Resin as well as preparation method and application thereof

Abstract

The invention discloses resin as well as a preparation method and application thereof, and belongs to the field of production of high polymer materials and semiconductors. The preparation method provided by the invention comprises the following steps: adding hexamethylenetetramine into a benzo-12-crown-4 solution, reacting with trifluoroacetic acid, and carrying out heating reflux, water addition, stirring and pH regulation to obtain 4 '-aldehyde benzo-12-crown-4; then, 4 '-aldehyde benzene-12-crown-4 and methylamine are subjected to a reaction in a tetrahydrofuran solution, acetic acid and sodium borohydride are added, and 4'-amine benzene-12-crown-4 is obtained; finally, 4 '-aminobenzene-12-crown-4 and acid anhydride are subjected to a reaction in dimethylacetamide, triethylamine is dropwise added, then heating is conducted, dialysis and freeze drying are conducted, and the 12-crown-4 functional resin is obtained. The prepared 12-crown-4 functional resin has a large specific surface area, and has the advantages of high adsorption efficiency, large adsorption capacity, easiness in regeneration and environmental friendliness on metal ions in NMP (N-Methyl Pyrrolidone).

Description

Technical Field

[0001] The invention belongs to the field of polymer materials and semiconductor production, and specifically relates to a resin and a preparation method and application thereof. Background Art

[0002] N-methylpyrrolidone (NMP), as an excellent solvent, has a wide range of solubility for organic and inorganic substances, and is particularly good at dissolving difficult-to-handle polymer materials such as polyvinyl chloride, polyacrylonitrile and polyamide. In the semiconductor industry, NMP occupies a pivotal position and is an indispensable solvent for key steps such as photoresist stripping and precision organic cleaning. It can effectively remove dust and residues on the surface of electronic components, significantly improve the efficiency of the production process, and ensure the purity and consistency of semiconductor products. With the vigorous development of the semiconductor and new energy industries, the demand for NMP continues to grow, consolidating its position as a core solvent.

[0003] However, trace amounts of metal ions in NMP may become a hidden danger in semiconductor production. These ions may introduce impurity energy levels, weaken carrier mobility, increase resistivity, and thus damage the electrical properties of semiconductor devices. More seriously, they may also cause imbalance in semiconductor devices, leading to performance fluctuations and shortening the service life and reliability of products. Therefore, effectively removing metal ions from NMP has become a key link in ensuring the high quality of semiconductor products.

[0004] The purity of NMP is directly related to the final quality of semiconductor products. High-purity NMP can minimize impurity interference, ensure the purity and consistency of the product, and achieve stable and reliable performance. On the contrary, if NMP is doped with impurities such as metal ions, it will inevitably affect the electrical properties, durability and overall quality of the semiconductor.

[0005] In view of the above challenges, it is particularly important to use efficient and accurate methods to remove metal ions from NMP. Adsorption methods, especially resin adsorption technology, stand out for its advantages of high efficiency, economy, environmental protection and easy automation. Resin adsorption technology not only has high selectivity and large adsorption capacity, but also shows excellent regeneration ability and stability. It can flexibly select different types of resins according to specific needs, accurately remove or recover target substances such as metal ions, and is widely used in chemical, environmental protection, medicine and other fields, providing strong support for semiconductor production. Summary of the invention

[0006] In view of the above-mentioned shortcomings of the prior art, the purpose of the present invention is to provide a resin and a preparation method and application thereof. The present invention prepares a resin that can effectively adsorb and remove metal ions in N-methylpyrrolidone, thereby overcoming the technical disadvantages of the prior art.

[0007] In order to achieve the above purpose or other purposes, the present invention is implemented through the following technical solutions.

[0008] A method for preparing a resin comprises the following steps: (1) adding hexamethylenetetramine to a benzo-12-crown-4 solution and then adding trifluoroacetic acid; heating the mixture under argon for reflux reaction, pouring water into the obtained red solution after the reflux reaction, and continuing to stir. After the stirring is completed, cooling to room temperature, and adjusting the pH of the reaction mixture to 7-8; then performing post-treatment to obtain 4′-aldehyde benzo-12-crown-4; (2) dissolving the 4′-aldehydebenzo-12-crown-4 obtained in step (1) and methylamine in a tetrahydrofuran solution, adding acetic acid to a pH of 4 to 6, and reacting under an argon atmosphere; then adding sodium borohydride to the reaction solution, and continuing to stir the reaction; after the reaction is completed, post-treating to obtain 4′-aminebenzo-12-crown-4; (3) The 4′-aminobenzo-12-crown-4 prepared in step (2) and the acid anhydride are dissolved in dimethylacetamide, and triethylamine is slowly added dropwise. After the addition is completed, the reaction mixture is transferred into a reactor for heating reaction. After the reaction is completed, the solution is transferred to a dialysis bag with a molecular weight cutoff of 1000 Da and dialyzed with DMF. The dialyzed solution is freeze-dried to obtain a 12-crown-4 functionalized resin.

[0009] Furthermore, in step (1), the mass ratio of hexamethylenetetramine to benzo-12-crown-4 is (0.2-2.5):1.

[0010] Furthermore, in step (1), the mass ratio of benzo-12-crown-4 to trifluoroacetic acid is (0.05~1.5):1.

[0011] Furthermore, the heating reflux reaction time in step (1) is 4 h-6 h.

[0012] Furthermore, the mass ratio of the red solution obtained by the reaction in step (1) to water is (1-4.5):1.

[0013] Furthermore, in step (1), the stirring temperature is 80°C to 120°C, and the stirring time is 60 min to 120 min.

[0014] Furthermore, in step (1), a saturated sodium bicarbonate solution is added to the reaction mixture to neutralize the pH thereof to 7-8.

[0015] Furthermore, the post-treatment in step (1) includes extraction, drying, and column chromatography separation. Preferably, the organic layer in the reaction mixture is extracted with dichloromethane, and then the organic layer is dried with anhydrous magnesium sulfate, and then the solvent is removed by rotary evaporation under reduced pressure. More preferably, ethyl acetate and petroleum ether in a ratio of (0.5-1.5):1 are used as eluents, and the organic layer after drying is separated by column chromatography.

[0016] Furthermore, in step (2), the mass ratio of 4′-aldehyde benzo-12-crown-4 and methylamine is (0.5~2.5):1.

[0017] Furthermore, in step (2), the mass ratio of 4′-formaldehyde benzo-12-crown-4 and tetrahydrofuran is (0.1-1.5):1.

[0018] Furthermore, in step (2), the reaction is carried out under an argon atmosphere for 2 h to 4 h, and the reaction temperature is 40° C. to 80° C.

[0019] Furthermore, in step (2), the mass ratio of the reaction solution to sodium borohydride is (0.8-3.5): 1 Furthermore, the stirring reaction time in step (2) is 60 min-120 min.

[0020] Furthermore, the post-treatment in step (2) includes extraction, drying and recrystallization. Preferably, ethyl acetate is used for extraction to obtain a mixture, followed by rotary evaporation under reduced pressure to remove the solvent, and then recrystallization in acetone.

[0021] Furthermore, the acid anhydride in step (3) is selected from but not limited to adipic anhydride and phthalic anhydride.

[0022] Furthermore, in step (3), the mass ratio of acid anhydride to 4′-aminobenzo-12-crown-4 is (0.5-5.5):1.

[0023] Furthermore, in step (3), the mass ratio of acid anhydride to triethylamine is (0.5-2.5):1.

[0024] Furthermore, in step (3), the solid-liquid ratio of acid anhydride to dimethylacetamide (g:mL) is 1 / 50 to 1 / 20.

[0025] Furthermore, in step (3), the temperature is heated to 40°C to 80°C, and the reaction time is 8 h to 16 h.

[0026] Furthermore, the freeze-drying in step (3) is performed for 24 h to 48 h.

[0027] The present invention further provides a resin prepared by the above method.

[0028] The third aspect of the present invention also discloses the use of the resin obtained above in removing metal ions in N-methylpyrrolidone.

[0029] In summary, the present invention provides a method for preparing a resin, and the prepared 12-crown-4 functionalized resin can be used to remove metal ions in N-methylpyrrolidone. The 12-crown-4 functionalized resin obtained by the present invention has high adsorption efficiency, large adsorption capacity, easy regeneration and environmental friendliness for metal ions in NMP. Due to the strong interaction between the 12-crown-4 functionalized resin obtained by the present invention and the metal ions, and the 12-crown-4 functionalized resin has a specific cavity structure, so that it has a high selectivity for platinum, thereby achieving efficient removal of trace metal ions. The contents of platinum ions, calcium ions, copper ions and magnesium ions in NMP after adsorption are all reduced to below 50 ppt.

[0030] The 12-crown-4 functionalized resin prepared by the present invention has a large specific surface area, which provides abundant active sites for the resin. These sites increase the surface area in contact with the adsorbate, thereby improving the adsorption efficiency. In addition, the size of the specific surface area is closely related to the pore size and pore volume of the resin. Generally, a larger specific surface area is associated with a smaller pore size, which helps to effectively adsorb metal ions or molecules of a specific size. Therefore, these characteristics of the 12-crown-4 functionalized resin give it significant advantages in adsorption applications. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 The schematic diagram is a reaction route of the preparation method of the present invention.

[0032] Figure 2 1 is a nitrogen adsorption-desorption isotherm diagram of the 12-crown-4 functionalized resin obtained in Example 1 of the present invention.

[0033] Figure 3 Schematic diagram of scanning electron microscopy of the 12-crown-4 functionalized resin obtained in Example 1 of the present invention. DETAILED DESCRIPTION

[0034] The following describes the embodiments of the present invention through specific embodiments, and those skilled in the art can easily understand other advantages and effects of the present invention from the contents disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments, and the details in this specification can also be modified or changed in various ways based on different viewpoints and applications without departing from the spirit of the present invention. It should be noted that the following embodiments and features in the embodiments can be combined with each other without conflict.

[0035] The present invention is described below by means of specific embodiments. Example 1

[0036] 2 g of hexamethylenetetramine was added to 4 g of benzo-12-crown-4 solution and added to 20 g of trifluoroacetic acid. The mixture was refluxed under argon for 4 hours, and then water was poured into the obtained red solution (the mass ratio of red solution to water was 2:1). Stir at 90 °C for 90 minutes. Cool to room temperature and add saturated sodium bicarbonate solution to neutralize it to pH = 7. The obtained mixture was extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate, and then the solvent was removed by rotary evaporation under reduced pressure. The crude oil was separated by column chromatography using ethyl acetate and petroleum ether in a ratio of 1.5:1 as eluent to obtain white solid 4′-aldehyde benzo-12-crown-4.

[0037] Dissolve 1 g of 4′-aldehydebenzo-12-crown-4 and 0.5 g of methylamine in 5 g of tetrahydrofuran solution. Add acetic acid to the mixture until the pH is 5 and react at 60°C under argon atmosphere for 3 hours. Add 1.25 g of sodium borohydride under argon atmosphere and continue to stir the reaction mixture for 90 minutes. Then, extract the mixture with ethyl acetate. Remove the solvent by rotary evaporation under reduced pressure, and recrystallize the crude oil in acetone to obtain 4′-aminebenzo-12-crown-4.

[0038] Dissolve 0.15 g of 4′-aminobenzo-12-crown-4 and 0.5 g of phthalic anhydride in 20 mL of dimethylacetamide in a beaker. Slowly drop 0.45 g of triethylamine into the beaker, and then transfer the reaction mixture into a reactor and heat it to 60°C for 12 hours. Transfer the solution after the reaction to a dialysis bag with a molecular weight cutoff (MW) of 1000 Da and dialyze it with DMF. The dialyzed solution was freeze-dried for 24 hours to obtain 12-crown-4 functionalized resin.

[0039] The prepared 12-crown-4 functionalized resin was used to adsorb and remove metal ions from NMP solution after distillation. An adsorption column with a diameter of 20 mm and a length of 300 mm was selected, and the 12-crown-4 functionalized resin was filled in the adsorption column with a filling rate of 80%. Under the conditions of adsorption pressure of 0.2 MPaG and adsorption temperature of 30°C, NMP solutions with platinum ion, calcium ion, copper ion and magnesium ion contents of 3000 ppb, 1500 ppb, 2000 ppb and 1500 ppb, respectively, were passed through the resin at a rate of 0.1 L / min, and the contents of platinum ion, calcium ion, copper ion and magnesium ion in the NMP solution after adsorption were measured. The results are shown in Table 1.

[0040] Table 1 Metal ions Content before adsorption / (ppb) Content after 12-crown-4 functionalized resin adsorption / (ppt) platinum 3000 27 calcium 1500 41 copper 2000 38 magnesium 1500 46 The obtained 12-crown-4 functionalized resin was measured by specific surface area (BET), and the obtained nitrogen adsorption-desorption isotherm diagram was as follows: Figure 2As shown in the figure, it can be seen that the prepared resin material exhibits a type IV isotherm, indicating that it has a mesoporous structure and the adsorption pore structure is relatively rich.

[0041] The obtained 12-crown-4 functionalized resin was photographed using a scanning electron microscope (SEM). Figure 3 As shown in the figure, it can be seen that the prepared material has abundant surface pores, which promotes the adsorption of metal ions. Example 2

[0042] 2 g of hexamethylenetetramine was added to 4 g of benzo-12-crown-4 solution and added to 20 g of trifluoroacetic acid. The mixture was refluxed under argon for 4 hours, and then water was poured into the obtained red solution (the mass ratio of red solution to water was 1:1). Stir at 90 °C for 90 minutes. Cool to room temperature and add saturated sodium bicarbonate solution to neutralize it to pH 7. The obtained mixture was extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate and then the solvent was removed by rotary evaporation under reduced pressure. The crude oil was separated by column chromatography using ethyl acetate and petroleum ether in a ratio of 0.5:1 as eluent to obtain 4′-aldehyde benzo-12-crown-4 as a white solid.

[0043] Dissolve 1 g of 4′-aldehydebenzo-12-crown-4 and 0.5 g of methylamine in 5 g of tetrahydrofuran solution. Add acetic acid to the mixture until the pH is 5 and react at 60°C under argon atmosphere for 3 hours. Add 1.25 g of sodium borohydride under argon atmosphere and continue to stir the reaction mixture for 90 min. Then, extract the mixture with ethyl acetate. Remove the solvent by rotary evaporation under reduced pressure, and recrystallize the crude oil in acetone to obtain 4′-aminobenzo-12-crown-4.

[0044] Dissolve 0.15 g of 4′-aminobenzo-12-crown-4 and 0.8 g of phthalic anhydride in 20 mL of dimethylacetamide in a beaker. Slowly drop 0.8 g of triethylamine into the beaker, and then transfer the reaction mixture into a reactor and heat it to 60°C for 12 hours. Transfer the solution after the reaction to a dialysis bag with a molecular weight cutoff (MW) of 1000 Da and dialyze it with DMF. The dialyzed solution was freeze-dried for 24 hours to obtain a 12-crown-4 functionalized resin.

[0045] The 12-crown-4 functionalized resin prepared by the present invention was used to adsorb and remove metal ions from a distilled NMP solution. An adsorption column with a diameter of 20 mm and a length of 300 mm was selected, and the adsorption column was filled with a 12-crown-4 functionalized phenolic resin with a filling rate of 80%. Under the conditions of an adsorption pressure of 0.2 MPaG and an adsorption temperature of 30°C, an NMP solution with platinum ion, calcium ion, copper ion and magnesium ion contents of 3000 ppb, 1500 ppb, 2000 ppb and 1500 ppb, respectively, was passed through the resin at a rate of 0.1 L / min, and the contents of platinum ion, calcium ion, copper ion and magnesium ion in the NMP solution after adsorption were measured. The results are shown in Table 2.

[0046] Table 2 Metal ions Content before adsorption / (ppb) Content after 12-crown-4 functionalized resin adsorption / (ppt) platinum 3000 39 calcium 1500 44 copper 2000 47 magnesium 1500 41 Example 3

[0047] 10 g of hexamethylenetetramine was added to 4 g of benzo-12-crown-4 solution and added to 80 g of trifluoroacetic acid. The mixture was refluxed under argon for 6 hours, and then water was poured into the obtained red solution (the mass ratio of red solution to water was 4.5:1). Stir at 80 °C for 120 minutes. Cool to room temperature and add saturated sodium bicarbonate solution to neutralize it to pH = 7. The obtained mixture was extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate and then the solvent was removed by rotary evaporation under reduced pressure. The crude oil was separated by column chromatography using ethyl acetate and petroleum ether in a ratio of 1:1 as eluent to obtain 4′-aldehyde benzo-12-crown-4 as a white solid.

[0048] Dissolve 1 g of 4′-aldehydebenzo-12-crown-4 and 2 g of methylamine in 10 g of tetrahydrofuran solution. Add acetic acid to the mixture until the pH is 4 and react at 40°C under argon atmosphere for 4 hours. Add 1.2 g of sodium borohydride under argon atmosphere and continue to stir the reaction mixture for 90 min. Then, extract the mixture with ethyl acetate. Remove the solvent by rotary evaporation under reduced pressure, and recrystallize the crude oil in acetone to obtain 4′-aminobenzo-12-crown-4.

[0049] Dissolve 0.15 g of 4′-aminobenzo-12-crown-4 and 0.8 g of phthalic anhydride in 16 mL of dimethylacetamide in a beaker. Slowly drop 0.32 g of triethylamine into the beaker, and then transfer the reaction mixture into a reactor and heat it to 40 °C for 16 hours. Transfer the solution after the reaction to a dialysis bag with a molecular weight cutoff (MW) of 1000 Da and dialyze it with DMF. The dialyzed solution was freeze-dried for 48 hours to obtain a 12-crown-4 functionalized resin.

[0050] The 12-crown-4 functionalized resin prepared by the present invention was used to adsorb and remove metal ions from NMP solution after distillation. An adsorption column with a diameter of 20 mm and a length of 300 mm was selected, and the adsorption column was filled with 12-crown-4 functionalized phenolic resin, and the filling rate was 80%. Under the conditions of adsorption pressure of 0.2 MPaG and adsorption temperature of 30°C, NMP solutions with platinum ion, calcium ion, copper ion and magnesium ion contents of 3000 ppb, 1500 ppb, 2000 ppb and 1500 ppb, respectively, were passed through the resin at a rate of 0.1 L / min, and the contents of platinum ion, calcium ion, copper ion and magnesium ion in the NMP solution after adsorption were measured. The results are shown in Table 3.

[0051] Table 3 Metal ions Content before adsorption / (ppb) Content after 12-crown-4 functionalized resin adsorption / (ppt) platinum 3000 31 calcium 1500 39 copper 2000 43 magnesium 1500 46 Example 4

[0052] 0.8 g of hexamethylenetetramine was added to 4 g of benzo-12-crown-4 solution and 2.6 g of trifluoroacetic acid was added. The mixture was refluxed under argon for 5 hours, and then water was poured into the obtained red solution (the mass ratio of red solution to water was 2:1). Stir at 120 °C for 60 minutes. Cool to room temperature and add saturated sodium bicarbonate solution to neutralize it to pH = 8. The obtained mixture was extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate and then the solvent was removed by rotary evaporation under reduced pressure. The crude oil was separated by column chromatography using ethyl acetate and petroleum ether in a ratio of 1:1 as eluent to obtain 4′-aldehyde benzo-12-crown-4 as a white solid.

[0053] Dissolve 1 g of 4′-aldehydebenzo-12-crown-4 and 0.4 g of methylamine in 0.6 g of tetrahydrofuran solution. Add acetic acid to the mixture until the pH is 6 and react at 80°C under argon atmosphere for 2 hours. Add 1 g of sodium borohydride under argon atmosphere and continue to stir the reaction mixture for 90 min. Then, extract the mixture with ethyl acetate. Remove the solvent by rotary evaporation under reduced pressure, and recrystallize the crude oil in acetone to obtain 4′-aminobenzo-12-crown-4.

[0054] Dissolve 1.6 g of 4′-aminobenzo-12-crown-4 and 0.8 g of phthalic anhydride in 40 mL of dimethylacetamide in a beaker. Slowly add 1.6 g of triethylamine to the beaker, then transfer the reaction mixture into a reactor and heat it to 80°C for 8 hours. Transfer the solution after the reaction to a dialysis bag with a molecular weight cutoff (MW) of 1000 Da and dialyze it with DMF. The dialyzed solution was freeze-dried for 36 hours to obtain a 12-crown-4 functionalized resin.

[0055] The 12-crown-4 functionalized resin prepared by the present invention was used to adsorb and remove metal ions from NMP solution that had been distilled. An adsorption column with a diameter of 20 mm and a length of 300 mm was selected, and the adsorption column was filled with 12-crown-4 functionalized phenolic resin, with a filling rate of 80%. Under the conditions of an adsorption pressure of 0.2 MPaG and an adsorption temperature of 30°C, NMP solutions with platinum ion, calcium ion, copper ion and magnesium ion contents of 3000 ppb, 1500 ppb, 2000 ppb and 1500 ppb, respectively, were passed through the resin at a rate of 0.1 L / min, and the contents of platinum ion, calcium ion, copper ion and magnesium ion in the NMP solution after adsorption were measured. The results are shown in Table 4.

[0056] Table 4 Metal ions Content before adsorption / (ppb) Content after 12-crown-4 functionalized resin adsorption / (ppt) platinum 3000 41 calcium 1500 47 copper 2000 34 magnesium 1500 41 In summary, it can be seen that the functionalized resin prepared by the present invention has excellent adsorption performance for platinum ions, calcium ions, copper ions and magnesium ions, and can be used to remove trace metal ions in NMP solutions. By adjusting the feeding amount of anhydride and crown ether, adsorption conditions, and parameters of adsorption column and adsorbent, the adsorption performance can be further optimized. The resin prepared by the present invention can remove trace metal ions in NMP solutions by virtue of its advantages such as efficient adsorption performance, good thermal stability, easy preparation, good operational adaptability, environmental protection and safety.

[0057] The above embodiments are merely illustrative of the principles and effects of the present invention, and are not intended to limit the present invention. Anyone familiar with the art may modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by a person of ordinary skill in the art without departing from the spirit and technical concept disclosed by the present invention shall still be covered by the claims of the present invention.

Claims

1. A method for preparing a resin, characterized in that: The following steps are involved: (1) adding hexamethylenetetramine to a benzo-12-crown-4 solution and then adding trifluoroacetic acid; heating the mixture under argon for reflux reaction, pouring water into the obtained red solution after the reflux reaction, and continuing to stir. After the stirring is completed, cooling to room temperature, and adjusting the pH of the reaction mixture to 7-8; then performing post-treatment to obtain 4′-aldehyde benzo-12-crown-4; (2) dissolving the 4′-aldehydebenzo-12-crown-4 obtained in step (1) and methylamine in a tetrahydrofuran solution, adding acetic acid to a pH of 4 to 6, reacting under an argon atmosphere, then adding sodium borohydride to the reaction solution, and continuing to stir the reaction; after the reaction is completed, post-treating to obtain 4′-aminebenzo-12-crown-4; (3) The 4′-aminobenzo-12-crown-4 prepared in step (2) and the acid anhydride are dissolved in dimethylacetamide, and triethylamine is slowly added dropwise. After the addition is completed, the reaction mixture is transferred into a reactor for heating reaction. After the reaction is completed, the solution is transferred to a dialysis bag with a molecular weight cutoff of 1000 Da and dialyzed with DMF. The dialyzed solution is freeze-dried to obtain a 12-crown-4 functionalized resin.

2. The preparation method according to claim 1, characterized in that In step (1), the mass ratio of hexamethylenetetramine to benzo-12-crown-4 is (0.2-2.5):

1.

3. The preparation method according to claim 1, characterized in that: The mass ratio of benzo-12-crown-4 and trifluoroacetic acid in step (1) is (0.05~1.5):

1.

4. The preparation method according to claim 1, characterized in that: Include one or more of the following technical features: The heating reflux reaction time in step (1) is 4 h-6 h; Step (1) The stirring temperature is 80°C to 120°C, and the stirring time is 60 min to 120 min; Step (1) Add saturated sodium bicarbonate solution to the reaction mixture to neutralize the pH to 7-8.

5. The preparation method according to claim 1, characterized in that: In step (2), the mass ratio of 4′-aldehyde benzo-12-crown-4 and methylamine is (0.5~2.5):

1.

6. The preparation method according to claim 1, characterized in that: In step (2), the mass ratio of 4′-formaldehyde benzo-12-crown-4 and tetrahydrofuran is (0.1-1.5):

1.

7. The preparation method according to claim 1, characterized in that: In step (3), the mass ratio of acid anhydride to 4′-aminobenzo-12-crown-4 is (0.5-5.5):

1.

8. The preparation method according to claim 1, characterized in that: Include one or more of the following technical features: In step (3), the mass ratio of acid anhydride to triethylamine is (0.5-2.5): 1; In step (3), the solid-liquid ratio of acid anhydride to dimethylacetamide is 1 / 50 to 1 / 20 in g:mL; In step (3), the temperature is heated to 40°C to 80°C, and the reaction time is 8 h to 16 h; In step (3), freeze drying is performed for 24 h to 48 h.

9. The resin prepared by the preparation method according to any one of claims 1 to 8.

10. Use of the resin prepared by the preparation method according to any one of claims 1 to 8 in removing metal ions from N-methylpyrrolidone.

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