Method and system for preparing sulfonium salt photoacid generator based on microchannel technology

Abstract

The invention relates to the technical field of preparation of photoacid generators, in particular to a method and system for preparing a sulfonium salt photoacid generator based on a microchannel technology. The method comprises the following steps: under the action of an activating agent, carrying out substitution reaction on an aromatic compound and an aromatic sulfoxide compound in a solution form in a microchannel reactor to obtain a sulfonium salt compound; sequentially quenching and distilling the sulfonium salt compound to obtain a sulfonium salt photoacid generator product; wherein the aromatic hydrocarbon compound is shown as a formula 1, and the formula 1 is shown in the description; the aromatic sulfoxide compound is shown as a formula 2; the activating agent is shown as a formula 3. According to the method, the yield of the sulfonium salt photoacid generator reaches 80% or above and the purity reaches 98% or above based on the cooperation among the core advantages of the microchannel reactor, the structural adaptability of reactants and an activating agent and the precise control of the quenching process.

Description

Technical Field

[0001] This application relates to the field of photoacid-generating agent preparation technology, and in particular to a method and system for preparing sulfonium salt-based photoacid-generating agents based on microchannel technology. Background Technology

[0002] Microchannel reactor (MCR) technology is one of the core technologies in the field of process intensification and is known as the "chip of the chemical plant". MCR technology reduces the size of the reaction channels in the reactor to the micrometer level (usually 10 μm to 500 μm). Its advantages are mainly reflected in the following aspects: (1) Extremely high efficiency: fast heat and mass transfer, good mixing effect, which can significantly improve the reaction rate and product yield. (2) Safe and reliable: the liquid holding capacity in the reactor is very small, which can inherently safely handle high temperature, high pressure, flammable and explosive dangerous chemical reactions. (3) Precise control: precise control of parameters such as reaction temperature and residence time, fewer side reactions, and high and stable product quality. (4) Seamless scale-up: by increasing the number of reaction channels (rather than increasing the size), the production capacity can be increased, avoiding the difficulties of traditional chemical scale-up and shortening the research and development production cycle. (5) Green and environmentally friendly: the reactor consumes less reagents and has high reaction selectivity, which reduces waste generation from the source. Photoresist is an essential material in the semiconductor chip industry. Its main components are polymer resin, photoacid generator, and corresponding additives (alkaline additives, dissolution inhibitors, etc.) and solvents. The photoacid generator (PAG) is the core component of chemically amplified photoresist; it does not directly participate in film formation but releases hydrogen ions (H2O) after exposure. + Ions, through an acid-catalyzed chain reaction, alter the solubility of the resin, enabling micro- and nano-scale pattern transfer. This reaction process is a chemically amplified process, greatly improving the sensitivity and efficiency of the photolithography process. Without high-performance PAGs, modern advanced photolithography technologies (such as DUV and EUV) would not be possible.

[0003] Among different types of photoacid generators, sulfonium salts have attracted much attention due to their excellent solubility, photosensitivity and thermal stability. This has led to the synthesis of sulfonium salts being a key focus of research and development in the chemical industry. At present, the main methods for preparing sulfonium salts include: (1) Cu(II) catalytic reaction of aryl sulfides with aryl iodine salts. This process requires only one step and can produce sulfonium salts with high yield under relatively mild conditions. It is currently the mainstream synthesis process. However, since the key raw material aryl iodine salt is used at the equivalent level, there are drawbacks such as difficulty in synthesizing aryl iodine salt and high price; (2) Aryl Grignard reagent and aryl sulfoxide reaction process. This process requires the preparation of the corresponding aryl Grignard reagent first. The reaction between the Grignard reagent and aryl sulfoxide is relatively violent, and the occurrence of side reactions will lead to a high defect rate of sulfonium salts. In addition, the high risk of active metals and Grignard reagents further limits the industrial application of this process; (3) the reaction process of aryl compounds and sulfone compounds under perfluorosulfonic anhydride catalysis. This process can obtain high yields of sulfonium salt photoacid generator products through a one-step reaction at room temperature. However, in actual production, due to the violent exothermic reaction, in order to reduce the generation of reaction impurities, the reaction temperature needs to be lowered to -40℃ or even lower to avoid possible side reactions such as multiple substitution. Summary of the Invention

[0004] This application provides a method and system for preparing sulfonium salt-based photoacid generators based on microchannel technology, in order to solve the following technical problem: how to simultaneously improve the yield and purity of sulfonium salt-based photoacid generators.

[0005] In a first aspect, embodiments of this application provide a method for preparing sulfonium salt-based photoacid-generating agents based on microchannel technology, the method comprising: Under the action of an activator, aromatic compounds and aromatic sulfoxide compounds are subjected to a substitution reaction in solution form in a microchannel reactor to obtain sulfonium salt compounds; The sulfonium salt compounds were sequentially quenched and distilled to obtain sulfonium salt photoacid-producing agents; wherein the aromatic compounds have the molecular structure shown in Formula 1. , Formula 1; In Formula 1, R1 includes at least one of fluorine, chlorine, bromine, iodine, hydrogen, methyl, ethyl, n-butyl, tert-butyl, methoxy, phenoxy, and phenylthio; R2 includes at least one of fluorine, chlorine, bromine, iodine, hydrogen, methyl, ethyl, n-butyl, tert-butyl, methoxy, phenoxy, and phenylthio; R3 includes at least one of fluorine, chlorine, bromine, iodine, hydrogen, methyl, ethyl, n-butyl, tert-butyl, methoxy, phenoxy, and phenylthio. The aromatic sulfoxide compound has the molecular structure shown in Formula 2. , Equation 2, In Formula 2, R4 includes at least one of fluorine, iodine, hydrogen, methyl and tert-butyl; R5 includes at least one of fluorine, iodine, hydrogen, methyl and tert-butyl; R6 includes at least one of fluorine, iodine, hydrogen, methyl and tert-butyl. The activator has a molecular structure as shown in Formula 3. , Formula 3, In Formula 3, R7 is any one of C1-containing perfluoroalkyl to C10-containing perfluoroalkyl.

[0006] Optionally, the amount of the aromatic compound n1 and the amount of the aromatic sulfoxide compound n2 satisfy: n1:n2 = (5:1) to (1:5). The amount of the activator n3 and the amount of the aromatic sulfoxide compound n4 satisfy: n3:n4 = (5:1) to (1:5).

[0007] Optionally, the sulfonium salt photoacid-generating agent product has a molecular structure as shown in Formula 4. , Equation 4, In Formula 4, R1 includes at least one of fluorine, chlorine, bromine, iodine, hydrogen, methyl, ethyl, n-butyl, tert-butyl, methoxy, phenoxy, and phenylthio; R2 includes at least one of fluorine, chlorine, bromine, iodine, hydrogen, methyl, ethyl, n-butyl, tert-butyl, methoxy, phenoxy, and phenylthio; R3 includes at least one of fluorine, chlorine, bromine, iodine, hydrogen, methyl, ethyl, n-butyl, tert-butyl, methoxy, phenoxy, and phenylthio; R4 includes at least one of fluorine, iodine, hydrogen, methyl, and tert-butyl; R5 includes at least one of fluorine, iodine, hydrogen, methyl, and tert-butyl; R6 includes at least one of fluorine, iodine, hydrogen, methyl, and tert-butyl; and R7 is any one of C1-containing perfluoroalkyl to C10-containing perfluoroalkyl.

[0008] Optionally, R7 includes trifluoromethyl or nonafluorobutyl.

[0009] Optionally, the temperature of the substitution reaction is from -40°C to 60°C, and the duration of the substitution reaction is from 1 min to 60 min; and / or The quenching temperature is from -20°C to 40°C, and the quenching time is from 1 min to 10 min.

[0010] Optionally, the solvent used in the substitution reaction includes at least one of benzene, toluene, tert-butylbenzene, carbon tetrachloride, chloroform, dichloromethane, and 1,2-dichloroethane.

[0011] Optionally, under the solution conditions, the activator has a mass concentration of 5% to 80%, the aromatic compound has a mass concentration of 5% to 80%, and the aromatic sulfoxide compound has a mass concentration of 5% to 80%.

[0012] Optionally, the activator has a mass concentration of 5% to 40%, and the aromatic compound and the aromatic sulfoxide compound have mass concentrations of 30% to 60%, respectively.

[0013] Optionally, the microchannel reactor includes a first pipeline and a second pipeline, wherein the volumetric flow rates of the first pipeline and the second pipeline are 0.1 mL / min to 180 mL / min, respectively.

[0014] Secondly, embodiments of this application provide a system for preparing sulfonium salt photoacid-generating agents based on microchannel technology, the system being adapted to the method described in the first aspect, the system comprising: The microchannel reaction unit includes a first mixing tank, a second mixing tank, a first pipeline, a second pipeline, and a microchannel reactor. The inlet of the first pipeline is connected to the outlet of the first mixing tank, the inlet of the second pipeline is connected to the outlet of the second mixing tank, the outlet of the first pipeline is connected to the inlet of the microchannel reactor, and the outlet of the second pipeline is connected to the inlet of the microchannel reactor. The quenching reaction section includes a pure water storage tank and a quenching reactor. The inlet of the quenching reactor is connected to the outlet of the microchannel reactor, and the outlet of the pure water storage tank is connected to the inlet of the quenching reactor. A distillation reactor, wherein the outlet of the quenching reactor is connected to the inlet of the distillation reactor; The metering pump assembly includes a first metering pump, a second metering pump, a third metering pump, and a fourth metering pump. The first metering pump is fixedly connected between the first pipeline and the microchannel reactor. The second metering pump is fixedly connected between the second pipeline and the microchannel reactor. The third metering pump is fixedly connected between the pure water storage tank and the quenching reactor. The fourth metering pump is fixedly connected between the quenching reactor and the quenching reactor.

[0015] The technical solutions provided in this application have the following advantages compared with the prior art: This application provides a method for preparing sulfonium salt-based photoacid generators based on microchannel technology. This method leverages the excellent mass transfer, heat transfer, and uniform dispersion characteristics of microchannel reactors, allowing for thorough mixing and reaction between aromatic compounds, aromatic sulfoxide compounds, and activators during the substitution reaction stage. This results in the large-scale and directional formation of the target sulfonium salt-based photoacid generator, improving its yield and purity. Furthermore, designing specific structures for the aromatic compounds, aromatic sulfoxide compounds, and activators can promote selective reaction of their functional groups, reducing side reactions and increasing the purity of the sulfonium salt-based photoacid generator. In addition, designing a quenching process allows for precise control of the substitution reaction's progress, effectively improving the accuracy of the sulfonium salt-based photoacid generator's structure. Attached Figure Description

[0016] The accompanying drawings, which are incorporated in and form part of this specification, illustrate embodiments consistent with this application and, together with the description, serve to explain the principles of this application.

[0017] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, for those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0018] Figure 1 A schematic flowchart of a method for preparing sulfonium salt photoacid generators based on microchannel technology is provided for embodiments of this application; Figure 2 A schematic diagram illustrating the reaction principle of a method for preparing sulfonium salt photoacid-generating agents based on microchannel technology, provided in this application embodiment; Figure 3 A schematic diagram of the system logic structure for preparing sulfonium salt photoacid-generating agents based on microchannel technology is provided for embodiments of this application; Figure 4 A schematic diagram of the actual structure of a system for preparing sulfonium salt photoacid generators based on microchannel technology, provided for embodiments of this application; Figure 5 This is a schematic diagram illustrating the reaction principle of a method for preparing sulfonium salt photoacid generators based on microchannel technology, as provided in Embodiment 1 of this application. Figure 6 This is a schematic diagram illustrating the reaction principle of a method for preparing sulfonium salt photoacid generators based on microchannel technology, as provided in Embodiment 2 of this application. Figure 7 This is a schematic diagram illustrating the reaction principle of a method for preparing sulfonium salt photoacid generators based on microchannel technology, as provided in Embodiment 3 of this application. Figure 8This is a schematic diagram illustrating the reaction principle of a method for preparing sulfonium salt photoacid generators based on microchannel technology, as provided in Embodiment 4 of this application. Figure 9 This is a schematic diagram illustrating the reaction principle of a method for preparing sulfonium salt photoacid generators based on microchannel technology, as provided in Embodiment 5 of this application. Figure 10 This is a schematic diagram illustrating the reaction principle of a method for preparing sulfonium salt photoacid generators based on microchannel technology, as provided in Embodiment 6 of this application. Figure 11 This is a schematic diagram illustrating the reaction principle of a method for preparing sulfonium salt photoacid generators based on microchannel technology, as provided in Embodiment 7 of this application. Among them, 1-first mixing tank, 2-second mixing tank, 3-first pipeline, 4-second pipeline, 5-microchannel reactor, 6-pure water storage tank, 7-quenching reactor, 8-distillation reactor, 9-metering pump group, 901-first metering pump, 902-second metering pump, 903-third metering pump, 904-fourth metering pump. Detailed Implementation

[0019] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.

[0020] The range descriptions used in this application, such as numerical ranges and proportional ranges, include all possible sub-ranges and single numerical values ​​within that range. For example, the range descriptions of "1 to 6" or "1~6" cover all sub-ranges (such as 1 to 3, 2 to 5, etc.) and single numbers (such as 1, 2, 3, 4, 5, 6) between 1 and 6. Unless otherwise specified, the terms "comprising" and others used herein mean "including but not limited to"; relational terms such as "first" and "second" are used only to distinguish different entities or operations and do not imply an actual order or relationship; "and / or" indicates that multiple situations can exist individually or simultaneously; expressions such as "at least one," "multiple," and "at least one" refer to any combination of the corresponding objects, including combinations of single or multiple objects. The proportional relationships involved in this document, such as mass ratios and molar ratios, should be understood as the correspondence between the first and second terms of a proportional formula, according to the order of description. The raw materials, reagents, instruments, and equipment used herein can all be obtained by purchasing from the market or by existing methods.

[0021] Figure 1An exemplary embodiment of this application provides a schematic flowchart of a method for preparing sulfonium salt photoacid generators based on microchannel technology; like Figure 1 and Figure 2 As shown in the embodiments of this application, a method for preparing sulfonium salt photoacid-generating agents based on microchannel technology is provided, the method comprising: S1. Under the action of an activator, aromatic compounds and aromatic sulfoxide compounds are subjected to a substitution reaction in solution form in microchannel reactor 5 to obtain sulfonium salt compounds; S2. The sulfonium salt compound is sequentially quenched and distilled to obtain a sulfonium salt photoacid-producing agent product; wherein the aromatic compound has the molecular structure shown in Formula 1. , Formula 1; In Formula 1, R1 includes at least one of fluorine, chlorine, bromine, iodine, hydrogen, methyl, ethyl, n-butyl, tert-butyl, methoxy, phenoxy, and phenylthio; R2 includes at least one of fluorine, chlorine, bromine, iodine, hydrogen, methyl, ethyl, n-butyl, tert-butyl, methoxy, phenoxy, and phenylthio; R3 includes at least one of fluorine, chlorine, bromine, iodine, hydrogen, methyl, ethyl, n-butyl, tert-butyl, methoxy, phenoxy, and phenylthio. The aromatic sulfoxide compound has the molecular structure shown in Formula 2. , Equation 2, In Formula 2, R4 includes at least one of fluorine, iodine, hydrogen, methyl and tert-butyl; R5 includes at least one of fluorine, iodine, hydrogen, methyl and tert-butyl; R6 includes at least one of fluorine, iodine, hydrogen, methyl and tert-butyl. The activator has a molecular structure as shown in Formula 3. , Formula 3, In Formula 3, R7 is any one of C1-containing perfluoroalkyl to C10-containing perfluoroalkyl.

[0022] It should be noted that the quenching and distillation can be performed multiple times with ultrapure water to remove unreacted raw materials and impurities in the reaction solution.

[0023] It should be noted that the method for preparing sulfonium salt-based photoacid-generating agents based on microchannel technology provided in this application embodiment is based on the synergistic effect of the core advantages of the microchannel reactor 5, the structural compatibility between reactants and activators, and the precise control of the quenching process. This method simultaneously improves the yield and purity of sulfonium salt-based photoacid-generating agents from three dimensions: promoting the target reaction, inhibiting side reactions, and reducing impurity formation. The specific mechanism is as follows: 1. Microchannel Reactor 5: Reducing side reactions and improving conversion efficiency from the perspectives of mass transfer, heat transfer, and time control. The microscale structure of the microchannel reactor 5 (channel size is typically in the micrometer range) is the core hardware support for achieving improved yield and purity, and its advantages directly benefit key aspects of the substitution reaction: 1. Enhance mass transfer to avoid side reactions caused by uneven local concentrations. Aromatic compounds and aromatic sulfoxide compounds require a substitution reaction (the formation of thionium ions) under the action of an activator. In traditional batch reactors, reactants are prone to forming localized high-concentration zones due to uneven stirring (e.g., localized excess of activator, localized accumulation of a certain reactant, etc.). (1) If the activator is in excess locally, it may lead to over-activation of aromatic compounds and trigger multiple substitution side reactions (for example, multiple sites on the aromatic ring are attacked, generating non-target sulfonium salt impurities). (2) If reactants accumulate locally, self-polymerization or disproportionation reactions may occur (for example, the sulfur atoms of aromatic sulfoxides are excessively attacked, generating sulfides or sulfones as impurities). The material in the microchannel reactor 5 will be in a state of laminar flow or enhanced turbulence. The material in this state can achieve instantaneous and uniform mixing of reactants and activators, ensuring that the concentration of the three is uniform in the entire reaction system. This reduces the side reactions caused by local high concentrations from the source, allowing the raw materials to be converted into the target sulfonium salt photoacid generator more efficiently, improving the yield of sulfonium salt photoacid generator products, while reducing the generation of impurities and improving the purity of sulfonium salt photoacid generator products.

[0024] 2. Precise temperature control to suppress thermally induced side reactions and product decomposition. Substitution reactions (especially thionium ion formation reactions) are usually accompanied by some exothermic reaction. Traditional batch reactors are prone to local overheating due to their low heat transfer efficiency. (1) Overheating may cause the sulfur-oxygen bond of aromatic sulfoxides to break, generating impurities such as thiols and alkenes; (2) Overheating may also cause the generated sulfonium salt photoacid-producing agent to decompose (e.g., CS bond breakage), reducing the yield of the target product. The microchannel reactor 5 has a very large specific surface area, which can realize the immediate removal of reaction heat and control the reaction temperature within a low temperature range. This completely suppresses the side reactions and decomposition of sulfonium salt photoacid-producing agent caused by overheating, ensuring both full conversion of raw materials (increased yield) and avoiding the introduction of pyrolysis impurities (increased purity).

[0025] 3. Precise timing control to avoid overreaction or incomplete response. The microchannel reactor 5 has the characteristic of a fixed liquid holding volume, which allows for precise control of the residence time of the reactants. (1) The residence time is too short: the substitution reaction is incomplete, there is a lot of raw material residue, and the yield is low; (2) Excessive residence time: The target sulfonium salt may undergo secondary reactions with excess reactants (e.g., continued coupling with unreacted aromatic compounds to generate polyaryl sulfonium salt impurities). The residence time can be precisely controlled by adjusting the flow rate to ensure that the reaction proceeds completely (no raw material residue, maximizing yield) and is not excessive (no secondary side reactions, maximizing purity).

[0026] II. Structural Design of Reactants and Activators: Enhancing Reaction Selectivity and Reducing Ineffective Reactions By defining the substituents or structures of aromatic compounds (Formula 1), aromatic sulfoxide compounds (Formula 2), and activators (Formula 3), the substitution reaction can be directed at the molecular level, reducing ineffective side reactions. 1. Substituent compatibility between aromatic compounds (Formula 1) and aromatic sulfoxide compounds (Formula 2): (1) The selection of R1 to R3 (fluorine, methyl, tert-butyl, methoxy, etc.) in Formula 1 and R4 to R6 (fluorine, methyl, tert-butyl, etc.) in Formula 2 follows the principle of synergy between electronic and steric effects: 1) Electronic effects: Electron-donating groups such as methoxy and phenoxy can increase the electron cloud density of the aromatic ring, enhancing its ability to attack electron-deficient sulfur atoms in aromatic sulfoxides (promoting substitution reactions); electron-withdrawing groups such as fluorine and chlorine can moderately regulate the positive charge of sulfur atoms in aromatic sulfoxides, preventing them from being too reactive and triggering non-target attacks (such as attacking non-specific sites of other aromatics).

[0027] 2) Steric effect: Larger substituents such as tert-butyl and phenylthio can shield non-target reaction sites (e.g., ortho) on the aromatic ring, forcing the substitution reaction to occur at the para or meta position, reducing the formation of polysubstituted impurities. This substituent adaptability greatly improves the orientation of the substitution reaction, with almost all raw materials converted into the target sulfonium salt photoacid-producing agent (increasing yield) and without structural isomer impurities (increasing purity).

[0028] 2. The perfluoroalkyl structure of the activator (Formula 3): highly efficient activation + no residual impurities (1) In formula 3, R7 is a C1 perfluoroalkyl to C10 perfluoroalkyl group, and its core function is to efficiently activate the sulfur atom of aromatic sulfoxide without introducing impurities: 1) Perfluoroalkyl groups are strong electron-withdrawing groups. They can reduce the electron cloud density of sulfur atoms in aromatic sulfoxides through inductive effects, making them electrophilic centers that are easily attacked by aromatic compounds, thus greatly increasing the rate and conversion of substitution reactions (increasing yield). 2) Perfluoroalkyl groups are chemically stable and can be completely removed after the substitution reaction is completed by simple acid-base adjustment or extraction separation. They will not undergo side reactions with reactants or sulfonium salt photoacid generator products (for example, they will not couple with aromatic rings to form fluorinated impurities), thus avoiding the influence of activator residues on the purity of sulfonium salt photoacid generator products.

[0029] III. Quenching process: Rapidly terminates the reaction and locks in the target product. The core purpose of quenching is to terminate the reaction immediately and prevent the target product from further transforming into impurities. The precision of controlling the substitution reaction directly affects the final yield and purity. In traditional autoclave quenching, the quenching agent (such as a weak alkali or water) needs a period of time to diffuse after being added, which may result in unfinished reactions in some areas and the formation of hydrolysis products of sulfonium salts (such as sulfides or phenols). This application utilizes a microchannel reactor 5 to instantly mix the quencher and reaction solution at a microscale, enabling the quenching reaction to be completed in an extremely short time, completely avoiding subsequent decomposition or side reactions of the target product. Simultaneously, by controlling the concentration of the quencher (e.g., the pH value of a weak base) and the temperature, the stable existence of the quenching product (the target sulfonium salt photoacid generator) can be ensured, and the excess of the quencher will not lead to salt impurities (e.g., metal salts generated by excessive alkali), further improving purity.

[0030] In summary, this application provides a method for preparing sulfonium salt photoacid-generating agents based on microchannel technology. This method achieves simultaneous improvement in yield and purity through multi-stage synergy. It is based on a synergistic design of hardware (microchannel reactor 5) and software (molecular structure design + process control): (1) The microchannel reactor 5 solves the problems of poor mass transfer, difficult temperature control, and coarse time control in traditional batch reactors, and reduces side reactions at the process level; (2) The structural design of reactants and activators solves the problem of low reaction selectivity and ensures that the reaction occurs in a directional manner at the molecular level; (3) Precise quenching solves the problem of untimely reaction termination and targets the sulfonium salt photoacid generator from the post-processing level. Through the combined effect of the above three modules, the raw materials are converted into the target product to the greatest extent (increasing the yield) and the generation of impurities is suppressed throughout the process (increasing the purity), ultimately achieving a simultaneous increase in the yield and purity of the sulfonium salt photoacid generator.

[0031] In some alternative embodiments, the amount of the aromatic compound n1 and the amount of the aromatic sulfoxide compound n2 satisfy: n1:n2 = (5:1) to (1:5). The amount of the activator n3 and the amount of the aromatic sulfoxide compound n4 satisfy: n3:n4 = (5:1) to (1:5).

[0032] In these embodiments, the molar ratio of aromatic compounds and aromatic sulfoxide compounds in the range of (5:1) to (1:5) significantly enhances the orientation of the substitution reaction through a synergistic effect of electronic and steric effects. The raw materials are almost entirely converted into the target sulfonium salt photoacid-producing agent, with no structural isomer impurities. The molar ratio of activator and aromatic sulfoxide compounds in the range of (5:1) to (1:5) ensures sufficient activator in the substitution reaction. The perfluoroalkyl groups in the activator can significantly increase the rate and conversion of the substitution reaction, while avoiding the influence of activator residues on the purity of the sulfonium salt photoacid-producing agent product.

[0033] The amounts of the aromatic compound n1 and the aromatic sulfoxide compound n2 satisfy the following: n1:n2 = 5:1, 4:2, 3:3, 2:4 or 1:5.

[0034] The amount of the activator n3 and the amount of the aromatic sulfoxide compound n4 satisfy the following: n3:n4 = 5:1, 4:2, 3:3, 2:4 or 1:5.

[0035] In some alternative embodiments, the sulfonium salt photoacid-generating agent product has a molecular structure as shown in Formula 4. , Equation 4, In Formula 4, R1 includes at least one of fluorine, chlorine, bromine, iodine, hydrogen, methyl, ethyl, n-butyl, tert-butyl, methoxy, phenoxy, and phenylthio; R2 includes at least one of fluorine, chlorine, bromine, iodine, hydrogen, methyl, ethyl, n-butyl, tert-butyl, methoxy, phenoxy, and phenylthio; R3 includes at least one of fluorine, chlorine, bromine, iodine, hydrogen, methyl, ethyl, n-butyl, tert-butyl, methoxy, phenoxy, and phenylthio; R4 includes at least one of fluorine, iodine, hydrogen, methyl, and tert-butyl; R5 includes at least one of fluorine, iodine, hydrogen, methyl, and tert-butyl; R6 includes at least one of fluorine, iodine, hydrogen, methyl, and tert-butyl; and R7 is any one of C1-containing perfluoroalkyl to C10-containing perfluoroalkyl.

[0036] In these embodiments, by controlling the specific molecular structure of the sulfonium salt photoacid generator product, the reaction sites of aromatic compounds and aromatic sulfoxide compounds under the action of the activator during the substitution reaction can be clearly identified, thereby accurately obtaining the target sulfonium salt photoacid generator product.

[0037] In some alternative embodiments, R7 comprises trifluoromethyl or nonafluorobutyl.

[0038] In these embodiments, using R7 of trifluoromethyl or nonafluoro-n-butyl can clearly identify the specific type of perfluoroalkyl group in the activator, thereby further improving the rate and conversion of the substitution reaction and avoiding the influence of activator residue on the purity of the sulfonium salt photoacid generator product.

[0039] In some optional embodiments, the substitution reaction is carried out at a temperature of -40°C to 60°C, and the duration of the substitution reaction is from 1 min to 60 min; and / or The quenching temperature is from -20°C to 40°C, and the quenching time is from 1 min to 10 min.

[0040] In these embodiments, substitution reactions at temperatures ranging from -40°C to 60°C and lasting for 1 to 60 minutes promote the full reaction of aromatic compounds and aromatic sulfoxide compounds under the action of an activator, forming sulfonium salt-based photoacid-generating agents with specific structures. Furthermore, quenching reactions at temperatures ranging from -20°C to 40°C and lasting for 1 to 10 minutes allow for precise termination of the substitution reaction, yielding sulfonium salt-based photoacid-generating agents with specific structures.

[0041] The temperature for this substitution reaction can be -40℃, -30℃, -20℃, -10℃, 0℃, 10℃, 20℃, 30℃, 40℃, 50℃, or 60℃.

[0042] The duration of the substitution reaction can be 1 min, 2 min, 3 min, 4 min, 5 min, 6 min, 7 min, 8 min, 9 min, 10 min, 20 min, 30 min, 40 min, 50 min, or 60 min.

[0043] The quenching temperature can be -20℃, -10℃, 0℃, 10℃, 20℃, 30℃ or 40℃.

[0044] The quenching time can be 1 min, 2 min, 3 min, 4 min, 5 min, 6 min, 7 min, 8 min, 9 min, or 10 min.

[0045] In some alternative embodiments, the solvent used in the substitution reaction includes at least one of benzene, toluene, tert-butylbenzene, carbon tetrachloride, chloroform, dichloromethane, and 1,2-dichloroethane.

[0046] In these embodiments, the use of a solvent including at least one of benzene, toluene, tert-butylbenzene, carbon tetrachloride, chloroform, dichloromethane, and 1,2-dichloroethane can facilitate the substitution reaction of the activator, aromatic compound, and aromatic sulfoxide compound in solution to form a sulfonium salt photoacid generator with a specific structure.

[0047] In some alternative embodiments, under the solution conditions, the activator has a mass concentration of 5% to 80%, the aromatic compound has a mass concentration of 5% to 80%, and the aromatic sulfoxide compound has a mass concentration of 5% to 80%.

[0048] In these embodiments, the activator, the aromatic compound, and the aromatic sulfoxide compound at a mass concentration of 5% to 80% allow the three to undergo a substitution reaction in solution to form a sulfonium salt photoacid generator with a specific structure.

[0049] The mass concentration of the activator can be 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 50%, 60%, 70%, or 80%.

[0050] The mass concentration of the aromatic compound can be 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 50%, 60%, 70%, or 80%.

[0051] The mass concentration of the aromatic sulfoxide compound can be 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 50%, 60%, 70%, or 80%.

[0052] In some alternative embodiments, the activator has a mass concentration of 5% to 40%, and the aromatic compound and the aromatic sulfoxide compound have mass concentrations of 30% to 60%, respectively.

[0053] In these embodiments, the activator at a mass concentration of 5% to 40% and the aromatic compound and aromatic sulfoxide compound at mass concentrations of 30% to 60% respectively enable the three to undergo a substitution reaction in solution to form a sulfonium salt photoacid generator with a specific structure.

[0054] The mass concentration of the activator can be 5%, 10%, 15%, 20%, 25%, 30%, 35%, or 40%.

[0055] The mass concentrations of the aromatic compound and the aromatic sulfoxide compound can be 30%, 35%, 40%, 45%, 50%, 55%, or 60%, respectively.

[0056] In some alternative embodiments, the microchannel reactor 5 includes a first conduit 3 and a second conduit 4, the volumetric flow rates of the first conduit 3 and the second conduit 4 being 0.1 mL / min to 180 mL / min, respectively.

[0057] In these embodiments, the first line 3 and the second line 4, with volumetric flow rates of 0.1 mL / min to 180 mL / min, can facilitate the substitution reaction stage, ensuring thorough mixing between the aromatic compound, the aromatic sulfoxide compound, and the activator, thereby enabling the substitution reaction to proceed fully and forming a sulfonium salt photoacid generator with a specific structure.

[0058] The volumetric flow rates of the first pipeline 3 and the second pipeline 4 can be 0.1 mL / min, 0.2 mL / min, 0.3 mL / min, 0.4 mL / min, 0.5 mL / min, 1.0 mL / min, 2.0 mL / min, 3.0 mL / min, 4.0 mL / min, 5.0 mL / min, 10.0 mL / min, 15.0 mL / min, 20.0 mL / min, 30.0 mL / min, 40.0 mL / min, 50.0 mL / min, 100.0 mL / min, 150.0 mL / min, or 180.0 mL / min, respectively.

[0059] Figure 3 An exemplary schematic diagram of the system logic structure for preparing sulfonium salt photoacid generators based on microchannel technology is shown in an embodiment of this application. Figure 4 An exemplary schematic diagram of the actual structure of a system for preparing sulfonium salt photoacid generators based on microchannel technology provided in this application embodiment is shown; Based on a general inventive concept, such as Figure 3 and Figure 4 As shown in the embodiments of this application, a system for preparing sulfonium salt photoacid-generating agents based on microchannel technology is provided. The system is adapted to the method described above and includes: The microchannel reaction unit includes a first mixing tank 1, a second mixing tank 2, a first pipeline 3, a second pipeline 4, and a microchannel reactor 5. The inlet of the first pipeline 3 is connected to the outlet of the first mixing tank 1, the inlet of the second pipeline 4 is connected to the outlet of the second mixing tank 2, the outlet of the first pipeline 3 is connected to the inlet of the microchannel reactor 5, and the outlet of the second pipeline 4 is connected to the inlet of the microchannel reactor 5. The quenching reaction section includes a pure water storage tank 6 and a quenching reactor 7. The inlet of the quenching reactor 7 is connected to the outlet of the microchannel reactor 5, and the outlet of the pure water storage tank 6 is connected to the inlet of the quenching reactor 7. Distillation reactor 8, the outlet of the quenching reactor 7 is connected to the inlet of the distillation reactor 8; The metering pump group 9 includes a first metering pump 901, a second metering pump 902, a third metering pump 903, and a fourth metering pump 904. The first metering pump 901 is fixedly connected between the first pipeline 3 and the microchannel reactor 5. The second metering pump 902 is fixedly connected between the second pipeline 4 and the microchannel reactor 5. The third metering pump 903 is fixedly connected between the pure water storage tank 6 and the quenching reactor 7. The fourth metering pump 904 is fixedly connected between the quenching reactor 7 and the quenching reactor 7.

[0060] The system is implemented based on the above method. The specific steps of the method can be referred to the above embodiments. Since the system adopts some or all of the technical solutions of the above embodiments, it has at least all the beneficial effects brought about by the technical solutions of the above embodiments, which will not be elaborated here.

[0061] It should be noted that the microchannel reactor 5 includes an inner cylinder and an outer cylinder, and the gap between the inner cylinder and the outer cylinder of the microchannel reactor 5 is 1 mm to 2 mm.

[0062] It should be noted that the quenching reactor 7 can be a coil reactor.

[0063] It should be noted that both the microchannel reactor 5 and the quenching reactor 7 are equipped with an inlet and an outlet for heat transfer oil to maintain the temperature stability within the microchannel reactor 5 and the quenching reactor 7.

[0064] It should be noted that the first mixing vessel 1 and the second mixing vessel 2 can use 3L four-necked flasks equipped with a stirrer, a condenser and a thermometer, while the distillation reactor 8 can use 5L four-necked flasks equipped with a stirrer, a condenser and a thermometer.

[0065] It should be noted that a pressure gauge can be installed at the outlet of the first metering pump 901, the second metering pump 902, the third metering pump 903, and the fourth metering pump 904. A pressure gauge can also be installed between the microchannel reactor 5 and the quenching reactor 7 to monitor the material flow rate from different metering pumps in real time. This is beneficial for the entire system to adjust the material flow rate in real time (which can be achieved by the combined action of multiple sensors and controllers) and promote the full operation of each stage.

[0066] The present application is further illustrated below with reference to specific embodiments. Experimental methods in the following embodiments that do not specify specific conditions are generally determined according to national / industry standards; if there is no corresponding national / industry standard, they are performed according to general international standards, conventional conditions, or conditions recommended by the manufacturer.

[0067] Example 1 Figure 5An exemplary schematic diagram of the reaction principle of a method for preparing sulfonium salt photoacid generators based on microchannel technology provided in Embodiment 1 of this application is shown. like Figure 1 , Figure 2 and Figure 5 As shown, a method for preparing sulfonium salt photoacid-generating agents based on microchannel technology includes: S1. Under the action of an activator, aromatic compounds and aromatic sulfoxide compounds are subjected to a substitution reaction in solution form in microchannel reactor 5 to obtain sulfonium salt compounds; specific steps: 1400 mL of dichloromethane, 505.7 g of diphenyl sulfoxide (1.0 eq) and 293 g of benzene (1.5 eq) were first stirred and then introduced into the microchannel reactor 5 through the first pipeline 3; Then, 1100 mL of dichloromethane and 1058 g of trifluoromethanesulfonic anhydride (1.5 eq) were stirred and mixed, and introduced into the microchannel reactor 5 through the second pipeline 4; By controlling the temperature of the microchannel reactor 5, a substitution reaction is induced in the material inside the microchannel reactor 5 to obtain sulfonium salt compounds; S2. The sulfonium salt compounds are sequentially quenched and distilled to obtain sulfonium salt photoacid-generating agents; specific steps: The sulfonium salt compounds in the microchannel reactor 5 were quenched with water to obtain a quenching reaction solution. The quenching reaction solution was stirred and washed for 10 minutes with 1L of purified water, allowed to stand and separate into layers, the organic phase was retained, and the wastewater containing trifluoromethanesulfonic acid was stored separately for further recovery. The stirring and washing process was repeated twice to obtain the washed quenching reaction solution. The washing and quenching reaction solution was distilled to obtain sulfonium salt-based photoacid-generating agents.

[0068] Aromatic compounds have molecular structures as shown in Formula 1. , Formula 1; In Equation 1, R1 is hydrogen; R2 is hydrogen; R3 is hydrogen; Aromatic sulfoxide compounds have the molecular structure shown in Formula 2. , Equation 2, In Equation 2, R4 is hydrogen; R5 is hydrogen; R6 is hydrogen; The activator has a molecular structure as shown in Formula 3. , Formula 3, In Equation 3, R7 is CF3.

[0069] The amounts of the aromatic compound n1 and the aromatic sulfoxide compound n2 satisfy the following: n1:n2 = 1.5:1; The amount of activator n3 and the amount of aromatic sulfoxide compound n4 satisfy the following ratio: n3:n4 = 1.5:1.

[0070] R7 includes trifluoromethyl.

[0071] The substitution reaction was carried out at a temperature of 5°C for 40 minutes. The quenching temperature was 10℃ and the quenching time was 10 min.

[0072] The solvent used in the substitution reaction is dichloromethane.

[0073] Under solution conditions, the activator has a mass concentration of 5% to 40%, and the aromatic compounds and aromatic sulfoxide compounds have mass concentrations of 30% to 60%, respectively.

[0074] The microchannel reactor 5 includes a first pipeline 3 and a second pipeline 4, with volumetric flow rates of 45 mL / min for the first pipeline 3 and the second pipeline 4, respectively.

[0075] like Figure 3 and Figure 4 As shown, a system for preparing sulfonium salt photoacid-generating agents based on microchannel technology, and a system adaptation method, include: The microchannel reaction unit includes a first mixing tank 1, a second mixing tank 2, a first pipeline 3, a second pipeline 4, and a microchannel reactor 5. The inlet of the first pipeline 3 is connected to the outlet of the first mixing tank 1, the inlet of the second pipeline 4 is connected to the outlet of the second mixing tank 2, the outlet of the first pipeline 3 is connected to the inlet of the microchannel reactor 5, and the outlet of the second pipeline 4 is connected to the inlet of the microchannel reactor 5. The quenching reaction section includes a pure water storage tank 6 and a quenching reactor 7. The inlet of the quenching reactor 7 is connected to the outlet of the microchannel reactor 5, and the outlet of the pure water storage tank 6 is connected to the inlet of the quenching reactor 7. The outlet of the distillation reactor 8 and the quenching reactor 7 are connected to the inlet of the distillation reactor 8. The metering pump group 9 includes a first metering pump 901, a second metering pump 902, a third metering pump 903, and a fourth metering pump 904. The first metering pump 901 is fixedly connected between the first pipeline 3 and the microchannel reactor 5. The second metering pump 902 is fixedly connected between the second pipeline 4 and the microchannel reactor 5. The third metering pump 903 is fixedly connected between the pure water storage tank 6 and the quenching reactor 7. The fourth metering pump 904 is fixedly connected between the quenching reactor 7 and the quenching reactor 7.

[0076] Example 2

[0077] Compared to Example 1, the differences in this example are as follows, while the rest are the same: 1400 mL of dichloromethane, 505.7 g of diphenyl sulfoxide (1.0 eq) and 503 g of tert-butylbenzene (1.5 eq) were first stirred and then introduced into the microchannel reactor 5 through the first pipeline 3; Then, 1100 mL of dichloromethane and 1058 g of trifluoromethanesulfonic anhydride (1.5 eq) were stirred and mixed, and introduced into the microchannel reactor 5 through the second pipeline 4.

[0078] Figure 6 An exemplary schematic diagram of the reaction principle of a method for preparing sulfonium salt photoacid generators based on microchannel technology provided in Embodiment 2 of this application is shown. like Figure 6 As shown, aromatic compounds have molecular structures as shown in Formula 1. , Formula 1; In Formula 1, R1 is hydrogen; R2 is hydrogen; R3 is tert-butyl; Aromatic sulfoxide compounds have the molecular structure shown in Formula 2. , Equation 2, In Equation 2, R4 is hydrogen; R5 is hydrogen; R6 is hydrogen; The activator has a molecular structure as shown in Formula 3. , Formula 3, In Equation 3, R7 is CF3.

[0079] The amounts of the aromatic compound n1 and the aromatic sulfoxide compound n2 satisfy the following: n1:n2 = 1.5:1; The amount of activator n3 and the amount of aromatic sulfoxide compound n4 satisfy the following ratio: n3:n4 = 1.5:1.

[0080] R7 includes trifluoromethyl.

[0081] The substitution reaction was carried out at a temperature of 15°C for 40 minutes. The quenching temperature was 5℃ and the quenching time was 10 min.

[0082] The solvent used in the substitution reaction is dichloromethane.

[0083] The microchannel reactor 5 includes a first pipeline 3 and a second pipeline 4, with volumetric flow rates of 45 mL / min for the first pipeline 3 and the second pipeline 4, respectively.

[0084] Example 3 Compared to Example 1, the differences in this example are as follows, while the rest are the same: 1400 mL of dichloromethane, 505.7 g of diphenyl sulfoxide (1.0 eq) and 360 g of fluorobenzene (1.5 eq) were first stirred and then introduced into the microchannel reactor 5 through the first pipeline 3; Then, 1100 mL of dichloromethane and 1058 g of trifluoromethanesulfonic anhydride (1.5 eq) were stirred and mixed, and introduced into the microchannel reactor 5 through the second pipeline 4.

[0085] Figure 7 An exemplary schematic diagram of the reaction principle of a method for preparing sulfonium salt photoacid generators based on microchannel technology provided in Embodiment 3 of this application is shown. like Figure 7 As shown, aromatic compounds have molecular structures as shown in Formula 1. , Formula 1; In Formula 1, R1 is hydrogen; R2 is hydrogen; R3 is fluorine; Aromatic sulfoxide compounds have the molecular structure shown in Formula 2. , Equation 2, In Equation 2, R4 is hydrogen; R5 is hydrogen; R6 is hydrogen; The activator has a molecular structure as shown in Formula 3. , Formula 3, In Equation 3, R7 is CF3.

[0086] The amounts of the aromatic compound n1 and the aromatic sulfoxide compound n2 satisfy the following: n1:n2 = 1.5:1; The amount of activator n3 and the amount of aromatic sulfoxide compound n4 satisfy the following ratio: n3:n4 = 1.5:1.

[0087] R7 includes trifluoromethyl.

[0088] The substitution reaction was carried out at a temperature of 10°C for 40 minutes. The quenching temperature was 10℃ and the quenching time was 10 min.

[0089] The solvent used in the substitution reaction is dichloromethane.

[0090] The microchannel reactor 5 includes a first pipeline 3 and a second pipeline 4, with volumetric flow rates of 45 mL / min for the first pipeline 3 and the second pipeline 4, respectively.

[0091] Example 4 Compared to Example 1, the differences in this example are as follows, while the rest are the same: 1400 mL of dichloromethane, 575.8 g of xylene sulfoxide (1.0 eq) and 345.5 g of toluene (1.5 eq) were first stirred and then introduced into the microchannel reactor 5 through the first pipeline 3; Then, 1100 mL of dichloromethane and 1058 g of trifluoromethanesulfonic anhydride (1.5 eq) were stirred and mixed, and introduced into the microchannel reactor 5 through the second pipeline 4.

[0092] Figure 8 An exemplary schematic diagram of the reaction principle of a method for preparing sulfonium salt photoacid generators based on microchannel technology provided in Embodiment 4 of this application is shown. like Figure 8 As shown, aromatic compounds have molecular structures as shown in Formula 1. , Formula 1; In Formula 1, R1 is hydrogen; R2 is hydrogen; R3 is methyl; Aromatic sulfoxide compounds have the molecular structure shown in Formula 2. , Equation 2, In Formula 2, R4 is methyl; R5 is hydrogen; R6 is hydrogen; The activator has a molecular structure as shown in Formula 3. , Formula 3, In Equation 3, R7 is CF3.

[0093] The amounts of the aromatic compound n1 and the aromatic sulfoxide compound n2 satisfy the following: n1:n2 = 1.5:1; The amount of activator n3 and the amount of aromatic sulfoxide compound n4 satisfy the following ratio: n3:n4 = 1.5:1.

[0094] R7 includes trifluoromethyl.

[0095] The substitution reaction was carried out at a temperature of 20°C for 40 minutes. The quenching temperature was 5℃ and the quenching time was 10 min.

[0096] The solvent used in the substitution reaction is dichloromethane.

[0097] The microchannel reactor 5 includes a first pipeline 3 and a second pipeline 4, with volumetric flow rates of 45 mL / min for the first pipeline 3 and the second pipeline 4, respectively.

[0098] Example 5 Compared to Example 1, the differences in this example are as follows, while the rest are the same: 1400 mL of dichloromethane, 505.7 g of diphenyl sulfoxide (1.0 eq) and 576 g of toluene (2.5 eq) were first stirred and then introduced into the microchannel reactor 5 through the first pipeline 3; Then, 1100 mL of dichloromethane and 1058 g of trifluoromethanesulfonic anhydride (1.5 eq) were stirred and mixed, and introduced into the microchannel reactor 5 through the second pipeline 4.

[0099] Figure 9 An exemplary schematic diagram of the reaction principle of a method for preparing sulfonium salt photoacid generators based on microchannel technology provided in Embodiment 2 of this application is shown. like Figure 9 As shown, aromatic compounds have molecular structures as shown in Formula 1. , Formula 1; In Formula 1, R1 is hydrogen; R2 is hydrogen; R3 is methyl; Aromatic sulfoxide compounds have the molecular structure shown in Formula 2. , Equation 2, In Equation 2, R4 is hydrogen; R5 is hydrogen; R6 is hydrogen; The activator has a molecular structure as shown in Formula 3. , Formula 3, In Equation 3, R7 is CF3.

[0100] The amounts of the aromatic compound n1 and the aromatic sulfoxide compound n2 satisfy the following: n1:n2 = 2.5:1; The amount of activator n3 and the amount of aromatic sulfoxide compound n4 satisfy the following ratio: n3:n4 = 1.5:1.

[0101] R7 includes trifluoromethyl.

[0102] The substitution reaction was carried out at a temperature of 10°C for 40 minutes. The quenching temperature was 10℃ and the quenching time was 10 min.

[0103] The solvent used in the substitution reaction is dichloromethane.

[0104] The microchannel reactor 5 includes a first pipeline 3 and a second pipeline 4, with volumetric flow rates of 45 mL / min for the first pipeline 3 and the second pipeline 4, respectively.

[0105] Example 6 Compared to Example 1, the differences in this example are as follows, while the rest are the same: 1400 mL of dichloromethane, 505.7 g of diphenyl sulfoxide (1.0 eq) and 699 g of phenyl sulfide (1.5 eq) were first stirred and then introduced into the microchannel reactor 5 through the first pipeline 3. Then, 1100 mL of dichloromethane and 1058 g of trifluoromethanesulfonic anhydride (1.5 eq) were stirred and mixed, and introduced into the microchannel reactor 5 through the second pipeline 4.

[0106] Figure 10 An exemplary schematic diagram of the reaction principle of a method for preparing sulfonium salt photoacid generators based on microchannel technology provided in Embodiment 2 of this application is shown. like Figure 10 As shown, aromatic compounds have molecular structures as shown in Formula 1. , Formula 1; In Formula 1, R1 is hydrogen; R2 is hydrogen; R3 is phenylthio; Aromatic sulfoxide compounds have the molecular structure shown in Formula 2. , Equation 2, In Equation 2, R4 is hydrogen; R5 is hydrogen; R6 is hydrogen; The activator has a molecular structure as shown in Formula 3. , Formula 3, In Equation 3, R7 is CF3.

[0107] The amounts of the aromatic compound n1 and the aromatic sulfoxide compound n2 satisfy the following: n1:n2 = 1.5:1; The amount of activator n3 and the amount of aromatic sulfoxide compound n4 satisfy the following ratio: n3:n4 = 1.5:1.

[0108] R7 includes trifluoromethyl.

[0109] The substitution reaction was carried out at a temperature of 15°C for 40 minutes. The quenching temperature was 5℃ and the quenching time was 10 min.

[0110] The solvent used in the substitution reaction is dichloromethane.

[0111] The microchannel reactor 5 includes a first pipeline 3 and a second pipeline 4, with volumetric flow rates of 45 mL / min for the first pipeline 3 and the second pipeline 4, respectively.

[0112] Example 7 Compared to Example 1, the differences in this example are as follows, while the rest are the same: 1400 mL of dichloromethane, 505.7 g of diphenyl sulfoxide (1.0 eq) and 293 g of benzene (1.5 eq) were first stirred and then introduced into the microchannel reactor 5 through the first pipeline 3; Then, 1100 mL of dichloromethane and 2183 g of nonafluoro-n-butylsulfonic anhydride (1.5 eq) were stirred and mixed, and introduced into the microchannel reactor 5 through the second pipeline 4.

[0113] Figure 11 An exemplary schematic diagram of the reaction principle of a method for preparing sulfonium salt photoacid generators based on microchannel technology provided in Embodiment 2 of this application is shown. like Figure 11 As shown, aromatic compounds have molecular structures as shown in Formula 1. , Formula 1; In Equation 1, R1 is hydrogen; R2 is hydrogen; R3 is hydrogen; Aromatic sulfoxide compounds have the molecular structure shown in Formula 2. , Equation 2, In Equation 2, R4 is hydrogen; R5 is hydrogen; R6 is hydrogen; The activator has a molecular structure as shown in Formula 3. , Formula 3, In Equation 3, R7 is (CF2)3CF3.

[0114] The amounts of the aromatic compound n1 and the aromatic sulfoxide compound n2 satisfy the following: n1:n2 = 1.5:1; The amount of activator n3 and the amount of aromatic sulfoxide compound n4 satisfy the following ratio: n3:n4 = 1.5:1.

[0115] R7 includes nonafluorobutylene.

[0116] The substitution reaction was carried out at a temperature of 5°C for 40 minutes. The quenching temperature was 10℃ and the quenching time was 10 min.

[0117] The solvent used in the substitution reaction is dichloromethane.

[0118] The microchannel reactor 5 includes a first pipeline 3 and a second pipeline 4, with volumetric flow rates of 45 mL / min for the first pipeline 3 and the second pipeline 4, respectively.

[0119] Comparative Example 1 Compared to Example 1, the differences in this example are as follows, while the rest are the same: The conventional process for synthesizing a matonium salt photoacid-generating agent—triphenylthionium trifluoromethanesulfonate—is as follows: Take a 5L four-necked flask equipped with a stirrer, condenser, and thermometer. Add 2500mL of dichloromethane, 505.7g of diphenyl sulfoxide (1.0eq), and 293g of benzene (1.5eq) to the flask and stir until the solution is clear to obtain the raw material solution. Cool the raw material solution to -60℃ in a cold bath, and add 1058g of trifluoromethanesulfonic anhydride (1.5eq) dropwise under stirring, controlling the internal temperature not to exceed -50℃. The entire reaction process takes 4 hours. After the trifluoromethanesulfonic anhydride addition is complete, slowly raise the temperature to room temperature and continue stirring for 2 hours. After the reaction is complete, add 1L of purified water to the reaction product, stir for 10 minutes, and then allow to stand and separate the liquids. Retain the organic phase, wash the organic phase twice with water, collect the washed organic phase, and then evaporate the solvent from the organic phase to obtain triphenylthionium trifluoromethanesulfonate product.

[0120] Comparative Example 2 Compared to Example 1, the differences in this example are as follows, while the rest are the same: The sulfonium salt photoacid generator triphenylthionium trifluoromethanesulfonate was synthesized by reacting aryl sulfides with aryl iodonium salts under Cu(II) catalysis. The specific steps are as follows: Take a 5L four-necked flask equipped with a stirrer, condenser, and thermometer. Add 3000mL of dichloromethane, 408g of iodobenzene (1.0eq), and 609g of m-chloroperoxybenzoic acid (mCPBA, 85%, 1.5eq) to the flask and stir until the solution is clear to obtain the raw material solution. Cool the raw material solution to 0℃ in a cold bath, and add 234g of benzene (1.5eq) and 450g of trifluoromethanesulfonic acid (TfOH, 1.5eq) dropwise under stirring, controlling the internal temperature not to exceed 5℃. The entire reaction process takes 2 hours. After the trifluoromethanesulfonic anhydride is added, slowly raise the temperature to room temperature and continue stirring for 12 hours. After the reaction is complete, add 1L of purified water to the reaction product, stir for 10 minutes, and then allow it to stand and separate the liquids. Retain the organic phase, wash the organic phase twice with water, collect the washed organic phase, and then evaporate the solvent in the organic phase to obtain diphenyliodonium trifluoromethanesulfonate product.

[0121] Relevant experimental and effect data: The yield, production rate, and purity of sulfonium salt photoacid generators obtained from each implementation and comparative example were statistically analyzed, and the results are shown in Table 1.

[0122] Table 1. Yield, yield, and purity data of sulfonium salt photoacid generators in each example and comparative example.

[0123] As shown in Table 1, the method for preparing sulfonium salt-based photoacid generators based on microchannel technology provided in this application leverages the core advantages of the microchannel reactor 5, the structural compatibility between reactants and activators, and the synergistic effect of precise control over the quenching process. This method simultaneously improves the yield and purity of sulfonium salt-based photoacid generators from three dimensions: promoting the target reaction, inhibiting side reactions, and reducing impurity formation. The yield of sulfonium salt-based photoacid generators reaches over 80%, and the purity reaches over 98%.

[0124] Compared to Example 1, Comparative Example 1 uses a conventional process to synthesize sulfonium salt-based photoacid generators, which results in a lower overall yield and lower purity of sulfonium salt-based photoacid generators.

[0125] Compared to Example 1, Comparative Example 2 used a Cu(II) catalyzed reaction process between aryl sulfides and aryl iodonium salts. Although the purity of the final sulfonium salt photoacid generator was higher, the overall yield and productivity of the sulfonium salt photoacid generator were lower.

[0126] In summary, the embodiments of this application provide a method for preparing sulfonium salt photoacid generators based on microchannel technology. This method, based on the core advantages of the microchannel reactor 5, the structural compatibility between the reactants and activators, and the synergistic effect of precise control of the quenching process, enables the yield of sulfonium salt photoacid generators to reach more than 80% and the purity to reach more than 98%.

[0127] In addition, this application provides a method for preparing sulfonium salt photoacid generators based on microchannel technology. This method can not only obtain high-purity sulfonium salt photoacid generator products with higher yield and lower impurity content under milder conditions, but also effectively improve the safety and production efficiency of the reaction based on the advantages of microchannel technology.

[0128] Furthermore, this application provides a method for preparing sulfonium salt-based photoacid generators based on microchannel technology. This method solves the problems of harsh conditions and violent reactions in the synthesis of sulfonium salt-based photoacid generators. Microchannel technology improves the safety of the substitution reaction, making the reaction process more gentle and precisely controllable, and has the advantages of high production efficiency, low impurity generation, high yield, and stable quality. In addition, based on the specific structural design of the reaction raw materials in this application, this method also features high atom utilization, reduced solvent usage, and the ability to further recycle fluorine-containing byproducts, which not only meets the requirements of green chemistry but also significantly reduces production costs.

[0129] The above description is merely a specific embodiment of this application, enabling those skilled in the art to understand or implement this application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of this application. Therefore, this application is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features claimed in this application.

Claims

1. A method for preparing a sulfonium salt-based photo-acid generator based on microchannel technology, characterized by, The method comprises: under the action of an activating agent, an aromatic compound and an aromatic sulfoxide compound are subjected to a substitution reaction in a micro-channel reactor in a solution form to obtain a sulfonium salt compound; the sulfonium salt compound is subjected to quenching and distillation in sequence to obtain a sulfonium salt photo-acid generator product; wherein the aromatic compound has a molecular structure as shown in formula 1, ， Formula 1; in formula 1, R1 includes at least one of fluorine, chlorine, bromine, iodine, hydrogen, methyl, ethyl, n-butyl, tert-butyl, methoxy, phenoxy and phenylthio; R2 includes at least one of fluorine, chlorine, bromine, iodine, hydrogen, methyl, ethyl, n-butyl, tert-butyl, methoxy, phenoxy and phenylthio; and R3 includes at least one of fluorine, chlorine, bromine, iodine, hydrogen, methyl, ethyl, n-butyl, tert-butyl, methoxy, phenoxy and phenylthio; the aromatic sulfoxide compound has a molecular structure as shown in formula 2, ， Formula 2, in formula 2, R4 includes at least one of fluorine, iodine, hydrogen, methyl and tert-butyl; R5 includes at least one of fluorine, iodine, hydrogen, methyl and tert-butyl; and R6 includes at least one of fluorine, iodine, hydrogen, methyl and tert-butyl; the activating agent has a molecular structure as shown in formula 3, ， Formula 3, in formula 3, R7 is any one of a C1-containing perfluoroalkyl group to a C10-containing perfluoroalkyl group.

2. The method of claim 1, wherein, The amount of substance n1 of the aromatic compound and the amount of substance n2 of the aromatic sulfoxide compound satisfy: n1:n2=(5:1) to (1:5); The amount of substance n3 of the activating agent and the amount of substance n4 of the aromatic sulfoxide compound satisfy: n3:n4=(5:1) to (1:5).

3. The method of claim 1, wherein, The sulfonium salt photo-acid generator product has a molecular structure as shown in formula 4, ， Formula 4, in formula 4, R1 includes at least one of fluorine, chlorine, bromine, iodine, hydrogen, methyl, ethyl, n-butyl, tert-butyl, methoxy, phenoxy and phenylthio; R2 includes at least one of fluorine, chlorine, bromine, iodine, hydrogen, methyl, ethyl, n-butyl, tert-butyl, methoxy, phenoxy and phenylthio; R3 includes at least one of fluorine, chlorine, bromine, iodine, hydrogen, methyl, ethyl, n-butyl, tert-butyl, methoxy, phenoxy and phenylthio; R4 includes at least one of fluorine, iodine, hydrogen, methyl and tert-butyl; R5 includes at least one of fluorine, iodine, hydrogen, methyl and tert-butyl; R6 includes at least one of fluorine, iodine, hydrogen, methyl and tert-butyl; and R7 is any one of a C1-containing perfluoroalkyl group to a C10-containing perfluoroalkyl group.

4. The method according to claim 1 or 3, characterized in that, The R7 includes trifluoromethyl or nonafluoro-n-butyl.

5. The method of claim 1, wherein, The temperature of the substitution reaction is -40°C to 60°C, and the duration of the substitution reaction is 1 min to 60 min; and / or The temperature of the quenching is -20°C to 40°C, and the time of the quenching is 1 min to 10 min.

6. The method of claim 1, wherein, The kind of the solvent used in the substitution reaction includes at least one of benzene, toluene, tert-butylbenzene, carbon tetrachloride, chloroform, dichloromethane and 1,2-dichloroethane.

7. The method of claim 1, wherein, Under the solution state condition, the mass concentration of the activating agent is 5% to 80%, the mass concentration of the aromatic compound is 5% to 80%, and the mass concentration of the aromatic sulfoxide compound is 5% to 80%.

8. The method of claim 7, wherein, The mass concentration of the activator is 5% to 40%, and the mass concentrations of the aromatic hydrocarbon compound and the aromatic hydrocarbon sulfoxide compound are 30% to 60% respectively.

9. The method of claim 1, wherein, The micro-channel reactor comprises a first pipeline and a second pipeline, and the volume flow rates of the first pipeline and the second pipeline are 0.1 mL / min to 180 mL / min respectively.

10. A system for preparing onium salt-based photo-acid generators based on microchannel technology, characterized by, The system is adapted to the method according to any one of claims 1 to 9, and the system comprises: a micro-channel reaction part comprising a first mixing tank, a second mixing tank, a first pipeline, a second pipeline and a micro-channel reactor, a feed inlet of the first pipeline being communicated with a discharge outlet of the first mixing tank, a feed inlet of the second pipeline being communicated with a discharge outlet of the second mixing tank, a discharge outlet of the first pipeline being communicated with a feed inlet of the micro-channel reactor, and a discharge outlet of the second pipeline being communicated with a feed inlet of the micro-channel reactor; a quenching reaction part comprising a pure water storage tank and a quenching reactor, a feed inlet of the quenching reactor being communicated with a discharge outlet of the micro-channel reactor, and a liquid outlet of the pure water storage tank being communicated with a liquid inlet of the quenching reactor; a distillation reaction kettle, a discharge outlet of the quenching reactor being communicated with a feed inlet of the distillation reaction kettle; a metering pump group comprising a first metering pump, a second metering pump, a third metering pump and a fourth metering pump, the first metering pump being fixedly connected between the first pipeline and the micro-channel reactor, the second metering pump being fixedly connected between the second pipeline and the micro-channel reactor, the third metering pump being fixedly connected between the pure water storage tank and the quenching reactor, and the fourth metering pump being fixedly connected between the quenching reactor and the quenching reactor.

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