A method for synthesizing PHS resin with narrow molecular weight distribution

Abstract

This application belongs to the field of functional polymer materials, and specifically relates to a method for synthesizing a PHS-based resin with a narrow molecular weight distribution. The advantages include: 1. Continuous flow chemical synthesis of the PHS-based resin using a microchannel reaction system. 2. Initiation using a composite initiator composed of an azo-based and multifunctional peroxy initiator. This method solves the problems of poor production safety and unstable product quality caused by thermal instability during the polymerization process. The resulting PHS-based resin has a PDI of ≤1.2 and metal impurities of ≤0.5 ppb, making it suitable for the preparation of KrF photoresist films.

Description

Technical Field

[0001] The present invention belongs to the field of functional polymer materials, and specifically relates to a method for synthesizing a PHS resin with a narrow molecular weight distribution. Background Art

[0002] KrF photoresist is a key material in integrated circuit manufacturing, consisting of resin, photosensitizer, solvent, and additives. Poly(p-hydroxystyrene) resin (PHS resin) is the primary material for chemically amplified photoresist (KrF). PHS resins with a molecular weight distribution (PDI) of ≤1.2 are known as narrow molecular weight distribution PHS resins. These resins can be used to prepare thin films of KrF photoresist, offering high resolution after development and meeting the requirements of process nodes from 130nm to 180nm.

[0003] In the prior art, methods for obtaining PHS resins with narrow molecular weight distributions include anionic polymerization, RAFT living radical polymerization, and ATRP living radical polymerization. Although these methods can produce PHS resins with narrow molecular weight distributions, anionic polymerization faces the challenge of removing metal ions, while RAFT and ATRP living radical polymerization methods face the challenge of removing chain transfer agents. Furthermore, all of these methods utilize traditional kettle polymerization, which still faces issues such as slow heat and mass transfer, difficulty in precise temperature control, difficulty in efficiently removing oxygen, and batch-to-batch product instability caused by the volatility of solvents and monomers, poor process control, and significant scale-up effects. Summary of the Invention

[0004] In order to solve the above problems, the present invention provides a method for synthesizing a PHS-based resin with a narrow molecular weight distribution.

[0005] The specific technical solution provided by the present invention is as follows: A method for synthesizing a PHS resin with a narrow molecular weight distribution, characterized in that it comprises the following steps:

[0006] 1) Cleaning the microchannel reaction system, dissolving the monomer and the azo initiator into a solvent to prepare a liquid for use; mixing the organic base or organic acid with the solvent for use;

[0007] 2) Setting the microchannel reaction temperature to 60-70° C. in the first temperature zone, 70-95° C. in the second temperature zone, and 50-55° C. in the third temperature zone; starting the monomer feed pump, the azo initiator feed pump, the multifunctional peroxy initiator feed pump, and the organic base and / or organic acid feed pump;

[0008] 3) Monomers, azo initiators, multifunctional peroxidase initiators, organic bases or organic acids enter the microchannel reactor through a feed pump, and the reaction pressure in the microchannel is adjusted to 1.5-10 bar;

[0009] 4) Receive the reaction liquid sample at the sampling port for online analysis. If the test results are qualified, switch the terminal valve to the product tank, which contains pure water under stirring, and the product is precipitated in the water; after the reaction is completed, close the valve, filter the product, and send the product for sampling and testing.

[0010] The present application also provides a reaction system for running the synthesis method, characterized in that: the microchannel reaction system includes an injection pump, a micromixer, a microreactor, a back pressure valve, a sampling port, a waste liquid pipe and a product tank; wherein the number of the micromixer and the microreactor is multiple; micromixer 1, microreactor 1, micromixer 2, microreactor 2, micromixer 3 and microreactor 3 are connected in sequence;

[0011] Among them, pure water, monomer, azo initiator and solvent enter the micro mixer 1 through the injection pump respectively, and flow into the micro reactor 1 after being mixed;

[0012] The multifunctional peroxy initiator enters the micro mixer 2 through the feed pump and enters the microreactor 2 after mixing;

[0013] The organic acid / base enters the micro mixer 3 through the feed pump and enters the microreactor 3 after mixing; it can be switched to the waste liquid tank, product tank and sampling port through the back pressure valve; the back pressure valve is used to limit the pressure of the system and switch the pipeline connection.

[0014] The beneficial effects of the present invention are:

[0015] 1. The PHS resin obtained by this invention has a PDI of ≤1.2, belonging to a PHS resin with a narrow molecular weight distribution, and the metal ion impurity content of the product is ≤0.5ppb. It is suitable for the preparation of KrF photoresist films.

[0016] 2. This invention uses a microchannel reactor for flow chemistry reactions, avoiding the batch-to-batch instability, difficult process control, and significant scale-up issues associated with traditional kettle reactors. The preparation process of the present invention can be industrialized and scaled up, ensuring reliable product quality.

[0017] 3. Generally, azo initiators have a longer reaction time, but the molecular weight distribution of the product is wider. Peroxide initiators initiate the reaction faster, but the reaction speed is too fast to control. Compared with single-component initiators, the use of composite initiators can more effectively control the polymerization reaction.

[0018] 4. Typically, composite initiators face the problem of uneven initiation due to uneven initiator distribution, resulting from localized over-concentration of one type of initiator. This invention utilizes the powerful mass transfer capability of the microchannel reactor to more effectively mix the two initiators through a mixer, thus avoiding the problem of uneven initiation.

[0019] 5. This application uses general free radical polymerization to avoid the difficulty of removing chain transfer agents. At the same time, a composite initiator and a microchannel reactor are used to react, which enhances the mass transfer and mixing effect of the initiator. Different initiators are added to different degrees in the reaction to ensure the stability of the concentration of free radicals in the system. Multifunctional peroxidation initiators give the polymerization reaction the characteristics of easy control and high product conversion rate, thereby further reducing the PDI of the product. At the same time, the microchannel reactor has the advantages of enhanced heat transfer, enhanced mass transfer, precise temperature control, precise control of polymerization reaction rate and time, easy oxygen removal, no monomer solvent volatilization, etc., and the use of flow chemistry production gets rid of the problems of instability between batches of kettle reactions, difficult process control, and obvious amplification effect. The characteristics of efficient mass transfer and heat transfer and small liquid holding capacity also further reduce the PDI of the product. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 A schematic diagram of a detection system provided in one embodiment of the present application. DETAILED DESCRIPTION

[0021] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0022] One embodiment of the present application provides a method for synthesizing a PHS-based resin with a narrow molecular weight distribution, characterized by comprising the following steps:

[0023] 1) Cleaning the microchannel reaction system, dissolving the monomer and the azo initiator into a solvent to prepare a liquid for use; mixing the organic base or organic acid with the solvent for use;

[0024] 2) Setting the microchannel reaction temperature to 60-70° C. in the first temperature zone, 70-95° C. in the second temperature zone, and 50-55° C. in the third temperature zone; starting the monomer feed pump, the azo initiator feed pump, the multifunctional peroxy initiator feed pump, and the organic base and / or organic acid feed pump;

[0025] 3) Monomers, azo initiators, multifunctional peroxidase initiators, organic bases or organic acids enter the microchannel reactor through a feed pump, and the reaction pressure in the microchannel is adjusted to 1.5-10 bar;

[0026] 4) Receive the reaction liquid sample at the sampling port for online analysis. If the test results are qualified, switch the terminal valve to the product tank, which contains pure water under stirring, and the product is precipitated in the water; after the reaction is completed, close the valve, filter the product, and send the product for sampling and testing.

[0027] In one embodiment, the solvent is a water-soluble organic solvent, and the water-soluble solvent is one or more of ethanol, isopropanol, n-butanol, 1,4-dioxane, DMSO, DMF, NMP, and PGMEA.

[0028] In one embodiment, the monomer is one or more of styrene, p-tert-butoxystyrene, p-acetoxystyrene, p-(1-ethoxyethoxy)styrene, p-vinylphenyl tert-butyl carbonate, tert-butyl acrylate, and m-tert-butoxystyrene.

[0029] In one embodiment, the azo initiator is one or more of azobisisobutyronitrile, dimethyl azobisisobutyrate, azobisisobutyramidine hydrochloride, or azobisisobutylimidazoline hydrochloride;

[0030] The multifunctional peroxy initiator is one of 1,1-bis(tert-butylperoxy)cyclohexane, diperoxyester 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)ethane, 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxynonane, and tetra-tert-butylperoxytetracarbonate.

[0031] In one embodiment, the organic acid includes one or more of p-toluenesulfonic acid, acetic acid, methanesulfonic acid, trifluoroacetic acid, benzoic acid, oxalic acid, and aminosulfonic acid; the organic base includes one or more of ammonia water, ethylenediamine, hydrazine hydrate, diethylamine, triethylamine, and DMAP.

[0032] In one embodiment, the molar ratio of the synthesis process materials is monomer: azo initiator: peroxide initiator: organic acid / base = 1:2%-4%:1%-4%:20%-40%.

[0033] In one embodiment, the steps of cleaning the microchannel reaction system are as follows: first, start the feed pump, pass pure water into the microchannel reaction system, and wait until the water outlet at the tail connection is detected to be less than 0.1 ppb, then use electronic grade isopropyl alcohol to flush the microchannel reaction system, and wait until the isopropyl alcohol outlet at the tail connection is detected to be less than 0.1 ppb; and blow nitrogen through the microchannel reaction system for 5-8 hours.

[0034] One embodiment of the present application further provides a reaction system for running the synthesis method, characterized in that: the microchannel reaction system includes an injection pump, a micromixer, a microreactor, a back pressure valve, a sampling port, a waste liquid pipe and a product tank; wherein the number of the micromixer and the microreactor is multiple; micromixer 1, microreactor 1, micromixer 2, microreactor 2, micromixer 3 and microreactor 3 are connected in sequence;

[0035] Among them, pure water, monomer, azo initiator and solvent enter the micro mixer 1 through the injection pump respectively, and flow into the micro reactor 1 after being mixed;

[0036] The multifunctional peroxy initiator enters the micro mixer 2 through the feed pump and enters the microreactor 2 after mixing;

[0037] The organic acid / base enters the micro mixer 3 through the feed pump and enters the micro reactor 3 after mixing; it can be switched to the waste liquid tank, product tank and sampling port through the back pressure valve; the back pressure valve is used to limit the pressure of the system and switch the pipeline connection. Figure 1 .

[0038] Example 1

[0039] 1. Microchannel system cleaning. Install the equipment in place, turn on the pure water feed pump, and flush the pipeline with pure water. When the gold impurity concentration in the pure water at the sampling port is ≤0.1ppb, turn off the pure water feed pump, switch to isopropyl alcohol, and start cleaning the pipeline. When the isopropyl alcohol concentration at the sampling port is ≤0.1ppb, switch to high-purity nitrogen to purge the pipeline for 5-8 hours, close the valve and set aside.

[0040] 2. Prepare the ingredients before the reaction. Dissolve 12.5 kg of p-acetoxystyrene in 25 kg of DMSO and connect the solution to the monomer feed pump. Dissolve 0.35 kg of dimethyl azobisisobutyrate in 25 kg of DMSO and connect the solution to the azo initiator feed pump. Dissolve 0.8 kg of tetra-tert-butyl peroxytetracarbonate in 25 kg of DMSO and connect the solution to the multifunctional peroxy initiator feed pump. Dissolve 1.5 kg of triethylamine in 25 kg of DMSO and connect the solution to the organic acid / base feed pump.

[0041] Turn on the heater and set the first temperature zone to 70°C, the second temperature zone to 90°C, and the third temperature zone to 50°C.

[0042] 3. Start each feed pump at a flow rate of 0.2 mL / min: 0.2 mL / min: 0.2 mL / min: 0.2 mL / min. Adjust the reaction system pressure to 5 bar using the backpressure valve. Receive a sample of the reaction liquid at the sampling port for online analysis to test for single metal impurity content and molecular weight distribution. Once the test results are satisfactory, switch the terminal valve to the product tank. The product tank contains continuously stirred pure water. Any product that drips out will precipitate in the product tank. Filter the solid in the product tank under reduced pressure, and dry the residue in a vacuum oven at 80°C for 18 hours. This yields an off-white, yellowish solid. The product is then tested. The results are shown in Table 1.

[0043] Example 2

[0044] 1. Microchannel system cleaning. Install the equipment in place, turn on the pure water feed pump, and flush the pipeline with pure water. When the gold impurity concentration in the pure water at the sampling port is ≤0.1ppb, turn off the pure water feed pump, switch to isopropyl alcohol, and start cleaning the pipeline. When the isopropyl alcohol concentration at the sampling port is ≤0.1ppb, switch to high-purity nitrogen to purge the pipeline for 5-8 hours, close the valve and set aside.

[0045] 2. Preparation before the reaction. Dissolve 12.5 kg of p-acetoxystyrene in 25 kg of DMF and connect the solution to the monomer feed pump. Dissolve 0.25 kg of azobisisobutyronitrile in 25 kg of DMF and connect the solution to the azo initiator feed pump. Dissolve 0.2 kg of tetra-tert-butyl peroxytetracarbonate in 25 kg of DMF and connect the solution to the multifunctional peroxy initiator feed pump. Dissolve 1.5 kg of triethylamine in 25 kg of DMF and connect the solution to the organic acid / base feed pump.

[0046] Turn on the heater and set the first temperature zone to 70°C, the second temperature zone to 90°C, and the third temperature zone to 50°C.

[0047] 3. Start each feed pump at a flow rate of 0.2 mL / min: 0.2 mL / min: 0.2 mL / min: 0.2 mL / min. Adjust the reaction system pressure to 5 bar using the backpressure valve. Receive a sample of the reaction liquid at the sampling port for online analysis to test for single metal impurity content and molecular weight distribution. Once the test results are satisfactory, switch the terminal valve to the product tank. The product tank contains continuously stirred pure water. Any product that drips out will precipitate in the product tank. Filter the solid in the product tank under reduced pressure, and dry the residue in a vacuum oven at 80°C for 18 hours. This yields an off-white, yellowish solid. The product is then tested. The results are shown in Table 1.

[0048] Example 3

[0049] 1. Microchannel system cleaning. Install the equipment in place, turn on the pure water feed pump, and flush the pipeline with pure water. When the gold impurity concentration in the pure water at the sampling port is ≤0.1ppb, turn off the pure water feed pump, switch to isopropyl alcohol, and start cleaning the pipeline. When the isopropyl alcohol concentration at the sampling port is ≤0.1ppb, switch to high-purity nitrogen to purge the pipeline for 5-8 hours, close the valve and set aside.

[0050] 2. Prepare the ingredients before the reaction. Dissolve 5.1 kg of p-tert-butoxystyrene, 3.3 kg of styrene, and 4 kg of tert-butyl acrylate in 25 kg of DMSO and connect the solution to the monomer feed pump. Dissolve 0.35 kg of dimethyl azobisisobutyrate in 25 kg of DMSO and connect the solution to the azo initiator feed pump. Dissolve 0.8 kg of tetratert-butyl peroxytetracarbonate in 25 kg of DMSO and connect the solution to the multifunctional peroxy initiator feed pump. Dissolve 1.5 kg of triethylamine in 25 kg of DMSO and connect the solution to the organic acid / base feed pump.

[0051] Turn on the heater and set the first temperature zone to 70°C, the second temperature zone to 90°C, and the third temperature zone to 50°C.

[0052] 3. Start each feed pump at a flow rate of 0.2 mL / min: 0.2 mL / min: 0.2 mL / min: 0.2 mL / min. Adjust the reaction system pressure to 5 bar using the backpressure valve. Receive a sample of the reaction liquid at the sampling port for online analysis to test for single metal impurity content and molecular weight distribution. Once the test results are satisfactory, switch the terminal valve to the product tank. The product tank contains continuously stirred pure water. Any product that drips out will precipitate in the product tank. Filter the solid in the product tank under reduced pressure, and dry the residue in a vacuum oven at 80°C for 18 hours. This yields an off-white, yellowish solid. The product is then tested. The results are shown in Table 1.

[0053] Comparative Example 1

[0054] 1. Microchannel system cleaning. Install the equipment in place, turn on the pure water feed pump, and flush the pipeline with pure water. When the gold impurity concentration in the pure water at the sampling port is ≤0.1ppb, turn off the pure water feed pump, switch to isopropyl alcohol, and start cleaning the pipeline. When the isopropyl alcohol concentration at the sampling port is ≤0.1ppb, switch to high-purity nitrogen to purge the pipeline for 5-8 hours, close the valve and set aside.

[0055] 2. Prepare the ingredients before the reaction. Dissolve 12.5 kg of p-acetoxystyrene in 25 kg of DMSO and connect the solution to the monomer feed pump. Dissolve 0.35 kg of dimethyl azobisisobutyrate in 25 kg of DMSO and connect the solution to the azo initiator feed pump. Dissolve 0.37 kg of dibenzoyl peroxide in 25 kg of DMSO and connect the solution to the multifunctional peroxy initiator feed pump. Dissolve 1.5 kg of triethylamine in 25 kg of DMSO and connect the solution to the organic acid / base feed pump.

[0056] Turn on the heater and set the first temperature zone to 70°C, the second temperature zone to 90°C, and the third temperature zone to 50°C.

[0057] 3. Start each feed pump at a flow rate of 0.2 mL / min: 0.2 mL / min: 0.2 mL / min: 0.2 mL / min. Adjust the reaction system pressure to 5 bar using the backpressure valve. Receive a sample of the reaction liquid at the sampling port for online analysis to test for single metal impurity content and molecular weight distribution. Once the test results are satisfactory, switch the terminal valve to the product tank. The product tank contains continuously stirred pure water. Any product that drips out will precipitate in the product tank. Filter the solid in the product tank under reduced pressure, and dry the residue in a vacuum oven at 80°C for 18 hours. This yields an off-white, yellowish solid. The product is then tested. The results are shown in Table 1.

[0058] Comparative Example 2

[0059] 1. Microchannel system cleaning. Install the equipment in place, turn on the pure water feed pump, and flush the pipeline with pure water. When the gold impurity concentration in the pure water at the sampling port is ≤0.1ppb, turn off the pure water feed pump, switch to isopropyl alcohol, and start cleaning the pipeline. When the isopropyl alcohol concentration at the sampling port is ≤0.1ppb, switch to high-purity nitrogen to purge the pipeline for 5-8 hours, close the valve and set aside.

[0060] 2. Prepare the ingredients before the reaction. Dissolve 12.5 kg of p-acetoxystyrene in 25 kg of DMSO and connect the solution to the monomer feed pump. Dissolve 0.35 kg of dimethyl azobisisobutyrate in 25 kg of DMSO and connect the solution to the azo initiator feed pump. Dissolve 0.8 kg of tetra-tert-butyl peroxytetracarbonate in 25 kg of DMSO and connect the solution to the multifunctional peroxy initiator feed pump. Dissolve 1.5 kg of triethylamine in 25 kg of DMSO and connect the solution to the organic acid / base feed pump.

[0061] Turn on the heater and set the first temperature zone to 90°C, the second temperature zone to 90°C, and the third temperature zone to 50°C.

[0062] 3. Start each feed pump at a flow rate of 0.2 mL / min: 0.2 mL / min: 0.2 mL / min: 0.2 mL / min. Adjust the reaction system pressure to 5 bar using the backpressure valve. Receive a sample of the reaction liquid at the sampling port for online analysis to test for single metal impurity content and molecular weight distribution. Once the test results are satisfactory, switch the terminal valve to the product tank. The product tank contains continuously stirred pure water. Any product that drips out will precipitate in the product tank. Filter the solid in the product tank under reduced pressure, and dry the residue in a vacuum oven at 80°C for 18 hours. This yields an off-white, yellowish solid. The product is then tested. The results are shown in Table 1.

[0063] Comparative Example 3

[0064] Use a kettle reactor. First, clean the kettle reactor several times with pure water and isopropanol. Blow dry with nitrogen and set aside. Pour nitrogen into the reactor, and add 12.5kg of para-acetoxystyrene, 0.35kg of dimethyl azobisisobutyrate and 50kg of DMSO into the kettle. Stir and heat to 70°C. After a period of reaction, add a solution of 0.8kg of tetrabutyl peroxide tetracarbonate dissolved in 25kg of DMSO and heat to 90°C. React for 10h. After the reaction is completed, cool to 50°C and add a solution of 1.5kg of triethylamine dissolved in 25kg of DMSO. React for 5 hours. Slowly drip into the continuously stirred pure water, filter the precipitated solid under reduced pressure, and bake the residue in a vacuum oven at 80°C for 18h. A white to yellowish solid is obtained. The product is tested. The results are shown in Table 1

[0065] Table 1. Gold impurity content and molecular weight distribution test results

[0066] Metal ion content Molecular weight distribution Example 1 0.2ppb 1.05 Example 2 0.5ppb 1.13 Example 3 0.2ppb 1.05 Comparative Example 1 0.6ppb 1.33 Comparative Example 2 0.2ppb 1.42 Comparative Example 3 1ppb 1.76

[0067] According to the test results obtained in this example, the PHS resin prepared in this application has a PDI of ≤1.2, which is a PHS resin with a narrow molecular weight distribution, and the metal ion impurities in the product are ≤0.5ppb. However, the use of monofunctional dibenzoyl peroxide in Comparative Example 1 resulted in a chaotic initiation during polymerization, with the molecular weight distribution broadening to 1.33, no longer meeting the requirements for a PHS resin with a narrow molecular weight distribution. In Comparative Example 2, the temperature of the first temperature zone was set to 90 degrees. At this temperature, the initiation rate of the azo initiator was too fast, resulting in a broadening of the molecular weight distribution to 1.42 during polymerization, no longer meeting the requirements for a PHS resin with a narrow molecular weight distribution. In Comparative Example 3, the reaction was switched from a microchannel reactor to a kettle reactor. Kettle reactors are inferior to microchannel reactors in terms of heat and mass transfer, precise temperature control, accurate control of polymerization reaction rate and time, easy oxygen removal, and no monomer solvent volatilization. Furthermore, they have a large liquid holdup, which leads to an increase in molecular weight distribution during polymerization, resulting in a PDI of 1.76. Furthermore, kettle reactors are more susceptible to environmental influences, leading to metal ion concentrations reaching 1 ppb. This no longer satisfies the narrow molecular weight distribution requirements for PHS resins. Therefore, using a microchannel reactor, a multifunctional peroxide initiator, and a combination of an azo initiator and a multifunctional peroxide initiator in the aforementioned manner can achieve the required PHS resin PDI ≤ 1.2. This approach is suitable for the preparation of KrF photoresist films.

[0068] By comparing Comparative Examples 1, 2, and 3 with Example 1, it can be seen that the advantages of multifunctional oxygen-free initiators, precise temperature ranges, and microfluidic channel reactions are apparent.

[0069] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A method for synthesizing a PHS-based resin with a narrow molecular weight distribution, characterized in that: The steps include: 1) Cleaning the microchannel reaction system, dissolving the monomer and the azo initiator into a solvent to prepare a liquid for use; mixing the organic base or organic acid with the solvent for use; 2) Setting the microchannel reaction temperature to 60-70° C. in the first temperature zone, 70-95° C. in the second temperature zone, and 50-55° C. in the third temperature zone; starting the monomer feed pump, the azo initiator feed pump, the multifunctional peroxy initiator feed pump, and the organic base and / or organic acid feed pump; 3) Monomers, azo initiators, multifunctional peroxidase initiators, organic bases or organic acids enter the microchannel reactor through a feed pump, and the reaction pressure in the microchannel is adjusted to 1.5-10 bar; 4) Receive the reaction liquid sample at the sampling port for online analysis. If the test result is qualified, switch the terminal valve to the product tank, which contains pure water under stirring, and the product is precipitated in the water. After the reaction is completed, close the valve, filter the product, and send the product for sampling and testing; Wherein, the monomer is p-tert-butoxystyrene or p-acetoxystyrene; The microchannel reaction system includes an injection pump, a micromixer, a microreactor, a back pressure valve, a sampling port, a waste liquid pipe and a product tank; wherein the number of the micromixer and the microreactor is multiple; micromixer 1, microreactor 1, micromixer 2, microreactor 2, micromixer 3 and microreactor 3 are connected in sequence; Among them, pure water, monomer, azo initiator and solvent enter the micro mixer 1 through the injection pump respectively, and flow into the micro reactor 1 after being mixed; The multifunctional peroxidation initiator enters the micro mixer 2 through the feed pump and enters the micro reactor 2 after mixing; The organic acid / base enters the micro mixer 3 through the feed pump and enters the microreactor 3 after mixing; it can be switched to the waste liquid tank, product tank and sampling port through the back pressure valve; the back pressure valve is used to limit the pressure of the system and switch the pipeline connection.

2. The synthesis method according to claim 1, wherein: The solvent is one or more of ethanol, isopropanol, n-butanol, 1,4-dioxane, DMSO, DMF, NMP, and PGMEA.

3. The synthesis method according to claim 1, wherein: The azo initiator is one or more of azobisisobutyronitrile, dimethyl azobisisobutyrate, azobisisobutyramidine hydrochloride or azobisisobutylimidazoline hydrochloride; The multifunctional peroxy initiator is one of 1,1-bis(tert-butylperoxy)cyclohexane, diperoxyester 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)ethane, 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxynonane, and tetra-tert-butylperoxytetracarbonate.

4. The synthesis method according to claim 1, wherein: The organic acid includes one or more of p-toluenesulfonic acid, acetic acid, methanesulfonic acid, trifluoroacetic acid, benzoic acid, oxalic acid, and aminosulfonic acid; the organic base includes one or more of ammonia water, ethylenediamine, hydrazine hydrate, diethylamine, triethylamine, and DMAP.

5. The synthesis method according to claim 1, wherein: The material molar ratio of the synthesis method is monomer: azo initiator: peroxide initiator: organic acid / base = 1: 2%-4%: 1%-4%: 20%-40%.

6. The synthesis method according to claim 1, wherein: The cleaning process of the microchannel reaction system comprises the following steps: firstly starting the feed pump, introducing pure water into the microchannel reaction system, and detecting that the water output at the tail connection is less than 0.1 ppb; then flushing the microchannel reaction system with electronic-grade isopropyl alcohol, and detecting that the isopropyl alcohol output at the tail connection is less than 0.1 ppb; and blowing nitrogen through the microchannel reaction system for 5-8 hours.

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