonyl chloride in step one is 1:0.7-5.0, and the molar ratio of the diazonopyranosulfonyl chloride and the amino group in the acetic acid is 1:0.8-5.

[0017] In some embodiments, the polar solvent in step one is one or more of 1,2-dichloroethane, chloroform, carbon tetrachloride, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, toluene, xylene, N,N-dimethylformamide, or N,N-dimethylacetamide.

[0018] In some embodiments, the polar solvent in step one is dioxane or N,N-dimethylformamide.

[0019] In some embodiments, the preparation method of the amino-modified polystyrene porous microspheres in step one is as follows:

[0020] S1. Polystyrene microspheres were added to 98wt% concentrated sulfuric acid at a ratio of 1:30 g / mL, reacted at 50℃ for 12 h, filtered, washed with water, and dried under vacuum at 60℃ to obtain sulfonated polystyrene microspheres.

[0021] S2. The sulfonated polystyrene microspheres were reacted in diethylamine aqueous solution at 120°C for 24 hours, filtered, washed with water, then soaked and neutralized in dioxane at 60°C, filtered, and vacuum dried at 60°C to obtain amino-modified polystyrene porous microspheres.

[0022] Among them, using amino-modified polystyrene porous microspheres as an acid-absorbing agent can maintain a solid state in the reaction system, is easy to separate, does not introduce ammonium salts and metal impurities, is not easily lost, can be recycled and reused, and is suitable for industrial production.

[0023] In some implementations, the temperature for the heat preservation reaction in step one is -40 to 120°C.

[0024] In some implementations, the heat preservation reaction temperature in step one is 10-50°C.

[0025] In some embodiments, the amino-modified polystyrene porous microsphere hydrochloride recovered in step two is soaked and washed with 10 L of dioxane at 100°C for 5 h, then soaked and washed with 10 L of concentrated ammonia at 50°C for 10 h, then soaked and washed with 10 L of purified water at 90°C, and then vacuum dried at 100°C for 24 h. After cooling, the amino-modified polystyrene porous microspheres are obtained and then reused in the synthesis system.

[0026] In some implementations, the post-processing in step three includes vacuum distillation to recover the polar solvent or the addition of a poor solvent to precipitate the solid.

[0027] In some embodiments, the undesirable solvent is one or more of petroleum ether, n-hexane, isohexane, water, methanol, ethanol, or acetone.

[0028] In some implementations, the undesirable solvent is water.

[0029] In some implementations, the solvent in step four is petroleum ether.

[0030] The process involves the following steps: After the reaction is complete, the reaction product is filtered and recovered to obtain amination-modified polystyrene porous microspheres. These microspheres can be activated and reused in the synthesis system. A small amount of microspheres may be lost during the activation process; this loss should be controlled within the specified usage range. The filtrate is concentrated under reduced pressure to recover the polar solvent, which can also be reused in the synthesis system. A poor solvent is added to the distillation residue to precipitate a solid, yielding crude diazonoquinone sulfonate. This crude product is then purified by solvent extraction and vacuum dried to obtain diazonoquinone sulfonate. The yield of refined diazonoquinone sulfonate obtained using this method is consistently higher than 90%, and its total purity, as determined by HPLC, is ≥99.0%.

[0031] Beneficial effects: The raw materials used in this invention are all industrially available, inexpensive, and readily available commercially; in addition, the fusarium ether and polar solvent can be recycled and reused, which not only saves costs but also makes the synthesis process more environmentally friendly, avoiding the generation of more industrial waste liquid; the diazonaphthoquinone sulfonate obtained by this method has a very high yield, with a yield of more than 90%; electronic-grade diazonaphthoquinone sulfonate initiators can be easily obtained using electronic-grade raw materials and solvents to meet the requirements of high-end photoresists; the simple operation and low cost of the process make it very suitable for industrialization and can be widely promoted and used. Detailed Implementation

[0032] The present invention will be further described in detail below through embodiments.

[0033] The raw materials used in this scheme can be easily processed into low-metal-content electronic-grade materials. Electronic-grade solvents are commonly available commercially, and polystyrene microspheres (particle size: 50-100 micrometers) and chemical reagents are also commercially available. In addition, the fusible acid agent and polar solvent can be reused, resulting in low cost. It is convenient and controllable to obtain diazonaphthoquinone sulfonate initiators with low metal content suitable for lithography machines. Furthermore, the reaction temperature is not high, and the reaction environment is relatively mild, avoiding harsh and dangerous environments, making it suitable for industrial promotion.

[0034] Example 1: Synthesis of the diazonoquinone sulfonate photoinitiator PAC-3215

[0035]

[0036] or H

[0037] Under nitrogen protection, 8.0 L of dioxane and 0.46 kg (2.0 mol) of 2,3,4-trihydroxybenzophenone were added sequentially to a stirred 20 L reaction flask. 1.44 kg of amino-modified polystyrene porous microspheres were then added, and the mixture was stirred at 35 °C until fully combined. 1.34 kg (5.0 mol) of 2-diazo-1-naphthol-5-sulfonyl chloride was dissolved in 5 L of dioxane at room temperature. The sulfonyl chloride solution was slowly added dropwise to the 20 L reaction flask while stirring at 35 °C. After the addition was complete, the reaction was kept at a constant temperature for 12 hours until it was fully reacted. After cooling to room temperature, the amination-modified polystyrene porous microspheres were recovered by filtration. The dioxane was directly concentrated under reduced pressure to remove the dioxane (recycled). The crude product was washed with petroleum ether, filtered, and dried to obtain the yellow solid diazonoquinone sulfonate photoinitiator PAC-3215 with a yield of 92.2% (HPLC: 99.5%) and a total metal content of 23 ppb.

[0038] The obtained amino-modified polystyrene porous microspheres hydrochloride were washed with 10 L of dioxane at 100°C for 5 h, then with 10 L of concentrated ammonia at 50°C for 10 h, followed by washing with 10 L of purified water at 90°C. The microspheres were then vacuum dried at 100°C for 24 h. After cooling, 1.30 kg of amino-modified polystyrene porous microspheres were obtained, with a recovery rate of 97%. The recovered amino-modified polystyrene porous microspheres were reused 8 times (with new microspheres added to any insufficient quantity each time). The yield and quality of the resulting diazonoquinone sulfonate photoinitiator PAC-3215 remained almost unchanged.

[0039] Example 2: Synthesis of the diazonoquinone sulfonate photoinitiator PAC-4215

[0040]

[0041] Or H

[0042] Under nitrogen protection, 8.0 L of dioxane and 0.49 kg (2.0 mol) of 2,3,4,4'-tetrahydroxybenzophenone were added sequentially to a stirred 20 L reaction flask. 1.44 kg of amino-modified polystyrene porous microspheres were then added, and the mixture was stirred and stirred at 35 °C until fully combined. 1.34 kg (5.0 mol) of 2-diazo-1-naphthol-5-sulfonyl chloride was dissolved in 5 L of dioxane at room temperature. The sulfonyl chloride solution was slowly added dropwise to the 20 L reaction flask while stirring at 35 °C. After the addition was complete, the reaction was kept at a constant temperature for 12 hours until it was fully reacted. After cooling to room temperature, the amination-modified polystyrene porous microspheres were recovered by filtration. The dioxane was directly concentrated under reduced pressure to remove the dioxane (recycled). The crude product was washed with petroleum ether, filtered, and dried to obtain the yellow solid diazonoquinone sulfonate photoinitiator PAC-4215 with a yield of 95.2% (HPLC: 99.5%) and a total metal content of 18 ppb.

[0043] The obtained amino-modified polystyrene porous microspheres hydrochloride were washed with 10 L of dioxane at 100°C for 5 h, then with 10 L of concentrated ammonia at 50°C for 10 h, followed by washing with 10 L of purified water at 90°C. The microspheres were then vacuum dried at 100°C for 24 h. After cooling, 1.30 kg of amino-modified polystyrene porous microspheres were obtained, with a recovery rate of 97%. The recovered amino-modified polystyrene porous microspheres were reused 8 times (with new microspheres added to any insufficient quantity each time). The yield and quality of the resulting diazonium naphthoquinone sulfonate photoinitiator PAC-4215 remained almost unchanged.

[0044] Example 3: Synthesis of the diazonoquinone sulfonate photoinitiator PAC-TPPA

[0045]

[0046] Or H

[0047] Under nitrogen protection, 8.0 L of dioxane and 0.85 kg (2.0 mol) of 4-[4-[1,1-bis(4-hydroxyphenyl)ethyl]]-α,α-dimethylbenzylphenol (Trisp-PA) were added sequentially to a stirred 20 L reaction flask. 1.44 kg of amino-modified polystyrene porous microspheres were then added, and the mixture was stirred at 35 °C until fully combined. 1.34 kg (5.0 mol) of 2-diazo-1-naphthol-5-sulfonyl chloride was dissolved in 5 L of dioxane at room temperature. The sulfonyl chloride solution was slowly added dropwise to the 20 L reaction flask while stirring at 35 °C. After the addition was complete, the reaction was kept at a constant temperature for 12 hours until it was fully reacted. After cooling to room temperature, the amination-modified polystyrene porous microspheres were recovered by filtration. The dioxane was directly concentrated under reduced pressure to remove the dioxane (recycled). The crude product was washed with petroleum ether, filtered, and dried to obtain the solid diazonium naphthoquinone sulfonate photoinitiator PAC-TPPA with a yield of 96.2% (HPLC: 99.7%) and a total metal content of 15 ppb.

[0048] The obtained amino-modified polystyrene porous microspheres hydrochloride were washed with 10 L of dioxane at 100°C for 5 h, then with 10 L of concentrated ammonia at 50°C for 10 h, followed by washing with 10 L of purified water at 90°C. The microspheres were then vacuum dried at 100°C for 24 h. After cooling, 1.30 kg of amino-modified polystyrene porous microspheres were obtained, with a recovery rate of 97%. The recovered amino-modified polystyrene porous microspheres were reused 8 times (with new microspheres added to any insufficient quantity), and the yield and quality of the resulting diazonoquinone sulfonate photoinitiator PAC-TPPA remained almost unchanged.

[0049] Example 4: Synthesis of the diazonoquinone sulfonate photoinitiator PAC-TPBE

[0050]

[0051] Or H

[0052] Under nitrogen protection, 8.0 L of dioxane and 0.61 kg (2.0 mol) of tris(hydroquinone)methane were added sequentially to a stirred 20 L reaction flask. 1.44 kg of amino-modified polystyrene porous microspheres were then added, and the mixture was stirred at 35 °C until fully combined. 1.34 kg (5.0 mol) of 2-diazo-1-naphthol-5-sulfonyl chloride was dissolved in 5 L of dioxane at room temperature. The sulfonyl chloride solution was slowly added dropwise to the 20 L reaction flask while stirring at 35 °C. After the addition was complete, the reaction was maintained at this temperature for 12 hours until complete. The mixture was then cooled to room temperature, and the amino-modified polystyrene porous microspheres were recovered by filtration. The dioxane was directly concentrated under reduced pressure (recycled). The crude product was washed with petroleum ether, filtered, and dried to obtain the solid diazononaphthoquinone sulfonate photoinitiator PAC-TPBE with a yield of 97.1% (HPLC: 99.8%) and a total metal content of 30 ppb.

[0053] The obtained amino-modified polystyrene porous microspheres hydrochloride were washed with 10 L of dioxane at 100°C for 5 h, then with 10 L of concentrated ammonia at 50°C for 10 h, followed by washing with 10 L of purified water at 90°C. The microspheres were then vacuum dried at 100°C for 24 h. After cooling, 1.30 kg of amino-modified polystyrene porous microspheres were obtained, with a recovery rate of 97%. The recovered amino-modified polystyrene porous microspheres were reused 8 times (with new microspheres added to any insufficient quantity), and the yield and quality of the resulting diazonoquinone sulfonate photoinitiator PAC-TPBE remained almost unchanged.

[0054] Example 5: Synthesis of the diazonoquinone sulfonate photoinitiator PAC-DPBE

[0055]

[0056] Or H

[0057] Under nitrogen protection, 8.0 L of dioxane and 0.45 kg (2.0 mol) of bisphenol A were added sequentially to a stirred 20 L reaction flask. 1.44 kg of amino-modified polystyrene porous microspheres were then added, and the mixture was stirred at 35 °C until fully combined. 1.34 kg (5.0 mol) of 2-diazo-1-naphthol-5-sulfonyl chloride was dissolved in 5 L of dioxane at room temperature. The sulfonyl chloride solution was slowly added dropwise to the 20 L reaction flask while stirring at 35 °C. After the addition was complete, the reaction was maintained at this temperature for 12 hours until complete. The mixture was then cooled to room temperature, and the amino-modified polystyrene porous microspheres were recovered by filtration. The dioxane was directly concentrated under reduced pressure (recycled). The crude product was washed with petroleum ether, filtered, and dried to obtain the solid diazononaphthoquinone sulfonate photoinitiator PAC-DPBE with a yield of 93.1% (HPLC: 99.6%) and a total metal content of 26 ppb.

[0058] The obtained amino-modified polystyrene porous microspheres hydrochloride were washed with 10 L of dioxane at 100°C for 5 h, then with 10 L of concentrated ammonia at 50°C for 10 h, followed by washing with 10 L of purified water at 90°C. The microspheres were then vacuum dried at 100°C for 24 h. After cooling, 1.30 kg of amino-modified polystyrene porous microspheres were obtained, with a recovery rate of 97%. The recovered amino-modified polystyrene porous microspheres were reused 8 times (with new microspheres added to any insufficient quantity each time). The yield and quality of the resulting diazonoquinone sulfonate photoinitiator PAC-DPBE remained almost unchanged.

[0059] Example 6: Synthesis of the diazonoquinone sulfonate photoinitiator PAC-DOBO

[0060]

[0061] Or H

[0062] Under nitrogen protection, 8.0 L of dioxane and 0.49 kg (2.0 mol) of bisphenol A were added sequentially to a stirred 20 L reaction flask. 1.44 kg of amino-modified polystyrene porous microspheres were then added, and the mixture was stirred at 35 °C until fully combined. 1.34 kg (5.0 mol) of 2-diazo-1-naphthol-5-sulfonyl chloride was dissolved in 5 L of dioxane at room temperature. The sulfonyl chloride solution was slowly added dropwise to the 20 L reaction flask while stirring at 35 °C. After the addition was complete, the reaction was maintained at this temperature for 12 hours until complete. The mixture was then cooled to room temperature, and the amino-modified polystyrene porous microspheres were recovered by filtration. The dioxane was directly concentrated under reduced pressure (recycled). The crude product was washed with petroleum ether, filtered, and dried to obtain the solid diazononaphthoquinone sulfonate photoinitiator PAC-DOBO with a yield of 94.1% (HPLC: 99.8%) and a total metal content of 28 ppb.

[0063] The obtained amino-modified polystyrene porous microspheres hydrochloride were washed with 10 L of dioxane at 100°C for 5 h, then with 10 L of concentrated ammonia at 50°C for 10 h, followed by washing with 10 L of purified water at 90°C. The microspheres were then vacuum dried at 100°C for 24 h. After cooling, 1.30 kg of amino-modified polystyrene porous microspheres were obtained, with a recovery rate of 97%. The recovered amino-modified polystyrene porous microspheres were reused 8 times (with new microspheres added to any insufficient quantity each time). The yield and quality of the resulting diazonoquinone sulfonate photoinitiator PAC-DOBO remained almost unchanged.

[0064] In summary: the raw materials used in this invention are all industrially available, inexpensive, and readily available commercially; furthermore, the fusarium ether and polar solvent can be recycled and reused, which not only saves costs but also makes the synthesis process more environmentally friendly, avoiding the generation of more industrial waste liquid; the diazonaphthoquinone sulfonate obtained by this method has a very high yield, exceeding 90%; electronic-grade diazonaphthoquinone sulfonate initiators can be easily obtained using electronic-grade raw materials and solvents to meet the requirements of high-end photoresists; the simple operation and low cost of the process make it highly suitable for industrialization and can be widely promoted and used.

[0065] The above description is only a preferred embodiment of the present invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the inventive concept of the present invention, and these should also be considered within the scope of protection of the invention.

Claims

1. A method for synthesizing the photoinitiator diazonaquinone sulfonate, characterized in that: Includes the following steps: Step 1: Using diazonaphthol sulfonyl chloride and phenolic hydroxyl compounds as raw materials, and amino-modified polystyrene porous microspheres as acid-absorbing agents, the reaction is carried out in a polar solvent at a constant temperature to obtain the first product; Step 2: Filter the first product obtained in Step 1 to recover the amino-modified polystyrene porous microsphere hydrochloride. Step 3: Post-process the amino-modified polystyrene porous microsphere hydrochloride obtained in Step 2 to obtain crude diazonoquinone sulfonate; Step 4: The crude diazonoquinone sulfonate from Step 3 is pulped, washed, filtered, and dried to obtain the product diazonoquinone sulfonate.

2. The method for synthesizing the photoinitiator diazonoquinone sulfonate according to claim 1, characterized in that, The phenolic hydroxyl compound mentioned in step one is a monohydroxy substituted phenol, a polyhydroxy substituted phenol, or a compound having a phenolic hydroxyl structure.

3. The method for synthesizing the photoinitiator diazonoquinone sulfonate according to claim 1, characterized in that, In step one, the molar ratio of the phenolic hydroxyl compound and the diazonopyranosulfonyl chloride is 1:0.7-5.0, and the molar ratio of the amino groups in the diazonopyranosulfonyl chloride and the acetic acid is 1:0.8-5.

4. The method for synthesizing the photoinitiator diazonaquinone sulfonate according to claim 1, characterized in that, The polar solvent mentioned in step one is one or more of 1,2-dichloroethane, chloroform, carbon tetrachloride, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, toluene, xylene, N,N-dimethylformamide, or N,N-dimethylacetamide.

5. The method for synthesizing the photoinitiator diazonaquinone sulfonate according to claim 1, characterized in that, The preparation method of the amino-modified polystyrene porous microspheres in step one is as follows: S1. Polystyrene microspheres were added to 98wt% concentrated sulfuric acid at a ratio of 1:30 g / mL, reacted at 50℃ for 12 h, filtered, washed with water, and dried under vacuum at 60℃ to obtain sulfonated polystyrene microspheres. S2. The sulfonated polystyrene microspheres were reacted in diethylamine aqueous solution at 120°C for 24 hours, filtered, washed with water, then soaked and neutralized in dioxane at 60°C, filtered, and vacuum dried at 60°C to obtain amino-modified polystyrene porous microspheres.

6. The method for synthesizing the photoinitiator diazonaquinone sulfonate according to claim 1, characterized in that, The temperature for the heat preservation reaction in step one is -40 to 120℃.

7. The method for synthesizing the photoinitiator diazonaquinone sulfonate according to claim 6, characterized in that, The temperature for the heat preservation reaction in step one is 10-50℃.

8. The method for synthesizing the photoinitiator diazonoquinone sulfonate according to claim 1, characterized in that, The amino-modified polystyrene porous microsphere hydrochloride recovered in step two was soaked and washed with 10 L of dioxane at 100 °C for 5 h, then soaked and washed with 10 L of concentrated ammonia at 50 °C for 10 h, and then soaked and washed with 10 L of pure water at 90 °C. After being vacuum dried at 100 °C for 24 h, the amino-modified polystyrene porous microspheres were obtained by cooling and then put back into the synthesis system for reuse.

9. The method for synthesizing the photoinitiator diazonoquinone sulfonate according to claim 1, characterized in that, The post-processing in step three includes vacuum distillation to recover the polar solvent or adding a poor solvent to precipitate the solid; the poor solvent is one or more of petroleum ether, n-hexane, isohexane, water, methanol, ethanol or acetone.

10. The method for synthesizing the photoinitiator diazonoquinone sulfonate according to claim 9, characterized in that, The solvent mentioned in step four is petroleum ether.

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