Preparation method and preparation system of resin material

Abstract

The invention provides a preparation method and a preparation system of a resin material, and the preparation method comprises the following steps: enabling a raw material system containing monomers to continuously enter a first reactor for polymerization reaction to obtain a first material liquid; the first feed liquid is continuously output from the first reactor, a part of the first feed liquid is returned to the first reactor, and the remaining part of the first feed liquid continuously enters a second reactor for aging treatment, the feeding amount of the monomer-containing raw material system entering the first reactor is not less than the feeding amount of the rest part of the first material liquid entering the second reactor, so as to obtain the resin material. The method is helpful for preparing the resin with controllable molecular weight and narrow molecular weight distribution.

Description

Technical Field

[0001] The invention relates to the technical field of resins, and in particular to a method and system for preparing a resin material. Background Art

[0002] Photoresist, also known as "photoresist", is a material that uses photochemical reactions to transfer the required graphics from the mask to the substrate to be processed through photolithography processes such as exposure, development, etching, and degumming. According to different application fields, it can be divided into semiconductor photoresist, display panel photoresist and PCB photoresist. Semiconductor photoresist can be divided into G-line photoresist, I-line photoresist, KrF photoresist, ArF photoresist, EUV photoresist, etc. according to different exposure wavelengths. Among them, KrF photoresist is composed of resin (specifically KrF resin), photoinitiator, solvent and additives.

[0003] The traditional preparation process of resin is an intermittent or semi-batch process, which uses a large amount of raw materials to be put into production at one time or in batches. When the raw materials are exhausted and the reaction is completed, a batch of production is completed. Although the single batch production volume of this intermittent or semi-batch process is large, its production efficiency and reaction conversion rate are low, and the molecular weight fluctuation of the resin between batches is large and the molecular weight distribution is wide. Especially in the process from small-scale trials to industrial scale-up, the molecular weight and molecular weight distribution of the resin fluctuate more, reducing the quality of the resin and making it unable to meet the requirements. For example, the KrF resin prepared by the intermittent or semi-batch process is of low quality and cannot meet the demand for high-quality photoresist. Summary of the invention

[0004] The invention provides a method and system for preparing a resin material, which are helpful for preparing a resin with controllable molecular weight and narrow molecular weight distribution.

[0005] The present invention provides a method for preparing a resin material, comprising the following steps: continuously feeding a raw material system containing monomers into a first reactor for polymerization reaction to obtain a first feed liquid; continuously outputting the first feed liquid from the first reactor, returning part of the first feed liquid to the first reactor, and continuously feeding the remaining part of the first feed liquid into a second reactor for aging treatment, wherein the feed amount of the raw material system containing monomers entering the first reactor is not less than the feed amount of the remaining part of the first feed liquid entering the second reactor, to obtain the resin material.

[0006] Optionally, the monomers include one or more of aromatic olefins, paraacetoxystyrene, and acrylic ester monomers.

[0007] Optionally, the monomer includes paraacetoxystyrene; the method further includes: the remaining portion of the first feed liquid continuously enters a second reactor for aging treatment to obtain a second feed liquid; the second feed liquid is continuously output from the second reactor and continuously enters a third reactor for deprotection reaction to obtain a third feed liquid; the third feed liquid is subjected to solid-liquid separation, and the obtained solid product is dried to obtain the resin material.

[0008] Optionally, the monomers include one or more of aromatic olefins and acrylate monomers, and the method further includes: continuously introducing the remaining portion of the first liquid into a second reactor for aging treatment to obtain a second liquid; performing solid-liquid separation on the second liquid, and drying the obtained solid product to obtain the resin material.

[0009] Optionally, the process of allowing the raw material system containing monomers to continuously enter the first reactor for polymerization reaction includes: first introducing a solvent into the first reactor until the volume of the solvent entering the first reactor accounts for a ratio of the volume of the first reactor, and then stopping introducing the solvent; wherein, 20%≤a≤60%; allowing the raw material system containing monomers to continuously enter the first reactor for polymerization reaction until the volume of the first feed liquid in the first reactor accounts for b ratio of the volume of the first reactor, and then continuously outputting the first feed liquid from the first reactor; wherein, 80%≤b≤100%.

[0010] Optionally, the ratio of the volume of the part of the first feed liquid continuously discharged from the first reactor that returns to the first reactor to the volume of the remaining part of the first feed liquid that enters the second reactor is 2 to 50; and / or, the temperature of the polymerization reaction is 50 to 100°C; and / or, the residence time of the raw material system containing the monomer in the first reactor is 30 to 180 min; and / or, the raw material system containing the monomer also includes an initiator, and the initiator includes one or more of azobisisobutyronitrile and azobisisoheptylnitrile; and / or, the temperature of the aging treatment is 50 to 100°C and the time is 10 to 60 min.

[0011] Optionally, the flow rate of the second feed liquid continuously entering the third reactor is 800-1200 g / h; and / or, a neutralizer is continuously added to the third reactor, and the flow rate of the neutralizer is 800-1200 g / h, so that the second feed liquid undergoes the deprotection reaction to obtain a third feed liquid; the neutralizer includes one or more of sodium methoxide, sodium ethoxide, ethanolamine, triethylamine, and ammonia water; and / or, the temperature of the deprotection reaction is 30-60°C and the time is 10-60 min.

[0012] The present invention provides a system for preparing a resin material, comprising: a first reactor and a second reactor, wherein the first reactor is used for performing a polymerization reaction, and the second reactor is used for performing an aging treatment; the first reactor is provided with a first feed port, and a second discharge port and a third discharge port connected to the first feed port, and the second reactor is provided with a second feed port connected to the third discharge port.

[0013] Optionally, the first reactor is an elliptical ring reactor, and the ratio of the major axis to the minor axis of the elliptical ring reactor is (1.5-5):1; a static mixer is arranged in the elliptical ring reactor; and / or, the second reactor is a tubular reactor.

[0014] Optionally, a third reactor, a fourth reactor and a fifth reactor are further included; the third reactor is used for deprotection reaction, the fourth reactor is used for solid-liquid separation, and the fifth reactor is used for drying; the feed port of the third reactor is connected to the discharge port of the second reactor, the feed port of the fourth reactor is connected to the discharge port of the second reactor and / or the discharge port of the third reactor, and the feed port of the fifth reactor is connected to the discharge port of the fourth reactor; preferably, the third reactor is a tubular reactor or a kettle reactor; preferably, the fourth reactor is a filtration-washing two-in-one reactor or a kettle reactor; preferably, the fifth reactor 005 includes one or more of a vacuum drying oven, a freeze dryer, a vibration dryer, a spray dryer, a single cone dryer, and a double cone dryer.

[0015] The present invention provides a method and system for preparing a resin material. By continuously inputting a raw material system containing monomers into a first reactor and continuously outputting a first liquid feed from the first reactor, and satisfying that the feed amount of the raw material system containing monomers entering the first reactor is not less than the feed amount of the remaining first liquid feed entering a second reactor, continuous production of the resin material is achieved. In addition, in the above-mentioned system for continuously preparing the resin material, part of the first liquid feed will be returned to the first reactor, which ensures that various components in the reaction process are more uniform, makes the molecular weight of the resin material more controllable, and makes the molecular weight distribution narrower, effectively avoids the problem of large batch-to-batch fluctuations in the molecular weight of the resin material caused by intermittent and semi-intermittent preparation processes, and improves the quality of the resin material. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 Schematic diagram of the process for preparing resin materials in some embodiments.

[0017] Reference numerals:

[0018] 001 - first reactor; 002 - second reactor; 003 - third reactor; 004 - fourth reactor; 005 - fifth reactor; 101 - pump; A - raw material system containing monomers; B - resin material. DETAILED DESCRIPTION

[0019] In order to enable those skilled in the art to better understand the scheme of the present invention, the present invention is further described in detail below. The specific implementation methods listed below are only for describing the principles and features of the present invention. The examples are only used to explain the present invention and are not intended to limit the scope of the present invention. Based on the embodiments of the present invention, all other implementation methods obtained by ordinary technicians in the field without creative work are within the scope of protection of the present invention.

[0020] An embodiment of the present invention provides a method for preparing a resin material, comprising the following steps: continuously feeding a raw material system containing monomers into a first reactor for polymerization reaction to obtain a first feed liquid; continuously outputting the first feed liquid from the first reactor, returning part of the first feed liquid to the first reactor, and continuously feeding the remaining part of the first feed liquid into a second reactor for aging treatment, wherein the feed amount of the raw material system containing monomers entering the first reactor is not less than the feed amount of the remaining part of the first feed liquid entering the second reactor, to obtain a resin material.

[0021] According to the research and analysis of the inventors: by continuously inputting a raw material system containing monomers into the first reactor and continuously outputting the first liquid feed from the first reactor, and satisfying that the feed amount of the raw material system containing monomers entering the first reactor is not less than the feed amount of the remaining part of the first liquid feed entering the second reactor, the continuous production of the resin material is achieved, which helps to improve production efficiency. In addition, under the above-mentioned system for continuous preparation of resin materials, part of the first liquid feed will return to the first reactor, which ensures that the various components in the reaction process are more uniform, making the molecular weight of the resin material more controllable and the molecular weight distribution narrower, effectively avoiding the problem of large batch-to-batch fluctuations in the molecular weight of the resin material caused by intermittent and semi-batch preparation processes, and improving the quality of the resin material. In addition, traditional intermittent and semi-intermittent production processes mostly use kettle reactors for production, and the production volume of a single batch is large, which causes a large amount of raw materials to gather in the kettle reactor, resulting in serious material backmixing, low monomer conversion efficiency, uncontrollable reaction temperature, and high energy consumption. The preparation method of the resin material provided in the embodiment of the present invention adopts a multi-stage series production process, and the reaction materials are transported step by step in the production process, which can reduce the backmixing of materials, make the molecular weight of the resin more controllable, and the molecular weight distribution is narrower. At the same time, it also helps to improve the conversion rate of the monomer, improve the yield and production efficiency of the product, and also has the advantages of controllable temperature during the reaction process and lower energy consumption.

[0022] In some embodiments, the process of continuously allowing the raw material system containing monomers to enter the first reactor for polymerization reaction includes: firstly introducing a solvent (priming solvent) into the first reactor until the volume of the solvent entering the first reactor accounts for a ratio of the volume of the first reactor, and then stopping introducing the solvent; wherein 20%≤a≤60%; then continuously allowing the raw material system containing monomers to enter the first reactor for polymerization reaction until the volume of the first liquid (containing the resin intermediate) in the first reactor accounts for b ratio of the volume of the first reactor, and then continuously outputting the first liquid from the first reactor (i.e., continuously extracting the first liquid from the first reactor); wherein 80%≤b≤100%. Exemplarily, the above a is 20%, 30%, 40%, 50%, 60% or a range consisting of any two thereof, and b is 80%, 85%, 90%, 95%, 100% or a range consisting of any two thereof. It can be understood that when the above b is close to 100%, the interior of the first reactor is substantially filled with the solvent and the raw material system containing monomers.

[0023] The solvent may include one or more of methanol, isopropanol, propylene glycol methyl ether acetate, and 2-butanone.

[0024] In specific implementation, a solvent (priming solvent) is introduced into the first reactor until the volume of the solvent entering the first reactor accounts for a ratio of a to the volume of the first reactor. After the introduction of the solvent is stopped, the first reactor can be heated to a temperature of 50-100°C and not higher than the boiling point of the above-mentioned solvent, so that the temperature of the solvent in the first reactor reaches the temperature of the polymerization reaction.

[0025] In some embodiments, the polymerization reaction temperature (ie, the temperature of the first reactor) is 50-100°C, for example, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C or any two thereof.

[0026] The average residence time of the raw material system containing monomers in the first reactor (i.e., the polymerization reaction time) can be 30 to 180 min, for example, 30 min, 50 min, 100 min, 120 min, 150 min, 180 min or the range consisting of any two thereof.

[0027] The raw material system containing monomers also includes an initiator, and the initiator may include one or more of azobisisobutyronitrile and azobisisoheptanenitrile.

[0028] In some embodiments, the ratio of the volume of the part of the first liquid continuously output from the above-mentioned first reactor that returns to the first reactor to the volume of the remaining part of the first liquid entering the second reactor (reflux ratio) is 2 to 50, for example, 2, 5, 10, 20, 30, 40, 50 or a range composed of any two of them. By controlling the reflux ratio to meet the above range, most of the first liquid is returned to the first reactor for circulation to carry out the polymerization reaction, which can reduce the back mixing of the material and ensure that the various components in the polymerization reaction process and the aging treatment process are more uniform, which is beneficial to reduce the batch-to-batch fluctuation of the molecular weight of the resin material, making the molecular weight of the resin material more controllable and the molecular weight distribution narrower.

[0029] It is understandable that in order to ensure the continuous process of the resin preparation process, the feed amount of the raw material system including monomers continuously added to the first reactor is not less than the amount (output amount) of the remaining part of the first feed liquid continuously entering the second reactor.

[0030] The temperature of the aging treatment (i.e., the temperature of the second reactor) can be 50-100°C, for example, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C or a range consisting of any two thereof, and the time of the aging treatment (i.e., the residence time of the remaining part of the first liquid in the second reactor) can be 10-60min, for example, 10min, 20min, 30min, 40min, 50min, 60min or a range consisting of any two thereof, which helps to promote the unreacted monomers in the first liquid to continue the polymerization reaction and improve the conversion rate of the monomers.

[0031] The above-mentioned monomers may include one or more of aromatic olefins, paraacetoxystyrene, and acrylic acid monomers.

[0032] Specifically, the aromatic olefin may include styrene, and the acrylic monomer may include tert-butyl acrylate.

[0033] In some embodiments, the monomer includes p-acetoxystyrene. When the monomer includes p-acetoxystyrene, the product after aging treatment needs to be subjected to a deprotection reaction to obtain a resin material. The specific process includes: the remaining part of the first feed liquid is continuously fed into the second reactor for aging treatment to obtain a second feed liquid; the second feed liquid is continuously output from the second reactor and continuously fed into the third reactor for deprotection reaction to obtain a resin material.

[0034] Furthermore, a neutralizing agent can be continuously added to the third reactor to make the second feed liquid undergo a deprotection reaction to obtain a third feed liquid. Specifically, a neutralizing agent is continuously added to the third reactor, and the flow rate of the neutralizing agent can be 800 to 1200 g / h, so that the second feed liquid undergoes a deprotection reaction to obtain a third feed liquid. The neutralizing agent can include one or more of sodium methoxide, sodium ethoxide, ethanolamine, triethylamine, and ammonia water.

[0035] The temperature of the above-mentioned deprotection reaction (that is, the temperature of the third reactor) can be 30-60°C, for example, 30°C, 40°C, 50°C, 60°C or a range consisting of any two thereof, and the time of the deprotection reaction (that is, the residence time of the second liquid and the neutralizing agent in the third reactor) can be 10-60min, for example, 10min, 20min, 30min, 40min, 50min, 60min or a range consisting of any two thereof.

[0036] In addition, the flow rate of the second liquid continuously entering the third reactor can be 800-1200 g / h, for example, 800 g / h, 900 g / h, 1000 g / h, 1100 g / h, 1200 g / h or a range consisting of any two of them.

[0037] In specific implementation, the third feed liquid needs to be post-processed to obtain the resin material. For example, the second feed liquid is continuously output from the second reactor and continuously enters the third reactor for deprotection reaction to obtain the third feed liquid; the third feed liquid is subjected to solid-liquid separation, and the obtained solid product is dried to obtain the resin material.

[0038] When the above-mentioned monomer does not include para-acetoxystyrene, the above-mentioned deprotection reaction is not required, and the remaining part of the first feed liquid is continuously introduced into the second reactor for aging treatment to obtain the second feed liquid; the second feed liquid is subjected to solid-liquid separation, and the obtained solid product is dried to obtain the resin material.

[0039] After the solid-liquid separation of the third feed liquid or the solid-liquid separation of the second feed liquid (such as precipitation or filtration), the solid product is separated from the liquid phase. Further, the solid product can be washed to remove impurities such as residual monomers and metal ions to obtain a resin filter cake, and the time of this process can be 10 to 60 minutes. Then, the resin filter cake is dried to obtain a resin material.

[0040] The temperature of the drying (such as baking) can be 50-100° C. and the pressure can be 0-30 kPaA.

[0041] When the monomer does not include paraacetoxystyrene, the above-mentioned process of treating the first feed liquid may include: the remaining part of the first feed liquid continuously enters the second reactor for aging treatment to obtain the second feed liquid; the second feed liquid is subjected to solid-liquid separation, and the obtained solid product is dried to obtain a resin material.

[0042] In some embodiments, the resin includes krypton fluoride photoresist resin (KrF photoresist resin). According to the above preparation method, a krypton fluoride photoresist resin with good photolithography performance can be prepared.

[0043] An embodiment of the present invention also provides a system for preparing a resin material, comprising: a first reactor 001 and a second reactor 002, wherein the first reactor 001 is used for performing a polymerization reaction, and the second reactor 002 is used for performing an aging treatment; the first reactor 001 is provided with a first feed port, and a second discharge port and a third discharge port connected to the first feed port, and the second reactor 002 is provided with a second feed port connected to the third discharge port.

[0044] In some embodiments, the first reactor 001 is an elliptical ring reactor. Compared with a kettle reactor, it helps to increase the heat transfer area and mass transfer efficiency, and also helps to increase the monomer conversion rate, thereby increasing the reaction conversion rate and production efficiency, and increasing the product yield. In addition, it has the advantages of controllable temperature during the reaction and lower energy consumption.

[0045] Furthermore, the ratio of the major axis to the minor axis of the elliptical ring reactor can be (1.5-5):1, for example, 1.5:1, 2:1, 3:1, 4:1, 5:1 or a range consisting of any two thereof.

[0046] Traditional resin preparation reactors (such as kettle reactors) generally use mechanical stirring, and the sealing of the stirring (mechanical stirring) is generally single-face or double-face sealing. During long-term use, the wear of the dynamic ring and the static ring in the mechanical seal structure will enter the kettle and cause pollution. The leakage of the sealing liquid of the double-face seal will also affect the product quality.

[0047] The elliptical ring reactor in the embodiment of the present invention may be provided with a static mixer. The use of the static mixer for material mixing and mass transfer can reduce the degree of backmixing of the materials, making the molecular weight of the resin material more controllable and the molecular weight distribution narrower. It also avoids the contamination of the resin caused by mechanical seal wear and sealing liquid leakage caused by mechanical stirring of the kettle reactor, which helps to improve the purity of the resin.

[0048] The number of units of the static mixer in the elliptical ring reactor may be 1 to 1000.

[0049] In addition, the surface of the elliptical ring reactor may be covered with a jacket or a coil, and a heat-conducting medium is passed through the jacket or the coil. Preferably, the heat-conducting medium may be a mixture of water and ethylene glycol or heat-conducting oil.

[0050] The type of the static mixer may be selected from SV type, SK type, SX type, SH type or SL type.

[0051] In some embodiments, the second reactor 002 is a tubular reactor (eg, a tubular plug flow reactor) for aging the first feed liquid to improve the monomer conversion rate.

[0052] Furthermore, the preparation system may further include a third reactor 003 for performing a deprotection reaction; a fourth reactor 004 for performing solid-liquid separation; and a fifth reactor 005 for performing drying.

[0053] The feed port of the third reactor can be connected to the discharge port of the second reactor, the feed port of the fourth reactor can be connected to the discharge port of the second reactor and / or the discharge port of the third reactor, and the feed port of the fifth reactor can be connected to the discharge port of the fourth reactor.

[0054] In some embodiments, the third reactor 003 is a tubular reactor or a tank reactor.

[0055] In some embodiments, the fourth reactor 004 includes one or more of a filtration-washing two-in-one reactor or a tank reactor.

[0056] In some embodiments, the fifth reactor 005 may include one or more of a vacuum drying oven, a freeze dryer, a vibration dryer, a spray dryer, a single cone dryer, and a double cone dryer, and the above-mentioned drying is performed in the fifth reactor to obtain a resin material (resin solid powder).

[0057] like Figure 1As shown, in some embodiments, a raw material system A containing monomers is continuously fed into a first reactor 001 for polymerization reaction to obtain a first feed liquid; the first feed liquid is continuously discharged from the first reactor 001, and part of the first feed liquid is returned to the first reactor 001 under the drive of a pump 101, and the remaining part of the first feed liquid is continuously fed into a second reactor 002 for aging treatment to obtain a second feed liquid; the second feed liquid is continuously discharged from the second reactor 002 and continuously fed into a third reactor 003 for deprotection reaction to obtain a third feed liquid; the third feed liquid is continuously discharged from the third reactor 003 and continuously fed into a fourth reactor 004 for solid-liquid separation to obtain a solid product; the solid product is continuously discharged from the fourth reactor 004 and continuously fed into a fifth reactor 005 for drying to obtain a resin material B.

[0058] It can be understood that the feed amount of the remaining part of the first liquid continuously entering the second reactor 002 or the feed amount of the second liquid continuously entering the third reactor 003 is the actual output of the first reactor 001 .

[0059] Compared with the intermittent and semi-intermittent production processes carried out in a kettle reactor, the resin material preparation system provided by the embodiment of the present invention connects multiple reactors in series to form a multi-stage series production process that can be used for the continuous production of resin materials. The reaction materials are transported step by step in the production process, which can reduce the backmixing of materials, make the molecular weight of the resin more controllable and the molecular weight distribution narrower, and at the same time help to improve the conversion rate of the monomer, improve the yield and production efficiency of the product. In addition, it also has the advantages of controllable temperature during the reaction process and lower energy consumption.

[0060] The present invention is further described below by specific examples and comparative examples. Unless otherwise specified, the reagents, materials and instruments used below are all conventional reagents, conventional materials and conventional instruments, which can be commercially available, and the reagents and materials involved can also be synthesized by conventional synthesis methods.

[0061] The main raw material information is as follows:

[0062] Styrene, Wanhua Chemical Group Co., Ltd., purity ≥99.5%.

[0063] Para-acetoxystyrene, CECEP Wanrun Co., Ltd., electronic grade G3.

[0064] Tert-butyl acrylate, Ningbo Microchip Electronics Co., Ltd., purity ≥99.5%.

[0065] Methanol / isopropanol / propylene glycol methyl ether acetate / ammonia water, Jiangyin Jianghua Microelectronic Materials Co., Ltd., electronic grade G3.

[0066] Azobisisobutyronitrile / azobisisoheptanenitrile, Shanghai Aladdin Biochemical Technology Co., Ltd., purity ≥99.5%.

[0067] Sodium methoxide / sodium ethoxide / ethanolamine / methanol ammonia, Jiangsu Komiou Chemical Co., Ltd., purity ≥99.5%.

[0068] Example 1

[0069] This embodiment provides a method for preparing a resin, comprising the following steps:

[0070] Methanol (solvent) was introduced into the first reactor until the volume of methanol entering the first reactor accounted for a ratio of a to the volume of the first reactor (a=50%). After the introduction of methanol was stopped, the first reactor was heated to 62° C.; and then styrene, p-acetoxystyrene and a methanol solution of azobisisobutyronitrile (the mass percentage of azobisisobutyronitrile in the methanol solution of azobisisobutyronitrile was 20wt%) were continuously added into the first reactor at flow rates of 1000 g / h, 400 g / h and 250 g / h (the flow rates of monomers, initiators and their entry into the first reactor) for further treatment. Polymerization reaction to obtain a first feed liquid; until the volume of the first feed liquid in the first reactor accounts for a ratio of b (b=100%) to the volume of the first reactor, the first feed liquid is continuously discharged from the first reactor; at the same time, styrene, p-acetoxystyrene, and azobisisobutyronitrile methanol solution (monomer, initiator solution) are added to the first reactor at a flow rate of 2000 g / h (the flow rate of adding raw materials to the first reactor) according to the mass ratio of the above materials, and methanol is added to the first reactor at a flow rate of 2000 g / h (the flow rate of adding raw materials to the first reactor);

[0071] Part of the first feed liquid is returned to the first reactor, and the remaining part of the first feed liquid is continuously introduced into the second reactor for aging treatment, and the residence time of the reaction liquid in the second reactor (residence time of aging treatment or time of aging treatment) is 1 hour; wherein, the ratio of the volume of the part of the first feed liquid returned to the first reactor to the volume of the remaining part of the first feed liquid entering the second reactor (reflux ratio) is 5:1, and the residence time of the reaction liquid in the first reactor (average residence time of polymerization reaction) is 30 minutes, that is, the polymerization reaction temperature is 62° C. and the time is 30 minutes, to obtain the second feed liquid;

[0072] The second feed liquid is continuously discharged from the second reactor, and the second feed liquid and sodium methoxide (neutralizer) are respectively continuously fed into the third reactor at a flow rate of 800 g / h for deprotection reaction. The temperature of the deprotection reaction in the third reactor is 45° C., and the residence time of the reaction feed liquid (i.e., the deprotection reaction time) is 30 min, thereby obtaining a third feed liquid;

[0073] The third feed liquid is continuously discharged from the third reactor and continuously enters the fourth reactor for precipitation and washing for 60 minutes to obtain a KrF resin filter cake;

[0074] The KrF resin cake was continuously output from the fourth reactor and continuously fed into the fifth reactor to be dried at 65° C. and 10 kPaA to obtain a resin (resin solid).

[0075] Among them, the first reactor is an elliptical ring reactor, the ratio of the major axis to the minor axis of the elliptical ring reactor is 2:1, and a static mixer is arranged in the elliptical ring reactor, and the static mixer is of SK type; the second reactor is a tubular reactor; the third reactor is a tubular reactor; the fourth reactor is a kettle reactor; and the fifth reactor is a single cone dryer.

[0076] Comparative Example 1

[0077] This comparative example provides a method for preparing a resin, comprising the following steps:

[0078] Add 2000 g of methanol into a 10 L glass reactor, and heat the glass reactor to 62° C. using an oil bath;

[0079] Add 1000 g of styrene, 400 g of p-acetoxystyrene, and 300 g of azobisisobutyronitrile methanol solution (wherein the mass percentage of azobisisobutyronitrile is 20 wt %) into a 5 L glass narrow-necked bottle, and stir to mix well to obtain a monomer mixture;

[0080] The monomer mixture was added dropwise to the glass reactor for 3 hours and kept warm for 5 hours to obtain a resin intermediate; the glass reactor was then cooled to 45°C, 800 ml of sodium methoxide was added, and the mixture was reacted for 5 hours to obtain a mixed solution; the mixed solution was added dropwise to a mixed solution of methanol and water to precipitate a precipitate, and a filter cake was obtained by filtration;

[0081] The filter cake is placed in a vacuum drying oven and dried to obtain KrF resin.

[0082] Referring to the process of Example 1, the resins of Examples 2 to 10 and Comparative Example 2 were prepared, wherein the first reactor and the ratio of the major axis to the minor axis, the type of static mixer, the second reactor, the third reactor, the fourth reactor, the fifth reactor, the solvent, a and b, the monomer and its flow rate into the first reactor, the initiator and its flow rate into the first reactor of each Example and Comparative Example are summarized in Table 1, the flow rate of the raw material added to the first reactor, the temperature and time of the polymerization reaction, the temperature and time of the aging treatment, the reflux ratio, the flow rate of the second feed liquid and the neutralizer into the third reactor, the temperature and time of the deprotection reaction, the time of the precipitation washing, the temperature and pressure of the drying, etc. are summarized in Table 2, and the other conditions remain the same as in Example 1.

[0083] Table 1

[0084]

[0085]

[0086] Table 2

[0087]

[0088] Test example

[0089] The following parameters of the resins of the above embodiments and comparative examples were tested:

[0090] Molecular weight Mw and molecular weight distribution of resin: The molecular weight Mw and molecular weight distribution of resin were detected by gel permeation chromatography (GPC). Specifically, a chromatograph of Shimadzu LC-ADXR-2 was used. The standard product was polystyrene (PS). Tetrahydrofuran (THF) was used as a solvent to prepare a polystyrene THF solution with a polystyrene mass percentage of 1%. The test temperature was 35°C and the flow rate of the standard product was 1 mL / min. The specific results are shown in Table 3.

[0091] Test results

[0092] Table 3 Molecular weight Mw and molecular weight distribution of resin

[0093]

[0094]

[0095] By comparing Examples 1, 2, and 3 with Comparative Example 1, it can be seen that the molecular weight of the KrF resin obtained by the continuous preparation process of the embodiment of the present invention is controllable and has a narrower molecular weight distribution, which is beneficial to improving the lithography performance.

[0096] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing a resin material, characterized in that: The following steps are involved: Allowing a raw material system containing monomers to continuously enter a first reactor for polymerization reaction to obtain a first feed liquid; The first feed liquid is continuously output from the first reactor, and part of the first feed liquid is returned to the first reactor, and the remaining part of the first feed liquid is continuously fed into the second reactor for aging treatment to obtain the resin material, wherein the feed amount of the raw material system containing monomers entering the first reactor is not less than the feed amount of the remaining part of the first feed liquid entering the second reactor.

2. The method for preparing a resin material according to claim 1, characterized in that: The monomers include one or more of aromatic olefins, paraacetoxystyrene, and acrylic ester monomers.

3. The method for preparing a resin material according to claim 2, characterized in that: The monomer comprises p-acetoxystyrene; and the method further comprises: The remaining part of the first feed liquid continuously enters the second reactor for aging treatment to obtain a second feed liquid; The second feed liquid is continuously output from the second reactor and continuously enters the third reactor for deprotection reaction to obtain a third feed liquid; The third liquid feed is subjected to solid-liquid separation, and the obtained solid product is dried to obtain the resin material.

4. The method for preparing a resin material according to claim 2, characterized in that: The monomers include one or more of aromatic olefins and acrylic ester monomers, and the method further includes: The remaining part of the first feed liquid continuously enters the second reactor for aging treatment to obtain a second feed liquid; The second liquid feed is subjected to solid-liquid separation, and the obtained solid product is dried to obtain the resin material.

5. The method for preparing a resin material according to claim 1, characterized in that: The process of continuously allowing the raw material system containing monomers to enter the first reactor for polymerization reaction comprises: First, introducing a solvent into the first reactor until the volume of the solvent entering the first reactor accounts for a ratio of the volume of the first reactor, and then stopping introducing the solvent; wherein 20%≤a≤60%; The raw material system containing the monomer is continuously introduced into the first reactor for polymerization reaction until the volume of the first feed liquid in the first reactor accounts for a ratio b of the volume of the first reactor, and then the first feed liquid is continuously discharged from the first reactor; wherein 80%≤b≤100%.

6. The method for preparing a resin material according to claim 1, characterized in that: The ratio of the volume of the first feed liquid continuously discharged from the first reactor and returned to the first reactor to the volume of the remaining first feed liquid entering the second reactor is 2 to 50; And / or, the polymerization reaction temperature is 50 to 100° C.; and / or, the residence time of the raw material system containing the monomer in the first reactor is 30 to 180 minutes; And / or, the raw material system containing monomers further comprises an initiator, and the initiator comprises one or more of azobisisobutyronitrile and azobisisoheptanenitrile; And / or, the aging treatment is carried out at a temperature of 50 to 100° C. and for a time of 10 to 60 minutes.

7. The method for preparing a resin material according to claim 3, characterized in that: The flow rate of the second feed liquid continuously entering the third reactor is 800-1200 g / h; and / or, continuously adding a neutralizing agent to the third reactor at a flow rate of 800 to 1200 g / h, so that the second feed liquid undergoes the deprotection reaction to obtain a third feed liquid; the neutralizing agent comprises one or more of sodium methoxide, sodium ethoxide, ethanolamine, triethylamine, and aqueous ammonia; And / or, the temperature of the deprotection reaction is 30-60° C. and the time is 10-60 min.

8. A system for preparing a resin material, characterized in that: include: A first reactor and a second reactor, wherein the first reactor is used for polymerization reaction and the second reactor is used for aging treatment; the first reactor is provided with a first feed port, and a second discharge port and a third discharge port connected to the first feed port, and the second reactor is provided with a second feed port connected to the third discharge port.

9. The preparation system according to claim 8, characterized in that: The first reactor is an elliptical ring reactor, the ratio of the major axis to the minor axis of the elliptical ring reactor is (1.5-5):1; a static mixer is arranged in the elliptical ring reactor; And / or, the second reactor is a tubular reactor.

10. The preparation system according to claim 8, characterized in that: It also includes a third reactor, a fourth reactor, and a fifth reactor; the third reactor is used for deprotection reaction, the fourth reactor is used for solid-liquid separation, and the fifth reactor is used for drying; The feed port of the third reactor is connected to the discharge port of the second reactor, the feed port of the fourth reactor is connected to the discharge port of the second reactor and / or the discharge port of the third reactor, and the feed port of the fifth reactor is connected to the discharge port of the fourth reactor; Preferably, the third reactor is a tubular reactor or a tank reactor; Preferably, the fourth reactor is a filtering-washing two-in-one reactor or a kettle reactor; Preferably, the fifth reactor 005 includes one or more of a vacuum drying oven, a freeze dryer, a vibration dryer, a spray dryer, a single cone dryer, and a double cone dryer.

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