Polymer and deprotection system, method and application

Abstract

The invention discloses a polymer, a deprotection system, a deprotection method and application, and belongs to the technical field of photoresist. A polymer resin solution is prepared and subjected to deprotection in a deprotection system, so that a polymer with a specific protection ratio is prepared, and the system comprises a liquid storage tank, a pump, an ion exchange column and a sedimentation tank according to the flowing direction of a material, a special deprotection system and a deprotection method are adopted for deprotection of acetal protected poly (p-hydroxystyrene), all devices in the system cooperate to convey a polymer resin solution to an ion exchange column for deprotection, and then the deprotected solution is conveyed to a sedimentation tank for sedimentation. In the deprotection process, the acetal protection proportion of the acetal-protected poly (p-hydroxystyrene) can be controlled by adjusting the rate of the pump and the column temperature of the ion exchange column at any time, and the device is simple and easy to obtain, and convenient and easy to control to use.

Description

Technical Field

[0001] The invention relates to the technical field of photoresists, and in particular to a polymer and a deprotection system, method and application. Background Art

[0002] Photoresist refers to an etching-resistant film material whose solubility changes through irradiation or radiation of ultraviolet light, electron beam, ion beam, X-ray, etc. The solubility change of photoresist is closely related to the contrast ratio of photoresist. PHS resin (polyhydroxystyrene) is a resin used to produce photosensitive resins and other photosensitive imaging systems. Compared with traditional phenolic resins, PHS resin has the advantages of low absorption rate of deep ultraviolet light, high sensitivity, high resolution, and can improve the etching resistance of polymers. It is an important component of photoresist. The most commonly used protecting group in PHS resin is acetal group. The protection ratio of acetal group to PHS resin determines the dissolution rate of photoresist. Therefore, it is particularly important to determine the protection ratio of acetal group to PHS resin and prepare acetal-protected PHS resin with corresponding ratio.

[0003] The traditional method for preparing acetal-protected PHS resin is to prepare a PHS precursor resin, deprotect it to form a PHS resin, and then graft it. In this process, a large amount of chemicals are required, which is likely to cause residues and greatly increase the risk of introducing metal ion impurities. In addition, due to the numerous and complex process steps, continuous production is difficult. In order to meet the strict requirements of the photoresist industry for stability, it will greatly increase the difficulty of control and production costs.

[0004] Therefore, when preparing polymer resins with specific protection ratios, the grafting rate of the protecting groups cannot be controlled, other impurities will be introduced, and the waste and recycling caused by the large amount of chemicals required during the preparation process remain urgent issues to be resolved. Summary of the invention

[0005] In view of the above problems, the present invention provides a polymer and a deprotection system, method and application. The polymer resin solution is ion exchanged by the continuous flow deprotection system of the present invention to prepare a polymer resin with a desired protection ratio. The process is simple and easy to control.

[0006] The present invention provides a polymer, wherein the weight average molecular weight (Mw) of the polymer is 2000-200000, the molecular weight distribution (PDI) is 1.0-1.1, the content of total metal impurity ions in the polymer is 1-100 ppb, and the structure of the polymer is or , where X, Y, and Z are the molar percentages of the structural unit, X, Y, and Z are positive numbers or 0, X+Y+Z≤100%, and X and Y are not 0 at the same time, R 1 , R2 , R 3 and R 4 It includes one or more of H, alkyl, cycloalkyl and groups with aromatic rings; and the main chain also includes a structural unit A.

[0007] Furthermore, the alkyl group includes one or more of methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, neopentyl and isopentyl.

[0008] Furthermore, the cycloalkyl group includes one or more of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, ethylcyclopentyl and ethylcyclohexyl.

[0009] Furthermore, the group with an aromatic ring includes one or more of phenyl, naphthyl, anthracenyl, phenanthryl and benzyl.

[0010] Furthermore, the R 1 , R 2 , R 3 and R 4 Rings containing 5 or more carbon atoms are also included.

[0011] Furthermore, the structural unit A specifically includes one or more of a styrene structural unit, an ethylene structural unit, a cycloolefin structural unit, a vinyl ether structural unit, a vinyl alcohol ester structural unit, an acrylate structural unit and a methacrylate structural unit.

[0012] Furthermore, the styrene structural unit includes one or more of styrene, p-tert-butoxystyrene, p-benzyloxystyrene, p-acetoxystyrene, p-trimethylsilyloxystyrene, p-hexafluoroisopropanol styrene, p-isoamyloxystyrene and p-tert-butoxycarbonylstyrene.

[0013] Furthermore, the ethylene structural unit includes one or more of ethylene, propylene, butylene and isobutylene.

[0014] Furthermore, the cycloolefin structural unit includes one or more of cyclopentene, 1-ethylcyclopentene and cyclohexene.

[0015] Furthermore, the vinyl ether structural unit includes one or more of vinyl ethyl ether and vinyl benzyl ether.

[0016] Furthermore, the vinyl alcohol ester structural unit includes one or more of vinyl acetate and vinyl cinnamate.

[0017] Furthermore, the acrylic acid ester structural unit includes one or more of tert-butyl acrylate, benzyl acrylate and cyclopentyl acrylate.

[0018] Furthermore, the methacrylate structural unit includes one or more of tert-butyl methacrylate, benzyl methacrylate and cyclopentyl methacrylate.

[0019] Further, the molar percentage of acetal substituents in the polymer is equal to Y.

[0020] The present invention also provides a deprotection system, which includes a liquid storage tank, a pump, an ion exchange column and a sedimentation tank according to the flow direction of the material; the liquid storage tank, the pump, the ion exchange column and the sedimentation tank are connected in sequence through pipelines; The ion exchange column comprises, from bottom to top, a lower cover, a lower sealing plate, a cylinder, an upper sealing plate, a column height adjustment rod and an upper cover; The upper cover is connected to the top of the cylinder and is sealed with the top of the cylinder by bolts or buckles. A threaded opening is opened in the middle of the upper cover, and the upper sealing plate is movably connected to the top of the cylinder. The column height adjustment rod passes through the upper cover and is fixedly connected with the upper sealing plate. The column height adjustment rod is threadedly connected to the threaded opening of the upper cover. The column height adjustment rod adjusts the height of the upper sealing plate by rotating the thread. The column height adjustment rod is a hollow structure, and the material flows out of the hollow structure.

[0021] Furthermore, the diameters of the lower sealing plate and the upper sealing plate are the same as the inner diameter of the cylinder, and sealing rings are installed between the lower sealing plate, the upper sealing plate and the cylinder.

[0022] Furthermore, the lower sealing plate and the upper sealing plate both have sieve holes.

[0023] Furthermore, a liquid inlet is provided at the top of the sedimentation tank, and a stirring device is installed in the sedimentation tank.

[0024] Furthermore, a constant temperature device and a stirring device are provided in the liquid storage tank, and a liquid outlet is provided above the liquid storage tank.

[0025] Furthermore, the pump is provided with a liquid inlet and a liquid outlet, and the error of the pump is ≤1%.

[0026] Furthermore, the pump is one or more of a metering pump, a peristaltic pump and a gravity pump.

[0027] Furthermore, the lower cover is connected to the bottom of the cylinder and is sealed with the bottom of the cylinder by bolts or buckles. A liquid inlet is opened in the middle of the lower cover, and the lower sealing plate is fixed at the bottom of the cylinder, 10-12 cm away from the lower cover.

[0028] Furthermore, the movable distance of the upper sealing plate is 10-20 cm.

[0029] Furthermore, the material of the lower cover, the lower sealing plate, the upper sealing plate, the column height adjustment rod and the upper cover is polytetrafluoroethylene, and the pressure resistance of the lower cover and the upper cover is 0.3-0.5 MPa.

[0030] Furthermore, the aspect ratio of the cylinder is 15-20, the volume of the cylinder is 50-80 ml, and a constant temperature layer is provided on the outer wall of the cylinder.

[0031] The present invention also provides a method for preparing the polymer using the deprotection system, comprising the following steps: Step 1, dissolving a polymer resin in a solvent 1 to prepare a polymer resin solution, and placing the polymer resin solution in a liquid storage tank; Step 2, activating the cation exchange resin to obtain an activated cation exchange resin; Step 3, activating the anion exchange resin to obtain an activated anion exchange resin; Step 4, mixing the activated cation exchange resin and the activated anion exchange resin evenly, loading them between the lower sealing plate and the upper sealing plate in the ion exchange column, adjusting the column temperature of the ion exchange column, turning on the pump, and inputting the polymer resin solution in the liquid storage tank into the ion exchange column for quantitative deprotection; Step 5, establishing a working curve according to the molecular weight of a known resin material and the molar percentage of an acetal substituent, obtaining a relationship between the molecular weight of the known resin material and the molar percentage of an acetal substituent, collecting the quantitatively deprotected effluent from the ion exchange column, testing the molecular weight of the effluent after dilution, calculating the molar percentage of the substituent in the effluent according to the relationship, and adjusting the pump speed according to the measured molar percentage of the substituent until the molar percentage of the substituent in the effluent is close to the molar percentage of the target substituent; Step 6: The liquid continuously flowing out of the adjusted ion exchange column is transported to a sedimentation tank, and the solid matter is dried after sedimentation to obtain the solid polymer.

[0032] Furthermore, the mass percentage of the polymer resin solution in step 1 is 1-50%.

[0033] Furthermore, the structure of the polymer resin in step 1 is or , where m, n, o are the molar percentages of the structural unit, m, n, o are positive numbers or 0, m+n+o=100%, m+n= X+Y, o=Z, m+n≠0, R 1 , R 2 , R 3 and R 4It includes one or more of H, alkyl, cycloalkyl and groups with aromatic rings; and the main chain also includes a structural unit A.

[0034] Further, the molar percentage of acetal substituents in the polymer resin is equal to n.

[0035] Furthermore, the alkyl group includes one or more of methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, neopentyl and isopentyl.

[0036] Furthermore, the cycloalkyl group includes one or more of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, ethylcyclopentyl and ethylcyclohexyl.

[0037] Furthermore, the group with an aromatic ring includes one or more of phenyl, naphthyl, anthracenyl, phenanthryl and benzyl.

[0038] Furthermore, the R 1 , R 2 , R 3 and R 4 Rings containing 5 or more carbon atoms are also included.

[0039] Furthermore, the structural unit A specifically includes one or more of a styrene structural unit, an ethylene structural unit, a cycloolefin structural unit, a vinyl ether structural unit, a vinyl alcohol ester structural unit, an acrylate structural unit and a methacrylate structural unit.

[0040] Furthermore, the styrene structural unit includes one or more of styrene, p-tert-butoxystyrene, p-benzyloxystyrene, p-acetoxystyrene, p-trimethylsilyloxystyrene, p-hexafluoroisopropanol styrene, p-isoamyloxystyrene and p-tert-butoxycarbonylstyrene.

[0041] Furthermore, the ethylene structural unit includes one or more of ethylene, propylene, butylene and isobutylene.

[0042] Furthermore, the cycloolefin structural unit includes one or more of cyclopentene, 1-ethylcyclopentene and cyclohexene.

[0043] Furthermore, the vinyl ether structural unit includes one or more of vinyl ethyl ether and vinyl benzyl ether.

[0044] Furthermore, the vinyl alcohol ester structural unit includes one or more of vinyl acetate and vinyl cinnamate.

[0045] Furthermore, the acrylic acid ester structural unit includes one or more of tert-butyl acrylate, benzyl acrylate and cyclopentyl acrylate.

[0046] Furthermore, the methacrylate structural unit includes one or more of tert-butyl methacrylate, benzyl methacrylate and cyclopentyl methacrylate.

[0047] Furthermore, the solvent 1 in step 1 includes one or more of an ester solvent, an ether solvent, a ketone solvent and an alcohol solvent.

[0048] Furthermore, the ester solvent includes one or more of methyl formate, ethyl formate, methyl acetate, ethyl acetate, isopropyl acetate, isobutyl acetate, sec-butyl acetate, butyl butyrate, butyl benzoate and ethyl acetoacetate.

[0049] Furthermore, the ether solvent includes one or more of diethyl ether, isopropyl ether, tert-methyl ether, dipropyl ether, diisopropyl ether, ethyl butyl ether, tetrahydrofuran, dioxolane, 1,4-dichlorohexacyclopentane, trioxymethylene, propylene oxide, and ethylene glycol dimethyl ether.

[0050] Furthermore, the ketone solvent includes one or more of methyl ketone, hexanone, butanone, acetone, isobutyl ketone, methyl ethyl ketone and cyclohexanone.

[0051] Furthermore, the alcohol solvent includes one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol (tert-butanol), isobutanol, n-pentanol, 3-pentanol, tert-pentanol, isoamyl alcohol, n-hexanol, cyclohexanol, n-octanol, sec-octanol, n-nonanol, n-decanol, dodecanol, tetradecanol, hexadecanol, benzyl alcohol, tetrahydrofurfuryl alcohol, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 2,3-butanediol, glycerol, tetramethyl ethylene glycol, furfuryl alcohol, propylene glycol monomethyl ether and propylene glycol methyl ether acetate.

[0052] Furthermore, the cation exchange resin in step 2 includes one or more of macroporous strong acid, macroporous weak acid, strong acid and weak acid.

[0053] Furthermore, the acidic groups in the cation exchange resin in step 2 include -COOH, -SO 3 H, one or more of aminodiacetic acid, aminophosphoric acid and phenolic hydroxyl group.

[0054] Furthermore, the activation process in step 2 is: loading the cation exchange resin into an empty chromatography column 1 with a sand core, activating the cation exchange resin in the chromatography column 1 with acid circulation elution, then eluting with deionized water to adjust the pH, and finally washing with solvent 2.

[0055] Furthermore, the acid is a hydrogen chloride solution with a mass fraction of 1-30%.

[0056] Furthermore, the cycle elution activation time is 1-5h.

[0057] Furthermore, the volume ratio of the acid to the cation exchange resin is (2:1)-(5:1).

[0058] Furthermore, the pH value is 6-7.

[0059] Further, the solvent 2 includes methyl formate, ethyl formate, methyl acetate, ethyl acetate, isopropyl acetate, isobutyl acetate, sec-butyl acetate, butyl butyrate, butyl benzoate, ethyl acetoacetate, ethyl ether, isopropyl ether, tert-methyl ether, dipropyl ether, diisopropyl ether, ethyl butyl ether, tetrahydrofuran, dioxolane, 1,4-dichlorohexacyclo, trioxymethylene, propylene oxide, ethylene glycol dimethyl ether, ketone, hexanone, butanone, acetone, isobutyl ketone, methyl ethyl ketone, cyclohexanone, methanol, ethanol, anhydrous ethanol, One or more of propanol, isopropanol, n-butanol, sec-butanol, tert-butanol (tert-butanol), isobutanol, n-pentanol, 3-pentanol, tert-pentanol, isopentanol, n-hexanol, cyclohexanol, n-octanol, sec-octanol, n-nonanol, n-decanol, dodecanol, tetradecanol, hexadecanol, benzyl alcohol, tetrahydrofurfuryl alcohol, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 2,3-butanediol, glycerol, tetramethyl glycol, furfuryl alcohol, propylene glycol monomethyl ether and propylene glycol methyl ether acetate.

[0060] Furthermore, the second solvent is used for washing until the water content in the washing liquid is less than (0.1-1)%.

[0061] Furthermore, the anion exchange resin in step 3 includes one or more of macroporous strong alkalinity, macroporous weak alkalinity, strong alkalinity and weak alkalinity.

[0062] Furthermore, the basic groups in the anion exchange resin in step 3 include -N, -NH, -NH 2 、-N(CH 3 ) 2 and one or more of quaternary ammonium salts.

[0063] Furthermore, the activation process in step 3 is: loading the anion exchange resin into an empty chromatography column 2 with a sand core, activating the anion exchange resin in the chromatography column 2 with alkaline circulation elution, then eluting with deionized water to adjust the pH, and finally washing with solvent 3.

[0064] Furthermore, the alkali is a sodium hydroxide solution with a mass fraction of 1-30%.

[0065] Furthermore, the cycle elution activation time is 1-5h.

[0066] Furthermore, the volume ratio of the base to the anion exchange resin is (2:1)-(5:1).

[0067] Furthermore, the pH value is 6-7.

[0068] Further, the solvent three includes methyl formate, ethyl formate, methyl acetate, ethyl acetate, isopropyl acetate, isobutyl acetate, sec-butyl acetate, butyl butyrate, butyl benzoate, ethyl acetoacetate, ethyl ether, isopropyl ether, tert-methyl ether, dipropyl ether, diisopropyl ether, ethyl butyl ether, tetrahydrofuran, dioxolane, 1,4-dichlorohexacyclo, trioxymethylene, propylene oxide, ethylene glycol dimethyl ether, ketone, hexanone, butanone, acetone, isobutyl ketone, methyl ethyl ketone, cyclohexanone, methanol, ethanol, anhydrous ethanol, One or more of propanol, isopropanol, n-butanol, sec-butanol, tert-butanol (tert-butanol), isobutanol, n-pentanol, 3-pentanol, tert-pentanol, isopentanol, n-hexanol, cyclohexanol, n-octanol, sec-octanol, n-nonanol, n-decanol, dodecanol, tetradecanol, hexadecanol, benzyl alcohol, tetrahydrofurfuryl alcohol, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 2,3-butanediol, glycerol, tetramethyl glycol, furfuryl alcohol, propylene glycol monomethyl ether and propylene glycol methyl ether acetate.

[0069] Furthermore, the third washing with solvent is performed until the water content in the washing liquid is less than (0.1-1)%.

[0070] Furthermore, in step 4, the volume ratio of the activated cation exchange resin to the activated anion exchange resin is (1:1)-(1:100).

[0071] Furthermore, in the step 4, the particle size ratio of the activated cation exchange resin to the activated anion exchange resin is (1.5:1)-(1:1.5).

[0072] Furthermore, in step 4, the column temperature of the ion exchange column is -10 to 40°C.

[0073] Furthermore, the pump in step 4 is one of a metering pump and a peristaltic pump.

[0074] Furthermore, the metering pump or the peristaltic pump has a rate of 10-30 ml / min.

[0075] Furthermore, the retention time of the ion exchange column in step 4 is 2-5 min.

[0076] Furthermore, in step 4, the cation exchange resin plays a role in catalyzing the deprotection of the acetal substituent, and the anion exchange resin plays a role in controlling the degree of deprotection. The anion exchange resin does not react with the polymer resin solution.

[0077] Furthermore, the known resin material in step 5 has the same degree of polymerization as the polymer, but has different molar percentages of acetal substituents.

[0078] Furthermore, the molar percentage of the substituent of the known resin material in step 5 is determined by 13 carbon nuclear magnetic resonance.

[0079] Furthermore, the relationship in step 5 is: molar percentage of substituent = a*Mw-b, wherein a is 0.0001-10000, and b is 0.0001-10000.

[0080] Furthermore, the dilution concentration in step 5 is 1 mg / ml.

[0081] Furthermore, the method for testing the molecular weight of the effluent in step 5 is: adding the diluted effluent to a mixed solution of 80 ml of deionized water and 20 ml of methanol for complete precipitation, drying the precipitated solid at 0-70° C. for 10-120 hours, and then determining the molecular weight in gel permeation chromatography.

[0082] Furthermore, the method for adjusting the pump rate according to the measured molar percentage of the substituent in step 5 is: when the molar percentage of the substituent in the effluent is high, the pump rate is reduced and / or the temperature of the ion exchange column is increased to increase the retention time of the effluent; when the molar percentage of the substituent in the effluent is low, the pump rate is increased and / or the temperature of the ion exchange column is reduced to reduce the retention time of the effluent.

[0083] Furthermore, in the sedimentation tank in step 6, there are deionized water and methanol solution, and the mass ratio of the deionized water to the methanol solution is (50:50)-(100:0).

[0084] Furthermore, the methanol solution is electronic grade methanol, specifically one or more of grades G3, G4 or G5.

[0085] Furthermore, the drying temperature in step 6 is 0-70° C., and the drying time is 10-120 hours.

[0086] A photoresist, wherein the raw material of the photoresist includes the polymer.

[0087] An electronic product, wherein the raw material of the electronic product includes the photoresist.

[0088] Beneficial effects of the present invention: 1. The present invention adopts a special deprotection system and a deprotection method to deprotect the acetal-protected polymer resin solution. The various devices in the system cooperate to transport the polymer resin solution to the ion exchange column for deprotection, and then transport the deprotected solution to the sedimentation tank for sedimentation. During the deprotection process, the molar percentage of the acetal substituent of the polymer resin solution can be controlled by adjusting the pump speed and the column temperature of the ion exchange column at any time. The device in the present invention is simple and easy to obtain, easy to use and easy to control. The special design structure of the ion exchange column enables the capacity of the ion exchange column to be adjusted according to actual conditions to adapt to anion and cation exchange resins of different volumes. The upper cover of the ion exchange column is sealed and connected to the top of the cylinder by bolts or buckles to ensure sealing and facilitate disassembly and maintenance. The upper sealing plate is movably connected to the upper part of the cylinder, and its height is adjusted by a column height adjustment rod. According to different material processing requirements, the actual situation of ion exchange, etc., the position of the upper sealing plate is flexibly adjusted, thereby changing the effective space height for ion exchange in the ion exchange column, thereby improving the efficiency and effect of deprotection. 2. In the present invention, anion and cation exchange resins are mixed and loaded into an ion exchange column, wherein the cation exchange resin plays a role in catalyzing the deprotection of acetal substituents, and the anion exchange resin plays a role in controlling the degree of deprotection. The anion exchange resin does not react with the polymer resin solution, thereby controlling the molar percentage of the acetal substituent. The deprotection method of the present invention can prepare polymers with any protection ratio, and the protection ratio of the prepared polymer is accurate and stable and consistent. No other impurity ions will be introduced during the deprotection process. Compared with the traditional method of first preparing poly (p-tert-butoxystyrene), de-tert-butylating, and then grafting acetal groups, the method is simpler to operate, does not require more operating steps, is applicable to polymers with different protection ratios, has lower requirements on initial materials, has fewer restrictions, omits a complicated preparation process, saves raw material costs and time costs, has high production efficiency, and has high quality accuracy. BRIEF DESCRIPTION OF THE DRAWINGS

[0089] Figure 1 It is a structural schematic diagram of the deprotection system described in the present invention; Figure 2 It is a schematic diagram of the structure of the ion exchange column of the present invention; The names of the numbers in the figure are 1, liquid storage tank; 2, pump; 3, ion exchange column; 4, sedimentation tank; 301, lower cover; 302, lower sealing plate; 303, cylinder; 304, upper sealing plate; 305, column height adjustment rod; 306, upper cover. DETAILED DESCRIPTION

[0090] The invention is described in detail below with reference to the embodiments: The invention provides a polymer and a deprotection system, method and application. A polymer with a specific proportion of acetal protection is prepared by a specific deprotection system. The preparation process is simple and the grafting rate is controllable.

[0091] Example 1 The target structure of the polymer in this embodiment is , where 70 and 30 are the molar percentages of the structural units, where the target molar percentage of -OH is 70%, and the acetal group ( ) with a target mole percentage of 30%.

[0092] This embodiment provides a deprotection system, which includes a liquid storage tank 1, a pump 2, an ion exchange column 3 and a sedimentation tank 4 according to the flow direction of the material; the liquid storage tank 1, the pump 2, the ion exchange column 3 and the sedimentation tank 4 are connected in sequence through pipelines; The ion exchange column 3 includes, from bottom to top, a lower cover 301, a lower sealing plate 302, a cylinder 303, an upper sealing plate 304, a column height adjustment rod 305 and an upper cover 306; The upper cover 306 is connected to the top of the cylinder 303 and is sealed with the top of the cylinder 303 by bolts or buckles. A threaded opening is opened in the middle of the upper cover 306. The upper sealing plate 304 is movably connected to the top of the cylinder 303. The column height adjustment rod 305 passes through the upper cover 301 and is fixedly connected to the upper sealing plate 304. The column height adjustment rod 305 is threadedly connected to the threaded opening of the upper cover 301. The column height adjustment rod 305 adjusts the height of the upper sealing plate 304 by rotating the thread. The column height adjustment rod 305 is a hollow structure, and the material flows out of the hollow structure.

[0093] In this embodiment, the diameters of the lower sealing plate 302 and the upper sealing plate 304 are the same as the inner diameter of the cylinder 303, and sealing rings are installed between the lower sealing plate 302 and the upper sealing plate 304 and the cylinder 303; The lower sealing plate 302 and the upper sealing plate 304 both have sieve holes; A liquid inlet is provided at the top of the sedimentation tank 304, and a stirring device is installed in the sedimentation tank 304; The liquid storage tank 1 is provided with a constant temperature device and a stirring device, and a liquid outlet is provided above the liquid storage tank 1; The pump 2 is provided with a liquid inlet and a liquid outlet, and the error of the pump is ≤1%; The pump 2 is a metering pump; The lower cover 301 is connected to the bottom of the cylinder 303 and is sealed with the bottom of the cylinder 303 by bolts or buckles. A liquid inlet is opened in the middle of the lower cover 301. The lower sealing plate 302 is fixed at the bottom of the cylinder 303 and is 10 cm away from the lower cover 301. The movable distance of the upper sealing plate 304 is 10-20 cm; The material of the lower cover 301, the lower sealing plate 302, the upper sealing plate 304, the column height adjustment rod 305 and the upper cover 306 is polytetrafluoroethylene, and the pressure resistance of the lower cover 301 and the upper cover 306 is 0.3MPa; The aspect ratio of the cylinder 303 is 15, the volume of the cylinder 303 is 50 ml, and a constant temperature layer is provided on the outer wall of the cylinder 303 .

[0094] This embodiment also provides a method for preparing the polymer using the deprotection system, comprising the following steps: Step 1: 20000g polymer resin (Mw=26543, PDI=1.040, structure , the molar percentage of the acetal substituent is 100%) is dissolved in 70000g of ethyl acetate and 10000g of methanol to prepare a polymer resin solution with a mass fraction of 20%, and the polymer resin solution is placed in a liquid storage tank 1; Step 2, 7.5 g of a macroporous weakly acidic cation exchange resin (724) with a -COOH group is loaded into an empty 100 ml chromatography column 1 with a sand core, and activated by circulating elution with 250 ml of a 10% by mass hydrogen chloride solution for 3 h, then eluted with deionized water until the pH of the washing liquid is 6-7, and then washed with methanol until the water content in the washing liquid is ≤1%, to obtain an activated cation exchange resin; Step 3: 37.5 g of 2 The macroporous acrylic acid-based strongly basic anion exchange resin (D318) of the group was loaded into an empty 100 ml chromatography column 2 with a sand core, and activated by circulating elution with 500 ml of a 10% sodium hydroxide solution for 3 hours, then eluted with deionized water until the pH of the washing liquid was 6-7, and then washed with methanol until the water content in the washing liquid was ≤1%, thereby obtaining an activated anion exchange resin; Step 4, 7.5 g of the activated cation exchange resin and 37.5 g of the activated anion exchange resin are mixed evenly, and loaded into the lower sealing plate 302 and the upper sealing plate 304 in the ion exchange column 3, the ion exchange column 3 is kept at a constant temperature of 0° C., the metering pump 2 is turned on, and the polymer resin solution in the liquid storage tank 1 is input into the ion exchange column 3 at a rate of 15 ml / min for quantitative deprotection. The retention time of the polymer resin solution in the ion exchange column 3 is 3 min; Step 5: Establish a working curve based on the molecular weight of a known resin material and the molar percentage of the acetal substituent. The values ​​of the known resin material are shown in the table: , the relationship between the molecular weight of the known resin material and the molar percentage of the acetal substituent is obtained as follows: molar percentage of the acetal substituent=0.0111*molecular weight-192.38, wherein the known resin material and the polymer have the same degree of polymerization, but different molar percentages of the acetal substituent; After 16.5 min, the quantitatively deprotected effluent 1 in the ion exchange column 3 was collected, diluted to a concentration of 1 mg / ml, and then added to a mixed solution of 80 ml of deionized water and 20 ml of methanol for complete precipitation. The precipitated solid was dried at 70° C. for 24 h, and the molecular weight of the effluent 1 was determined to be 18992 by gel permeation chromatography. The molecular weight of the effluent 1 was substituted into the relationship, and the molar percentage of the acetal substituent in the effluent 1 was calculated to be 18.4%; The rate of the metering pump 2 is adjusted to 16 ml / min, and the quantitatively deprotected effluent 2 in the ion exchange column 3 is collected after 18 minutes, and after diluting to a concentration of 1 mg / ml, the diluted effluent 2 is added to a mixed solution of 80 ml of deionized water and 20 ml of methanol for complete precipitation, and the precipitated solid is dried at 70° C. for 24 hours, and the molecular weight of the effluent 2 is measured by gel permeation chromatography to be 20121, and the molecular weight of the effluent 2 is substituted into the relationship, and the molar percentage of the acetal substituent in the effluent 2 is calculated to be 30.9%; Step 6: The liquid continuously flowing out of the adjusted ion exchange column 3 is transported to the sedimentation tank 4, wherein the sedimentation tank 4 contains deionized water and methanol solution with a mass ratio of 80:20. After sedimentation, the solid matter is dried at 35° C. for 24 hours to obtain the solid polymer.

[0095] This embodiment provides a polymer having a weight average molecular weight of 20121, a molecular weight distribution of 1.075, a total metal impurity ion content of 10.9 ppb, and a structure of The molar percentage of acetal substituents in the polymer is 30.9%, and the error in the molar percentage of acetal substituents between the polymer and the target polymer is less than 1%.

[0096] Example 2 The target structure of the polymer in this embodiment is , where 65, 25 and 10 are the molar percentages of the structural units, wherein the target molar percentage of -OH is 65%, the tert-butoxy ( ) has a target molar percentage of 25%, and the acetal groups ( ) with a target mole percentage of 10%.

[0097] In this embodiment, a deprotection system is provided, and the deprotection system is consistent with the deprotection system in Example 1.

[0098] This embodiment also provides a method for preparing the polymer using the deprotection system, comprising the following steps: Step 1: 20000g polymer resin (Mw=27930, PDI=1.097, structure , the molar percentage of tert-butoxy is 24.3%, and the molar percentage of acetal substituent is 75.7%) is dissolved in 70000g of ethyl acetate and 10000g of methanol to prepare a polymer resin solution with a mass fraction of 20%, and the polymer resin solution is placed in a liquid storage tank 1; Step 2: 7.5g of -SO 3 The H-group macroporous strongly acidic cation exchange resin (D001) was loaded into an empty 100 ml chromatography column with a sand core, and activated by circulating elution with 250 ml of a 10% hydrogen chloride solution for 3 h, then eluted with deionized water until the pH of the washing liquid was 6-7, and then washed with methanol until the water content in the washing liquid was ≤1%, thereby obtaining an activated cation exchange resin; Step 3, 37.5 g of a strongly basic anion exchange resin (717) with a quaternary ammonium salt group is loaded into an empty 100 ml chromatography column 2 with a sand core, and activated by circulating elution with 500 ml of a 10% sodium hydroxide solution for 3 h, then eluted with deionized water until the pH of the washing liquid is 6-7, and then washed with methanol until the water content in the washing liquid is ≤1%, to obtain an activated anion exchange resin; Step 4, 7.5g of the activated cation exchange resin and 37.5g of the activated anion exchange resin are mixed evenly, and loaded into the lower sealing plate 302 and the upper sealing plate 304 in the ion exchange column 3, the ion exchange column 3 is kept at a constant temperature of 0°C, the metering pump 2 is turned on, and the polymer resin solution in the liquid storage tank 1 is input into the ion exchange column 3 at a rate of 30ml / min for quantitative deprotection, and the retention time of the polymer resin solution in the ion exchange column 3 is 1.5min; Step 5: Establish a working curve based on the molecular weight of a known resin material and the molar percentage of the acetal substituent. The values ​​of the known resin material are shown in the table: , the relationship between the molecular weight of the known resin material and the molar percentage of the acetal substituent is obtained as follows: molar percentage of the acetal substituent=0.00799*molecular weight-124.56, wherein the known resin material and the polymer have the same degree of polymerization, but different molar percentages of the acetal substituent; The acetal substituent in the polymer resin solution will be removed during the quantitative deprotection process of the ion exchange column 3, while the tert-butoxy group will not react with the anion and cation exchange resins; The quantitatively deprotected effluent 1 in the ion exchange column 3 after 16.5 minutes was collected, diluted to a concentration of 1 mg / ml, and the diluted effluent 1 was added to a mixed solution of 80 ml of deionized water and 20 ml of methanol for complete precipitation. The precipitated solid was dried at 70° C. for 24 hours, and the molecular weight of the effluent 1 was determined to be 22812 by gel permeation chromatography. The molecular weight of the effluent 1 was substituted into the relationship, and the total molar percentage of the acetal substituent and the tert-butoxy group in the effluent 1 was calculated to be 55.6%. After removing the fixed molar percentage of the tert-butoxy group of 24.3%, the molar percentage of the acetal substituent was 31.3%; The rate of the metering pump 2 is adjusted to 12 ml / min, and the quantitatively deprotected effluent 2 in the ion exchange column 3 is collected after 15 minutes, and after diluting to a concentration of 1 mg / ml, the diluted effluent 2 is added to a mixed solution of 80 ml of deionized water and 20 ml of methanol for complete precipitation, and the precipitated solid is dried at 70° C. for 24 hours, and the molecular weight of the effluent 2 is measured by gel permeation chromatography to be 20271, and the molecular weight of the effluent 2 is substituted into the relationship, and the total molar percentage of the acetal substituent and the tert-butoxy group of the effluent 2 is calculated to be 35.6%, and after removing the fixed molar percentage of the tert-butoxy group of 24.3%, the molar percentage of the acetal substituent is 11.3%; Step 6: The liquid continuously flowing out of the adjusted ion exchange column 3 is transported to a sedimentation tank 4, wherein the sedimentation tank 4 contains a deionized water and methanol solution with a mass ratio of 80:20. After sedimentation, the solid matter is dried at 70° C. for 24 hours to obtain a solid polymer. The total molar percentage of acetal substituents and tert-butoxy groups in the polymer is 34.8%. After removing the fixed molar percentage of tert-butoxy of 24.3%, the molar percentage of acetal substituents is 10.5%.

[0099] This embodiment provides a polymer, the weight average molecular weight of the polymer is 19941, the molecular weight distribution is 1.087, the content of total metal impurity ions in the polymer is 7.5 ppb, and the structure of the polymer is The total molar percentage of acetal substituents and tert-butoxy groups in the polymer is 34.8%. After removing the fixed molar percentage of tert-butoxy group of 24.3%, the molar percentage of acetal substituents obtained is 10.5%. The error between the molar percentage of acetal substituents in the polymer and the target polymer is less than 1%.

[0100] Example 3 The target structure of the polymer in this embodiment is , where 60 and 40 are the molar percentages of the structural units, wherein the target molar percentage of -OH is 60%, and the acetal group ( ) with a target mole percentage of 40%.

[0101] In this embodiment, a deprotection system is provided, and the deprotection system is consistent with the deprotection system in Example 1.

[0102] This embodiment also provides a method for preparing the polymer using the deprotection system, comprising the following steps: Step 1: 20000g polymer resin (Mw=30834, PDI=1.090, structure , the molar percentage of the acetal substituent is 100%) is dissolved in 70000g of ethyl acetate and 10000g of methanol to prepare a polymer resin solution with a mass fraction of 20%, and the polymer resin solution is placed in a liquid storage tank 1; Step 2: Replace 15g with -SO 3 The H-group macroporous strongly acidic cation exchange resin (D001) was loaded into an empty 100 ml chromatography column with a sand core, and activated by circulating elution with 250 ml of a 10% hydrogen chloride solution for 3 h, then eluted with deionized water until the pH of the washing liquid was 6-7, and then washed with methanol until the water content in the washing liquid was ≤1%, thereby obtaining an activated cation exchange resin; Step 3: 37.5 g of -N(CH 3 ) 2 The macroporous weakly basic anion exchange resin (D314) of the group was loaded into an empty 100 ml chromatography column 2 with a sand core, and activated by circulating elution with 500 ml of a 10% sodium hydroxide solution for 3 hours, then eluted with deionized water until the pH of the washing liquid was 6-7, and then washed with methanol until the water content in the washing liquid was ≤1%, thereby obtaining an activated anion exchange resin; Step 4, 15g of the activated cation exchange resin and 37.5g of the activated anion exchange resin are mixed evenly, and loaded into the lower sealing plate 302 and the upper sealing plate 304 in the ion exchange column 3, the ion exchange column 3 is kept at a constant temperature of -10°C, the metering pump 2 is turned on, and the polymer resin solution in the liquid storage tank 1 is input into the ion exchange column 3 at a rate of 25 ml / min for quantitative deprotection. The retention time of the polymer resin solution in the ion exchange column 3 is 2.1min; Step 5: Establish a working curve based on the molecular weight of a known resin material and the molar percentage of the acetal substituent. The values ​​of the known resin material are shown in the table: , the relationship between the molecular weight of the known resin material and the molar percentage of the acetal substituent is obtained as follows: molar percentage of the acetal substituent = 0.0129*molecular weight-292.95, wherein the known resin material and the polymer have the same degree of polymerization, but different molar percentages of the acetal substituent; The quantitatively deprotected effluent from the ion exchange column 3 after 16.5 min was collected, diluted to a concentration of 1 mg / ml, and the diluted effluent was added to a mixed solution of 80 ml of deionized water and 20 ml of methanol for complete precipitation. The precipitated solid was dried at 50° C. for 24 h, and the molecular weight of the effluent was measured by gel permeation chromatography to be 25791. The molecular weight of the effluent was substituted into the relationship to calculate the molar percentage of the acetal substituent in the effluent to be 39.7%; Step 6: The liquid continuously flowing out of the adjusted ion exchange column 3 is transported to the sedimentation tank 4, wherein the sedimentation tank 4 contains deionized water and methanol solution with a mass ratio of 80:20. After sedimentation, the solid matter is dried at 50° C. for 24 hours to obtain the solid polymer.

[0103] This embodiment provides a polymer, the weight average molecular weight of the polymer is 25791, the molecular weight distribution is 1.045, the content of total metal impurity ions in the polymer is 11.6 ppb, and the structure of the polymer is The molar percentage of acetal substituents in the polymer is 39.7%, and the error in the molar percentage of acetal substituents between the polymer and the target polymer is less than 1%.

[0104] Comparative Example 1 This comparative example only uses a cation exchange resin for deprotection. The target structure of the polymer in this comparative example is , wherein 70 and 30 are the mole percentages of the structural units, wherein the target mole percentage of -OH is 70% and the target mole percentage of acetal groups is 30%.

[0105] In this comparative example, a deprotection system is provided, and the deprotection system is consistent with the deprotection system in Example 1.

[0106] This comparative example also provides a method for preparing the polymer using the deprotection system, comprising the following steps: Step 1: 20000g polymer resin (Mw=26543, PDI=1.040, structure , the molar percentage of the acetal substituent is 100%) is dissolved in 70000g of ethyl acetate and 10000g of methanol to prepare a polymer resin solution with a mass fraction of 20%, and the polymer resin solution is placed in a liquid storage tank 1; Step 2, 45g of a macroporous strongly acidic cation exchange resin (D101) with a -COOH group is loaded into an empty 100ml chromatography column with a sand core, and activated by circulating elution with 250mL of a 10% by mass hydrogen chloride solution for 3h, then eluted with deionized water until the pH of the washing liquid is 6-7, and then washed with methanol until the water content in the washing liquid is ≤1%, to obtain an activated cation exchange resin; Step 3, 45 g of the activated cation exchange resin is loaded between the lower sealing plate 302 and the upper sealing plate 304 in the ion exchange column 3, the ion exchange column 3 is kept at a constant temperature of 0° C., the metering pump 2 is turned on, and the polymer resin solution in the liquid storage tank 1 is input into the ion exchange column 3 at a rate of 15 ml / min for quantitative deprotection. The retention time of the polymer resin solution in the ion exchange column 3 is 3 min; Step 4: Establish a working curve based on the molecular weight of a known resin material and the molar percentage of the acetal substituent. The values ​​of the known resin material are shown in the table: , The relationship between the molecular weight of the known resin material and the molar percentage of the acetal substituent is obtained as follows: molar percentage of the acetal substituent=0.0111*molecular weight-192.38, wherein the known resin material and the polymer have the same degree of polymerization, but different molar percentages of the acetal substituent; The quantitatively deprotected effluent 1 in the ion exchange column 3 after 16.5 minutes was collected, diluted to a concentration of 1 mg / ml, and then the diluted effluent 1 was added to a mixed solution of 80 ml of deionized water and 20 ml of methanol for complete precipitation. The precipitated solid was dried at 70° C. for 24 hours, and the molecular weight of the effluent 1 was determined to be 17101 by gel permeation chromatography. The molecular weight of the effluent 1 was substituted into the relationship to calculate the molar percentage of the acetal substituent in the effluent 1 to be less than 0.5%; The rate of the metering pump 2 is adjusted to 25 ml / min, and the quantitatively deprotected effluent 2 in the ion exchange column 3 is collected after 18 minutes, and after diluting to a concentration of 1 mg / ml, the diluted effluent 2 is added to a mixed solution of 80 ml of deionized water and 20 ml of methanol for complete precipitation, and the precipitated solid is dried at 70° C. for 24 hours, and the molecular weight of the effluent 2 is measured to be 17134 by gel permeation chromatography, and the molecular weight of the effluent 2 is substituted into the relationship to calculate that the protecting groups of the effluent 2 are completely removed; The column temperature of the ion exchange column 3 is lowered to -10°C, and the quantitatively deprotected effluent three in the ion exchange column 3 is collected after 18 minutes. After diluting to a concentration of 1 mg / ml, the diluted effluent three is added to a mixed solution of 80 ml of deionized water and 20 ml of methanol for complete precipitation. After the precipitated solid is dried at 70°C for 24 hours, the molecular weight of the effluent three is measured to be 17104 by gel permeation chromatography. The molecular weight of the effluent two is substituted into the relationship, and the protection ratio of the effluent two is calculated to be still completely removed.

[0107] This comparative example provides a polymer, wherein the weight average molecular weight of the polymer is 17104, the molecular weight distribution is 1.064, and the content of total metal impurity ions in the polymer is 12.5 ppb.

[0108] Comparative Example 2 This comparative example provides a polymer, wherein the weight average molecular weight of the polymer is 20199, the molecular weight distribution is 1.091, the content of total metal impurity ions in the polymer is 3964 ppb, and the protection ratio of acetal in the polymer is 28.7%.

[0109] This comparative example also provides a method for producing the polymer, comprising the following steps: Step 1: at -20°C, N 2 Under the protection, 10 ml of 2.5 M n-butyl lithium hexane solution was stirred and dissolved in 250 g of anhydrous tetrahydrofuran, and then 250 g of p-tert-butoxystyrene was added to carry out living anionic polymerization. After 60 min of polymerization, 20 ml of anhydrous methanol was added to terminate the reaction. The reaction solution after the termination of the reaction was precipitated in 1500 ml of methanol, and the solid was washed after filtration and dried at 50 ° C for 12 h to obtain 220 g of solid poly-p-tert-butoxystyrene (Mw=22079, PDI=1.094); Step 2: In N 2Under the protection, 220g of the poly(p-tert-butyloxystyrene) was dissolved in 200ml of acetone, 40ml of a 37.5% by volume hydrogen chloride solution was added, and the mixture was refluxed at 60°C for 5h to remove the tert-butyl group and then poured into 3000ml of deionized water for precipitation. The solid was washed after filtration and dried at 50°C for 12h to obtain 200g of de-tert-butylated poly(p-hydroxystyrene) (Mw=18236, PDI=1.076). Step 3: In N 2 Under the protection effect, 200g of de-tert-butylated poly(p-hydroxystyrene) was dissolved in 500ml of anhydrous N,N-diformamide, 7.6g of pyridinium p-toluenesulfonate and 37.3g of vinyl ethyl ether were added, and the mixture was reacted for 15h under sealed and constant temperature conditions of 30°C, and 5ml of triethylamine was added to terminate the reaction. After the reaction, the mixture was poured into 2000ml of deionized water for precipitation, and the solid matter was washed after filtration to obtain 180g of solid poly(hydroxystyrene) containing acetal protecting groups (Mw=20199, PDI=1.091). According to the molecular weight of the poly(hydroxystyrene) containing acetal protecting groups, the acetal protection ratio of the poly(hydroxystyrene) containing acetal protecting groups was 28.7% after 13 carbon nuclear magnetic resonance test. Step 4: The polyhydroxystyrene containing acetal protecting groups is dissolved in 750 ml of propylene glycol methyl ether acetate, and then rotary evaporated at 55° C. until the solid content is 30% of the total solid matter mass, to obtain the polymer.

[0110] Table 1 shows the properties of the polymers described in Examples 1-3 and Comparative Examples 1-2.

[0111] As shown in Table 1, the properties of the polymers in Examples 1-3 and Comparative Examples 1-2 of the present invention are shown. As can be seen from the table, the molecular weight distribution of the polymers in Examples 1-3 is narrow, and the error between the molar percentage of the acetal substituent and the set target molar percentage of the acetal substituent is less than 1%. At the same time, the content of impurity ions introduced in Examples 1-3 is extremely low, while in Comparative Example 1, only cation exchange resin is used for exchange. Due to the presence of the entire cation exchange system, all acetal substituents are removed, and the proportion of acetal substituents cannot be controlled. In Comparative Example 2, the polymer is prepared by a conventional deprotection method, resulting in a larger molecular weight distribution of the polymer and an extremely high content of impurity ions introduced.

[0112] Based on the above, it can be seen that the polymer and deprotection system of the present invention have a wide range of applications, low cost, and extremely high market prospects.

[0113] The above description is only a preferred embodiment of the present invention and does not constitute any other form of limitation to the present invention. Any modification or equivalent change made based on the technical essence of the present invention still falls within the scope of protection required by the present invention.

Claims

1. A polymer, characterized in that The weight average molecular weight of the polymer is 2000-200000, the molecular weight distribution is 1.0-1.1, the content of total metal impurity ions in the polymer is 1-100 ppb, and the structure of the polymer is or , wherein X, Y, and Z are the molar percentages of the structural unit, X, Y, and Z are positive numbers or 0, X+Y+Z≤100%, X and Y are not 0 at the same time, R1, R2, R3, and R4 include one or more of H, alkyl, cycloalkyl, and a group with an aromatic ring; and the main chain also includes a structural unit A.

2. A deprotection system, characterized in that: The system comprises a liquid storage tank (1), a pump (2), an ion exchange column (3) and a sedimentation tank (4) according to the flow direction of the material; the liquid storage tank (1), the pump (2), the ion exchange column (3) and the sedimentation tank (4) are connected in sequence through pipelines; The ion exchange column (3) comprises, from bottom to top, a lower cover (301), a lower sealing plate (302), a cylinder (303), an upper sealing plate (304), a column height adjustment rod (305) and an upper cover (306); The upper cover (306) is connected to the top of the cylinder (303) and is sealed with the top of the cylinder (303) by bolts or buckles. A threaded opening is provided in the middle of the upper cover (306). The upper sealing plate (304) is movably connected to the top of the cylinder (303). The column height adjustment rod (305) passes through the upper cover (306) and is fixedly connected to the upper sealing plate (304). The column height adjustment rod (305) is threadedly connected to the threaded opening of the upper cover (306). The column height adjustment rod (305) adjusts the height of the upper sealing plate (304) by rotating the thread. The column height adjustment rod (305) is a hollow structure, and materials flow out of the hollow structure.

3. A method for preparing the polymer according to claim 1 using the deprotection system according to claim 2, characterized in that: The following steps are involved: Step 1, dissolving a polymer resin in a solvent 1 to prepare a polymer resin solution, and placing the polymer resin solution in a liquid storage tank (1); Step 2, activating the cation exchange resin to obtain an activated cation exchange resin; Step 3, activating the anion exchange resin to obtain an activated anion exchange resin; Step 4, the activated cation exchange resin and the activated anion exchange resin are mixed evenly, and loaded into the space between the lower sealing plate (302) and the upper sealing plate (304) in the ion exchange column (3), the column temperature of the ion exchange column (3) is adjusted, the pump (2) is turned on, and the polymer resin solution in the liquid storage tank (1) is input into the ion exchange column (3) for quantitative deprotection; Step 5, establishing a working curve according to the molecular weight of the known resin material and the molar percentage of the acetal substituent, obtaining a relationship between the molecular weight of the known resin material and the molar percentage of the acetal substituent, collecting the quantitatively deprotected effluent from the ion exchange column (3), testing the molecular weight of the effluent after dilution, calculating the molar percentage of the substituent in the effluent according to the relationship, and adjusting the speed of the pump (2) according to the measured molar percentage of the substituent until the molar percentage of the substituent in the effluent is close to the molar percentage of the target substituent; Step 6: The liquid continuously flowing out of the adjusted ion exchange column (3) is transported to a sedimentation tank (4), and the solid matter is dried after sedimentation to obtain the solid polymer.

4. The method according to claim 3, characterized in that The mass percentage of the polymer resin solution in step 1 is 1-50%.

5. The method according to claim 3, characterized in that: In step 4, the volume ratio of the activated cation exchange resin to the activated anion exchange resin is (1:1)-(1:100).

6. The method according to claim 3, characterized in that The structure of the polymer resin in step 1 is or , wherein m, n, o are the molar percentages of the structural unit, m, n, o are positive numbers or 0, m+n+o=100%, m+n= X+Y, o=Z, m+n≠0, R1, R2, R3 and R4 include one or more of H, alkyl, cycloalkyl and groups with aromatic rings; and the main chain also includes the structural unit A.

7. The method according to claim 3, characterized in that The acidic groups in the cation exchange resin in step 2 include one or more of -COOH, -SO3H, aminodiacetic acid, aminophosphoric acid and phenolic hydroxyl group.

8. The method according to claim 3, characterized in that The basic groups in the anion exchange resin in step 3 include one or more of -N, -NH, -NH2, -N(CH3)2 and quaternary ammonium salts.

9. A photoresist, characterized in that: The raw material of the photoresist includes the polymer according to claim 1.

10. An electronic product, characterized in that: The raw material of the electronic product includes the photoresist as claimed in claim 9.

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