CN100509897C - Synthesis for resorcin-containing coarse-pore sphere type adsorption resin and application method thereof - Google Patents

Abstract

Synthesis and application method of macroporous spherical adsorption resin containing resorcinol. It relates to the synthesis and application method of an adsorption resin, in particular to the synthesis method of a macroporous spherical donor-type adsorption resin containing resorcinol, and utilizes the macroporous spherical donor-type adsorption resin to extract caffeine and theophylline from natural products. A method for extracting and separating caffeine, theophylline, and VB ₁₂ in an aqueous solution of VB ₁₂ . The synthesis of macroporous spherical donor-type adsorption resin containing resorcinol is based on paraformaldehyde (or formaldehyde aqueous solution), resorcinol, and phenol as raw materials, and in the presence of a special porogen, ethylene glycol, by reverse phase The suspension polycondensation method is used to synthesize, and the synthesis reaction is completed in the presence of an acidic catalyst. The synthesis method is simple, the reaction is completed in one step, the production process is simplified, and the cost is reduced. Moreover, the adsorption resin contains a large number of phenolic hydroxyl groups, has strong adsorption capacity for caffeine, theophylline, and VB ₁₂ that have hydrogen bond acceptors, is easy to desorb, has high efficiency, and can be reused after elution.

Description

Synthesis and Application of Resorcinol-Containing Macroporous Spherical Adsorbent Resin

technical field

The present invention relates to the synthesis and application method of a kind of adsorption resin, especially relate to the synthesis method of the macroporous spherical donor type adsorption resin containing resorcinol, and utilize this macroporous spherical donor type adsorption resin to obtain natural product caffeine, A method for extracting and separating caffeine, theophylline, and VB ₁₂ from an aqueous solution of theophylline and VB ₁₂ .

Background technique

Caffeine, also known as caffeine (1,3,7-trimethylxanthine), is an alkaloid in tea, coffee, cocoa and some other plants. The content in tea is relatively high, about 1% to 5%. As a central nervous system stimulant in medicine, it is used for the treatment of central respiratory failure, neurasthenia, and elimination of fatigue. The methods of extracting medicinal caffeine from tea include sublimation method, solvent method, adsorption method and supercritical _CO2 extraction. Method (Huang Jizhen, Chinese herbal medicine, 1999,30 (6): 473～475), the existing report (Kaz SaulNorman, EP, 0,076,620A2,1982) with active carbon adsorption caffeine, literature (He Binglin, Huang Wenqiang edited, ion exchange and Adsorption resin, Shanghai: Shanghai Science and Technology Education Press, 1995: 436) mentioned that there is a patent to use XAD-4, Duolite S-761 resin adsorption and separation of caffeine, therefore, extracting and separating caffeine from aqueous solution with the adsorption resin method is also a very important method.

Theophylline, a representative drug of methylxanthines, has been increasingly used in the treatment of patients with obstructive pulmonary disease (COPD). According to reports (Hu Xien, Bai Runsheng, Wang Xuejun, Journal of Tsinghua University (Natural Science Edition), 1996, 36 (12): 13～17) the annual production of 1000t caffeine factory theophylline mother liquor discharge is 12kt, if not reclaimed cause serious waste.

VB ₁₂ plays a very important role in life and chemical processes such as oxygen transfer, storage and activation, electron transfer and enzyme catalysis in the human body. In medicine, VB ₁₂ is an anti-anemia drug, which is used for the adjuvant treatment of megaloblastic anemia and neuritis. Vitamin VB ₁₂ preparation Visco plays an important role in promoting wound healing caused by burns and radiation. Vitamin VB ₁₂ is used to prevent and treat oral mucositis, and it has also achieved good prevention and treatment effects. Existing studies have found that the lack of VB ₁₂ is associated with related to diabetes. Due to the complex structure of VB ₁₂ , chemical synthesis is very difficult, and currently medicinal VB ₁₂ is still extracted from fermentation broth. Solvent method has been used to isolate VB ₁₂ from fermentation broth, which consumes a large amount of solvent and is difficult to remove various proteins therein. Later, the resin adsorption method was applied to adsorb and separate VB ₁₂ from the fermentation broth, and the product quality was improved to some extent (He Binglin, edited by Huang Wenqiang, Ion Exchange and Adsorption Resin, Shanghai: Shanghai Science and Technology Education Press, 1995), but the effect was not ideal.

Conventional resins have limited adsorption capacity for active ingredients of traditional Chinese medicines containing hydrogen bond acceptors, while phenolic hydroxyl is a good hydrogen bond donor and can easily form hydrogen bonds with active ingredients of traditional Chinese medicines containing hydrogen bond acceptors. Because caffeine and theophylline molecules are good hydrogen bond acceptors, and phenolic hydroxyl group is a good hydrogen bond donor, hydrogen bonds can be formed between them. In addition, VB ₁₂ contains a large number of amide functional groups. The carbonyl group can form a hydrogen bond with the phenolic hydroxyl group. According to this fact, we hope to synthesize the adsorption resin containing the phenolic hydroxyl group. The preparation of donor-type adsorption resins containing phenolic hydroxyl groups by copolymerization requires many reaction steps, the number of resins containing phenolic hydroxyl groups is small, and the adsorption capacity of organic matter containing hydrogen bond acceptors is limited (Li Aimin, Zhang Quanxing, Liu Fuqiang, Fei Zhenghao, Wang Xuejiang, Chen Jinlong, Ion Exchange and Adsorption, 2001, 17(6): 515～525; Xu Mingcheng, Liu Juxiang, Fan Yunge, Shi Zuoqing, Shi Rongfu, Jin Xiaonong, He Binglin, Xu Mancai, Ion Exchange and Adsorption, 2001, 16(1): 16～ 21) However, the preparation of resorcinol-containing macroporous spherical donor-type adsorption resin by reverse-phase suspension polycondensation method is simple, the number of phenolic hydroxyl groups is large, and the adsorption capacity of hydrogen bond acceptor organic matter is strong. The diphenol macroporous spherical donor-type adsorption resin is used for the extraction and separation of theophylline, caffeine and VB ₁₂ drugs in the water system, which opens up a new way for the extraction and separation of theophylline, caffeine and VB ₁₂ drugs.

At present, there is no report on the synthesis of macroporous spherical donor-type adsorption resin containing resorcinol at home and abroad. The macroporous spherical donor-type adsorbent resin containing resorcinol contains more strong polar groups of phenolic hydroxyl groups—OH, so the main mechanism of adsorption of caffeine, theophylline, and VB ₁₂ active ingredients in traditional Chinese medicine is the hydrogen bond adsorption mechanism.

The macroporous spherical donor-type adsorption resin containing resorcinol not only has good adsorption properties for theophylline, caffeine, and VB ₁₂ drugs, but also can be effectively adsorbed with methanol, or its aqueous solution, or a certain concentration of hydrochloric acid solution. The elution can be reused after elution.

Contents of the invention

The object of the present invention is to provide a synthesis method of a resorcinol-containing macroporous spherical donor-type adsorption resin and its application method in the extraction and separation of caffeine, theophylline and VB ₁₂ drugs in aqueous solution. The resorcinol-containing macroporous spherical donor-type adsorption resin is prepared by the reverse-phase suspension polycondensation method, the water content is relatively high, and the number of phenolic hydroxyl groups is also large, and the process is simple and completed in one step.

The purpose of the present invention is achieved through the following technical solutions:

Containing the synthesis of resorcinol macroporous spherical adsorption resin, the macroporous spherical donor type adsorption resin containing resorcinol is synthesized with paraformaldehyde, comprising the following components:

Oil phase: liquid wax;

Reactive monomers: paraformaldehyde, resorcinol, phenol;

Porogen: ethylene glycol;

Dispersant: Span80; (Sorbitan Monooleate)

Catalyst: concentrated hydrochloric acid containing (HCl) 36-38%.

Containing the synthesis of resorcinol macroporous spherical adsorption resin, the synthesis of resorcinol-containing macroporous spherical adsorption resin with formaldehyde solution comprises the following components:

Oil phase: liquid wax;

Reactive monomer: formaldehyde aqueous solution (the content of HCHO is 36-38%), resorcinol, phenol;

Porogen: ethylene glycol;

Dispersant: Span80;

Catalyst: concentrated hydrochloric acid containing (HCl) 36-38%.

Synthesis of the above-mentioned resorcinol-containing macroporous spherical adsorption resin, the appearance of this resin is a sphere, in brown, the diameter of the ball is 0.2-1mm, the surface has a sponge-like or honeycomb-like structure, and the surface has Porosity, the average pore diameter is 30-120nm, the skeleton density is 1.08-1.32g/cm ³ , the specific surface area is 60-100m ² /g, the water content is 30-50%, and the phenolic hydroxyl content is 2-3.72mmol/g.

The synthesis of the above-mentioned resorcinol-containing macroporous spherical adsorption resin, the appearance of this resin is a sphere, light yellow or yellow, the diameter of the sphere is 0.2-1mm, and the surface has a sponge-like or honeycomb-like structure. The surface is porous, with an average pore diameter of 50-300nm, a skeleton density of 1.08-1.32g/cm ³ , a specific surface area of 100-200m ² /g, a water content of 40-65%, and a phenolic hydroxyl content of 1.5-2.5mmol/g.

The synthesis of the above-mentioned macroporous spherical adsorption resin containing resorcinol, the preparation method of the macroporous spherical donor type adsorption resin containing resorcinol synthesized with paraformaldehyde, comprises the following steps:

(1) Mix ethylene glycol, paraformaldehyde, resorcinol, and phenol at a ratio of 10.9:3.7:0.7:1 (molar ratio), add 1-2% dispersant Span80 to the above system, and continue stirring until uniform . Oil phase: take 4 to 6 times the volume of liquid wax;

(2) Add the mixture in (1) into the liquid wax, start stirring, 100-150 rpm, raise the temperature to 70-75°C, and keep the temperature constant for 1-2 hours;

(3) Add 2 mL of concentrated hydrochloric acid containing (HCl) 36-38%, continue to stir and keep the temperature for 2 hours, adjust the stirring speed, so that the size of the oil droplets is suitable (to ensure the adsorption of the macroporous spherical donor containing resorcinol The diameter of the resin ball is appropriate), slowly raise the temperature to 82°C for 1 hour at a constant temperature, raise the temperature to 100°C for 1.5 hours, and raise the temperature to 130-140°C for 5 hours;

(4) After the polymerization reaction is completed, the material is discharged, the resin is filtered out, and it is repeatedly washed with an aqueous solution prepared by a surfactant, extracted with acetone, vacuum-dried, and sieved to prepare resorcinol-containing resin with a particle size of 0.2 to 1 mm. Macroporous spherical body-giving adsorption resin.

The synthesis of the above-mentioned macroporous spherical adsorption resin containing resorcinol, the preparation method of synthesizing the macroporous spherical donor type adsorption resin containing resorcinol with formaldehyde aqueous solution comprises the following steps:

(1) Mix ethylene glycol, formaldehyde aqueous solution HCHO content of 36-38%, resorcinol and phenol according to 10.9:3.7:0.7:1 (molar ratio), add 1-2% dispersant Span80 to the above In the system, continue to stir until uniform. Oil phase: take 4 to 6 times the volume of liquid wax;

(2) Add the mixture in (1) into the liquid wax, start stirring, 100-150 rpm, raise the temperature to 70-75°C, and keep the temperature constant for 1-2 hours;

(3) Add 2 mL of concentrated hydrochloric acid containing (HCl) 36-38%, continue to stir and keep the temperature for 2 hours, adjust the stirring speed, so that the size of the oil droplets is suitable (to ensure the adsorption of the macroporous spherical donor containing resorcinol The diameter of the resin ball is suitable), slowly raise the temperature to 82°C for 1 hour, and then raise the temperature to 100°C for 1.5 hours, then separate the water produced by the water separator, and when the amount of separated water no longer increases, raise the temperature to 130-140°C 5h;

(4) After the polymerization reaction is completed, the material is discharged, and the resin is filtered out, washed with an aqueous solution prepared by a surfactant, extracted with acetone, vacuum-dried, and sieved to prepare macropores containing resorcinol with a particle size of 0.2 to 1 mm. Spherical donor type adsorption resin.

The application method of macroporous spherical adsorption resin containing resorcinol, the resin can be reused after adsorption, desorption and elution of caffeine, theophylline and VB ₁₂ containing hydrogen bond acceptors.

The application method of the above-mentioned resorcinol-containing macroporous spherical adsorption resin, the method for extracting caffeine from the caffeine aqueous solution, comprises the following steps:

(1) Pack the adsorption resin in a glass adsorption column with a column diameter of 10-50mm and a resin volume of 5mL-2.5L, and install it into a resin column;

(2) The caffeine aqueous solution flows through the above-mentioned resin column, the caffeine is adsorbed in the resin, and is eluted with 1M HCl and 40% methanol solution after washing;

(3) The flow rate of adsorption, washing, and desorption is 1.5 to 2.5 bed volumes per hour, and the desorption liquid is vacuum-dried to obtain a powdery white caffeine product, and the recovery rate of caffeine is 90 to 95%. Resin can be reused.

The application method of the above-mentioned resorcinol-containing macroporous spherical adsorption resin, the method for extracting theophylline from theophylline aqueous solution, comprises the following steps:

(1) Pack the adsorption resin in a glass adsorption column with a column diameter of 10-50mm and a resin volume of 5mL-2.5L, and install it into a resin column;

(2) Theophylline aqueous solution flows through the above-mentioned resin column, theophylline is adsorbed in the resin, and is eluted with 1M HCl and 80% methanol solution after washing;

(3) The flow rate of adsorption, washing, and desorption is 1.5-3 bed volumes/hour, and the desorption solution is vacuum-dried to obtain a white powdered theophylline product, and the recovery rate of theophylline is 85-90%. Resin can be reused.

The above-mentioned application method containing resorcinol macroporous spherical adsorption resin, the method for extracting _VB12 from _VB12 aqueous solution, comprises the following steps:

(1) Pack the adsorption resin in a glass adsorption column with a column diameter of 10-50mm and a resin volume of 5mL-2.5L, and install it into a resin column;

(2) The VB ₁₂ aqueous solution flows through the above-mentioned resin column, and the VB ₁₂ is adsorbed in the resin, washed and eluted with 80% methanol solution;

(3) The flow rate of adsorption, washing, and desorption is 1.1-1.5 bed volumes/hour, and the desorption solution is vacuum-dried to obtain a red powder VB ₁₂ product, and the recovery rate of VB ₁₂ is 60-85%. Resin can be reused.

Advantage and effect of the present invention are:

The preparation of resorcinol-containing macroporous spherical donor-type adsorption resin by reverse suspension polycondensation method has a high water content and a large number of phenolic hydroxyl groups. The process is simple and can be completed in one step. The one-time investment cost is low and it is easy for large-scale industrial production. .

Extracting caffeine, theophylline, and VB ₁₂ from the aqueous solution of caffeine, theophylline, and VB ₁₂ using resorcinol-containing macroporous spherical donor-type adsorption resin has a simpler process and does not use Toxic and volatile organic solvents, safe and reliable, with low production costs.

The caffeine extracted by the invention can be used for treating central respiratory failure, neurasthenia and eliminating fatigue. The extracted theophylline can be used in the treatment of patients with obstructive pulmonary disease (COPD). The extracted VB ₁₂ can be used for adjuvant treatment of megaloblastic anemia and neuritis, and can also be used for prevention and treatment of oral mucositis. Its preparation, Visker, can promote wound healing caused by burns and radiation.

Description of drawings

Fig. 1 is the SEM photo figure (×80) of macroporous spherical donor type adsorption resin synthesized with resorcinol with paraformaldehyde;

Fig. 2 synthesizes the macroporous spherical donor type adsorption resin SEM photo figure (×80) containing resorcinol with formaldehyde solution;

Fig. 3 is a SEM photograph of a macroporous spherical donor-type adsorption resin containing resorcinol synthesized by paraformaldehyde (×10 ⁴ );

Fig. 4 is a SEM photograph of a macroporous spherical donor-type adsorption resin containing resorcinol synthesized by aqueous formaldehyde solution (×10 ⁴ );

Fig. 5 is a SEM photograph of a macroporous spherical donor-type adsorption resin containing resorcinol synthesized by paraformaldehyde (×2×10 ⁴ );

Fig. 6 is a SEM photograph (×2×10 ⁴ ) of macroporous spherical donor-type adsorption resin synthesized with resorcinol by using formaldehyde solution.

Detailed ways

The present invention will be described in detail below with reference to the accompanying drawings and embodiments.

Example 1

Step 1: Mix ethylene glycol 60mL, paraformaldehyde 11.0g, resorcinol 7.3g, phenol 9.4g according to 10.9:3.7:0.7:1 (molar ratio), add 1.5g dispersant Span80 (dehydrated sorrel Anhydrous sugar alcohol monooleate) in the above system, continue to stir until uniform. Oil phase: take 400mL liquid wax;

Step 2: Add the mixture in (1) into the liquid wax, start stirring, 100-150 rpm, raise the temperature to 70-75°C, and keep the temperature constant for 1-2 hours;

Step 3: Add 2 mL of concentrated hydrochloric acid containing (HCl) 36-38%, continue to stir and keep the temperature for 2 hours, adjust the stirring speed, so that the size of the oil droplets is suitable (to ensure the adsorption of the macroporous spherical donor containing resorcinol The diameter of the resin ball is appropriate), slowly raise the temperature to 82°C for 1 hour at a constant temperature, raise the temperature to 100°C for 1.5 hours, and raise the temperature to 130-140°C for 5 hours;

Step 4: After the polymerization reaction is completed, the material is discharged, the resin is filtered out, and the aqueous solution prepared with a surfactant is washed several times (so that most of the dispersant and porogen are removed), extracted with acetone, vacuum dried, and sieved to prepare A macroporous spherical donor-type adsorption resin containing resorcinol with a particle size of 0.2-1mm is produced.

Example 2

Step 1: Mix ethylene glycol 60mL, formaldehyde solution 27mL, resorcinol 7.3g, phenol 9.4g according to 10.9:3.7:0.7:1 (molar ratio), add 1.5g dispersant Span80 to the above system, continue Stir until smooth. Oil phase: take 400mL liquid wax;

Step 2: Add the mixture in (1) into the liquid wax, start stirring, 100-150 rpm, raise the temperature to 70-75°C, and keep the temperature constant for 1-2 hours;

Step 3: Add 2 mL of concentrated hydrochloric acid containing (HCl) 36-38%, continue to stir and keep the temperature for 2 hours, adjust the stirring speed, so that the size of the oil droplet (to ensure the macroporous spherical donor adsorption resin containing resorcinol generated) If the diameter of the ball is appropriate), slowly raise the temperature to 82°C for 1 hour, and then raise the temperature to 100°C for 1.5 hours. The water separator will separate the generated water. When the amount of separated water no longer increases, raise the temperature to 130-140°C for reaction. 5h;

Step 4: After the polymerization reaction is completed, the material is discharged, the resin is filtered out, and the aqueous solution prepared with a surfactant is washed several times (so that most of the dispersant and porogen are removed), extracted with acetone, vacuum dried, and sieved to prepare A macroporous spherical donor-type adsorption resin containing resorcinol with a particle size of 0.2-1mm is produced.

Example 3

Step 1: Put the adsorption resin in a glass adsorption column with a column diameter of 10mm, and a column with a resin volume of 5mL, and install it into a resin column;

Step 2: Flow 3000mg/L caffeine solution through the above resin column, caffeine is adsorbed in the resin, washed and eluted with 1M HCl and 40% methanol solution;

Step 3: The flow rate of adsorption, washing, and desorption is 1.5-2.5 bed volumes/hour, and the desorption solution is vacuum-dried to obtain a powdery white caffeine product. The recovery rate of caffeine is 90-95%. Resin can be reused.

Example 4

Step 1: Put the adsorption resin in a glass adsorption column with a column diameter of 10mm, and a column with a resin volume of 5mL, and install it into a resin column;

Step 2: Flow 3000mg/L theophylline aqueous solution through the above resin column, theophylline is adsorbed in the resin, washed and eluted with 1M HCl and 80% methanol solution;

Step 3: The flow rate of adsorption, washing, and desorption is 1.5-3 bed volumes/hour, and the desorption solution is vacuum-dried to obtain a white powdered theophylline product. The recovery rate of theophylline is 85-90%. Resin can be reused.

Example 5

Step 1: Put the adsorption resin in a glass adsorption column with a column diameter of 10mm, and a column with a resin volume of 5mL, and install it into a resin column;

Step 2: Flow 1000mg/L VB ₁₂ aqueous solution through the above resin column, VB ₁₂ is adsorbed in the resin, washed and eluted with 80% methanol solution;

Step 3: The flow rate of adsorption, washing and desorption is 1.1-1.5 bed volumes per hour, and the desorption solution is vacuum-dried to obtain a red powder VB ₁₂ product. The recovery rate of VB ₁₂ is 60-85%. Resin can be reused.

Because the accompanying drawings are photos, the small characters therein are not clear, but it does not affect the understanding of the technical solution.

Figure 1, Figure 3, and Figure 5 are the SEM photos of the macroporous spherical donor-type adsorption resin containing resorcinol synthesized by paraformaldehyde. The appearance of this resin is a sphere, which is brown in color, and the diameter of the ball is 0.2-1mm. , the surface has a sponge-like or honeycomb-like structure, the surface is porous, the average pore diameter is 30-120nm, the skeleton density is 1.08-1.32g/cm ³ , and the specific surface area is 60-100m ² /g.

Figure 2, Figure 4, and Figure 6 are the SEM photos of the macroporous spherical donor-type adsorption resin containing resorcinol synthesized with formaldehyde solution. 1mm, the surface has a sponge-like or honeycomb-like structure, the surface is porous, the average pore diameter is 50-300nm, the skeleton density is 1.08-1.32g/cm ³ , and the specific surface area is 100-200m ² /g.

Claims (5)

1. the synthetic method containing resorcinol macroporous spherical adsorption resin is characterized in that the macroporous spherical donor type adsorption resin containing resorcinol is synthesized with paraformaldehyde, and the steps are as follows: (1) Mix porogen: ethylene glycol, reactive monomer: paraformaldehyde, resorcinol, phenol in a molar ratio of 10.9:3.7:0.7:1, add 1-2% dispersant Span80, and continue stirring until uniform; oil phase: take 4 to 6 times the volume of liquid wax; (2) Add the mixture in (1) into the liquid wax, start stirring, 100-150 rpm, raise the temperature to 70-75°C, and keep the temperature constant for 1-2 hours; (3) Add 2 mL of catalyst: concentrated hydrochloric acid with an HCl content of 36-38%, continue to stir and keep the temperature constant for 2 hours, adjust the stirring speed to make the size of the oil droplet suitable, so as to ensure the macroporous spherical donor containing resorcinol generated The diameter of the adsorption resin ball is suitable, and the temperature is raised slowly to 82°C for 1 hour, then to 100°C for 1.5 hours, and then to 130-140°C for 5 hours; (4) After the polymerization reaction is completed, the material is discharged, the resin is filtered out, and it is repeatedly washed with an aqueous solution prepared by a surfactant, extracted with acetone, vacuum-dried, and sieved to prepare resorcinol-containing resin with a particle size of 0.2 to 1 mm. Macroporous spherical body-giving adsorption resin. 2. the synthetic method of resorcinol-containing macroporous spherical adsorption resin as claimed in claim 1 is characterized in that the appearance of this resin is a sphere, which is brown, and the diameter of the ball is 0.2～1mm, and the surface has sponge-like Like or honeycomb structure, the surface is porous, the average pore diameter is 30-120nm, the skeleton density is 1.08-1.32g/cm ³ , the specific surface area is 60-100m ² /g, the water content is 30-50%, and the phenolic hydroxyl content is 2 ~3.72mmol/g. 3. the synthetic method containing resorcinol macroporous spherical adsorption resin is characterized in that the macroporous spherical donor type adsorption resin containing resorcinol is synthesized with formaldehyde solution, and the steps are as follows: (1) Mix porogen: ethylene glycol, reactive monomer: formaldehyde solution with 36-38% HCHO content, resorcinol, and phenol in a molar ratio of 10.9:3.7:0.7:1, and add 1-2 % Dispersant Span80, continue to stir until uniform; oil phase: take 4 to 6 times the volume of liquid wax; (2) Add the mixture in (1) into the liquid wax, start stirring, 100-150 rpm, raise the temperature to 70-75°C, and keep the temperature constant for 1-2 hours; (3) Add 2 mL of catalyst: concentrated hydrochloric acid with an HCl content of 36-38%, continue to stir and keep the temperature constant for 2 hours, adjust the stirring speed to make the size of the oil droplet suitable, so as to ensure the macroporous spherical donor containing resorcinol generated The diameter of the adsorption resin ball is suitable. Slowly raise the temperature to 82°C for 1 hour, and then raise the temperature to 100°C for 1.5 hours. The water separator will separate the generated water. 5h; (4) After the polymerization reaction is completed, the material is discharged, the resin is filtered out, washed with an aqueous solution prepared by a surfactant, extracted with acetone, vacuum-dried, and sieved to prepare macropores containing resorcinol with a particle size of 0.2 to 1 mm. Spherical donor type adsorption resin. 4. the synthetic method of resorcinol-containing macroporous spherical adsorption resin as claimed in claim 3 is characterized in that the appearance of this resin is a sphere, which is light yellow or yellow, and the diameter of the ball is 0.2～1mm, and the surface has Sponge-like or honeycomb-like structure, the surface is porous, the average pore diameter is 50-300nm, the skeleton density is 1.08-1.32g/cm ³ , the specific surface area is 100200m ² /g, the water content is 40-65%, and the phenolic hydroxyl content is 1.5 ~2.5mmol/g. 5. The application method of the macroporous spherical adsorption resin containing resorcinol is characterized in that the methods for extracting caffeine, theophylline, and VB ₁₂ containing hydrogen bond acceptors in the aqueous solution are respectively: (1) The method for extracting caffeine from caffeine aqueous solution is: the adsorption resin is packed in the glass adsorption column that column diameter is 10～50mm, and resin volume is in the column of 5mL～2.5L, is installed into resin column; Caffeine The aqueous solution flows through the above-mentioned resin column, caffeine is adsorbed in the resin, and is eluted with 1M HCl and 40% methanol solution after washing; the flow rate of adsorption, washing, and desorption is 1.5-2.5 bed volumes/hour, and the desorption liquid After vacuum drying, the powdery white caffeine product can be obtained, the recovery rate of caffeine is 90-95%, and the eluted adsorption resin can be reused; (2) The method for extracting theophylline from theophylline aqueous solution is as follows: the adsorption resin is installed in a glass adsorption column with a column diameter of 10 to 50 mm, and the resin volume is 5 mL to 2.5 L in the column, and the device is formed into a resin column; the theophylline The aqueous solution flows through the above-mentioned resin column, theophylline is adsorbed in the resin, and is eluted with 1M HCl and 80% methanol solution after washing; the flow rate of adsorption, washing, and desorption is 1.5 to 3 bed volumes/hour, and the desorption solution is passed through Vacuum drying to obtain the white powdered theophylline product, the recovery rate of theophylline is 85-90%, and the eluted adsorption resin can be reused; (3) The method of extracting VB ₁₂ from the VB ₁₂ aqueous solution is as follows: the adsorption resin is packed in a glass adsorption column with a column diameter of 10-50mm, and the resin volume is 5mL-2.5L in the column, and the device is a resin column; the VB ₁₂ The aqueous solution flows through the above-mentioned resin column, VB ₁₂ is adsorbed in the resin, and is eluted with 80% methanol solution after washing; the flow rate of adsorption, washing, and desorption is 1.1-1.5 bed volumes/hour, and the desorption solution is vacuum-dried The VB ₁₂ product in the form of red powder is obtained, the recovery rate of VB ₁₂ is 60-85%, and the eluted adsorption resin can be reused.

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