阅读说明：本技术 一种萘修饰交联的β-环糊精凝胶、制备方法及应用 (Naphthalene-modified crosslinked beta-cyclodextrin gel, preparation method and application ) 是由 王志坤 吕强 李春玲 李君豪 冷震 王秀民 孙霜青 胡松青 于 2021-10-18 设计创作，主要内容包括：本发明公开了一种萘修饰交联的β-环糊精凝胶、制备方法及应用,属于高分子凝胶材料的处理水污染领域。该制备方法包括：首先利用1-萘甲酰氯与β-环糊精,通过亲核取代反应制备出6号位单取代的β-环糊精衍生物；将交联剂、碱性化合物与干燥后的β-环糊精衍生物混溶到溶剂中,无水无氧条件下,加热反应得到产物一；最后,将产物一冷却后用溶剂浸泡洗涤,再经过索式提取,真空干燥后得到萘修饰交联的β-环糊精凝胶。本发明通过对修饰剂及交联剂进行改进,且整个制备方法操作简便。本发明萘修饰β-环糊精凝胶吸附剂其比表面积为1.3893m～(2)/g,其溶胀率为75％。(The invention discloses naphthalene modified crosslinked beta-cyclodextrin gel, a preparation method and application thereof, and belongs to the field of treatment of water pollution by high polymer gel materials. The preparation method comprises the following steps: firstly, 1-naphthoyl chloride and beta-cyclodextrin are utilized to prepare a 6-position monosubstituted beta-cyclodextrin derivative through nucleophilic substitution reaction; mixing the cross-linking agent, alkaline compound and dried beta-cyclodextrin derivative in solvent, heating and reacting under anhydrous and oxygen-free conditions to obtain the productFirstly, performing primary filtration; and finally, cooling the product I, soaking and washing the product I by using a solvent, performing Soxhlet extraction, and drying in vacuum to obtain the naphthalene modified and crosslinked beta-cyclodextrin gel. The invention improves the modifier and the cross-linking agent, and the whole preparation method is simple and convenient to operate. The specific surface area of the naphthalene modified beta-cyclodextrin gel adsorbent is 1.3893m 2 The swelling ratio was 75% per gram.)

1. A preparation method of naphthalene modified cross-linked beta-cyclodextrin gel is characterized by sequentially comprising the following steps:

a. taking beta-cyclodextrin as a core unit, preparing a 6-position monosubstituted beta-cyclodextrin derivative by nucleophilic substitution reaction of 1-naphthoyl chloride and the beta-cyclodextrin, and drying the beta-cyclodextrin derivative;

b. dissolving a cross-linking agent, an alkaline compound and the dried beta-cyclodextrin derivative into a solvent, and heating and reacting under anhydrous and anaerobic conditions to obtain a product I;

c. and cooling the product I, soaking and washing the product I by using a solvent, performing Soxhlet extraction, and performing vacuum drying to obtain the naphthalene modified and crosslinked beta-cyclodextrin gel.

2. The method for preparing the naphthalene modified crosslinked beta-cyclodextrin gel according to claim 1, wherein: in the step a, 1-naphthoyl chloride is dissolved in acetonitrile to react with beta-cyclodextrin, and the reaction conditions are as follows: and (3) adjusting the pH to be neutral at the temperature of 0 ℃ for 2-4 h, and separating out at the temperature of 3-6 ℃ to obtain the beta-cyclodextrin derivative.

3. The method for preparing the naphthalene modified crosslinked beta-cyclodextrin gel according to claim 2, wherein: filtering the beta-cyclodextrin derivative before drying the beta-cyclodextrin derivative, and drying the filtered beta-cyclodextrin derivative in a vacuum drying mode; the weight-volume ratio of the beta-cyclodextrin to the 1-naphthoyl chloride is 11.928: 1.58g/mL, the weight-to-volume ratio of beta-cyclodextrin to acetonitrile is 11.928: 6 g/mL.

4. The method for preparing the naphthalene modified crosslinked beta-cyclodextrin gel according to claim 1, wherein: in the step b, the cross-linking agent is decafluorobiphenyl, the alkaline compound is anhydrous potassium carbonate, and the solvent is anhydrous dimethyl sulfoxide.

5. The method for preparing the naphthalene modified crosslinked beta-cyclodextrin gel according to claim 4, wherein: the weight ratio of the dried beta-cyclodextrin derivative to the decafluorobiphenyl is 1.36:1.06, and the reaction conditions are as follows: the temperature is 80-90 ℃, and the reaction time is 10-14 h.

6. The method for preparing the naphthalene modified crosslinked beta-cyclodextrin gel according to claim 1, wherein: in step c, the solvents used for washing are water, tetrahydrofuran and dichloromethane, respectively.

7. The method for preparing the naphthalene modified crosslinked beta-cyclodextrin gel according to claim 6, wherein: when the product is washed after cooling, it is separately in H₂Soaking in O for 10-20 min, soaking in THF for 20-40 min, and soaking in CH₂Cl₂Soaking for 10-25 min.

8. The naphthalene modified crosslinked beta-cyclodextrin gel prepared by the preparation method of the naphthalene modified crosslinked beta-cyclodextrin gel according to any one of claims 1 to 7.

9. The use of the naphthalene modified cross-linked β -cyclodextrin gel of claim 8 as an adsorbent in water pollution treatment.

10. Use according to claim 9, as an adsorbent in water pollution treatment comprising: firstly, measuring an adsorption concentration curve, and then further measuring the adsorption effect and the regenerability of the naphthalene modified crosslinked beta-cyclodextrin gel by changing the temperature and the pH value.

Technical Field

The invention relates to the field of treating water pollution by using a high-molecular gel material, in particular to a naphthalene modified and crosslinked beta-cyclodextrin gel adsorbent.

Background

With the progress of science and technology and the development of industry, pollutants which are wantonly discharged into water and contain benzene rings seriously harm the natural environment and the health of human beings. The cyclodextrin is a hot material concerned by researchers due to the special large cyclic hollow structure, low cost, stable chemical performance and the special properties of internal hydrophobicity and external hydrophilicity.

The prior art reports on the study of cyclodextrin core adsorbents mainly include:

application number 202010119377.4 discloses a porous beta-cyclodextrin cross-linked polymer nanofiber, a preparation method thereof and application thereof in removing bisphenol organic pollutants in water, wherein the porous beta-cyclodextrin cross-linked polymer nanofiber is mainly prepared by taking a beta-cyclodextrin-copper metal organic framework nano material as a template and 2, 4-toluene diisocyanate as a cross-linking agent, and the specific preparation method comprises the following steps: (1) taking water as a solvent, fully mixing and dissolving beta-cyclodextrin, sodium hydroxide and copper chloride dihydrate, filtering to remove insoluble substances, pouring absolute ethyl alcohol into filtrate, washing obtained precipitate with ethanol, and drying in vacuum to obtain a blue solid, namely the beta-cyclodextrin-copper metal organic framework template material; (2) stirring and reacting a beta-cyclodextrin-copper metal organic framework template material and 2, 4-toluene diisocyanate by taking anhydrous N, N-dimethylformamide as a solvent and dibutyltin dilaurate as a catalyst in an argon atmosphere; and after the reaction is finished, centrifuging a product obtained by the reaction, washing the product by using N, N-dimethylformamide, and then washing the product by using dilute hydrochloric acid and water respectively to obtain the milky porous beta-cyclodextrin crosslinked polymer nanofiber.

Application No. 201610913846.3 discloses a method for constructing a water-soluble network cyclodextrin crosslinked polymer, a crosslinked polymer, and a method for purifying organic wastewater. The cross-linked polymer takes the derivatization beta-cyclodextrin as a basic unit, hydrophobic cavities of different derivatization cyclodextrins are communicated by virtue of the series connection effect of a compound with a specific linear structure, a network structure is controllably constructed by virtue of the self-crosslinking effect between the multifunctional group small molecule weak cross-linking and the cyclodextrin substituent, and the compound with the linear structure is removed by elution to obtain a target product.

Although the prior art has made certain progress in the study of cyclodextrin, the cyclodextrin functions such as controllable modification and crosslinking of cyclodextrin still need to be improved, and the effect still needs to be enhanced.

Therefore, the prior art is still subject to further improvement.

Disclosure of Invention

One of the purposes of the invention is to provide a preparation method of naphthalene modified and crosslinked beta-cyclodextrin gel, which is characterized in that a modifier and a crosslinking agent are improved, so that the prepared beta-cyclodextrin gel has a good adsorption effect, and the whole preparation method is simple and convenient to operate.

In order to achieve the purpose, the invention adopts the following technical scheme:

a preparation method of naphthalene modified cross-linked beta-cyclodextrin gel sequentially comprises the following steps:

a. taking beta-cyclodextrin as a core unit, preparing a 6-position monosubstituted beta-cyclodextrin derivative by nucleophilic substitution reaction of 1-naphthoyl chloride and the beta-cyclodextrin, and drying the beta-cyclodextrin derivative;

b. dissolving a cross-linking agent, an alkaline compound and the dried beta-cyclodextrin derivative into a solvent, and heating and reacting under anhydrous and anaerobic conditions to obtain a product I;

c. and cooling the product I, soaking and washing the product I by using a solvent, performing Soxhlet extraction, and performing vacuum drying to obtain the naphthalene modified and crosslinked beta-cyclodextrin gel.

The beneficial technical effects directly brought by the technical scheme are as follows:

the invention utilizes 1-naphthoyl chloride to modify beta-cyclodextrin, modifies naphthalene-containing groups onto the beta-cyclodextrin through nucleophilic substitution reaction, constructs a cyclodextrin cavity and benzene ring pi-pi action basic adsorption system, and obtains beta-cyclodextrin gel through selecting proper cross-linking agent and cross-linking modification, wherein the beta-cyclodextrin gel can adsorb benzene-containing cyclic pollutants in water and has the best adsorption effect.

In a preferred embodiment of the invention, in step a, 1-naphthoyl chloride is dissolved in acetonitrile and reacted with beta-cyclodextrin, wherein the reaction conditions are as follows: and (3) adjusting the pH to be neutral at the temperature of 0 ℃ for 2-4 h, and separating out at the temperature of 3-6 ℃ to obtain the beta-cyclodextrin derivative.

As another preferred embodiment of the present invention, before drying the β -cyclodextrin derivative, filtering the β -cyclodextrin derivative, and drying the filtered β -cyclodextrin derivative in a vacuum drying manner; the weight-volume ratio of the beta-cyclodextrin to the 1-naphthoyl chloride is 11.928: 1.58g/mL, the weight-to-volume ratio of beta-cyclodextrin to acetonitrile is 11.928: 6 g/mL.

Preferably, in step b, the crosslinking agent is decafluorobiphenyl, the basic compound is anhydrous potassium carbonate, and the solvent is anhydrous dimethyl sulfoxide.

Further preferably, the weight ratio of the dried beta-cyclodextrin derivative to the decafluorobiphenyl is 1.36:1.06, and the reaction conditions are as follows: the temperature is 80-90 ℃, and the reaction time is 10-14 h.

Further preferably, in step c, the solvents used for washing are water, tetrahydrofuran and dichloromethane, respectively.

It is further preferred that the products, when washed once cooled, are each in H₂Soaking in O for 10-20 min, soaking in THF for 20-40 min, and soaking in CH₂Cl₂Soaking for 10-25 min.

The invention also aims to provide the naphthalene modified cross-linked beta-cyclodextrin gel prepared by the preparation method of the naphthalene modified cross-linked beta-cyclodextrin gel.

It is still another object of the present invention to provide the use of the above-mentioned naphthalene modified crosslinked beta-cyclodextrin gel as an adsorbent in water pollution treatment.

Further, the application of the adsorbent in water pollution treatment comprises the following steps: firstly, measuring an adsorption concentration curve, and then further measuring the adsorption effect and the regenerability of the naphthalene modified crosslinked beta-cyclodextrin gel by changing the temperature and the pH value.

The preparation principle of the naphthalene modified crosslinked beta-cyclodextrin gel is as follows:

beta-cyclodextrin is selected as a core unit, primary hydroxyl at the 6 th position of the cyclodextrin is subjected to single substitution modification through nucleophilic substitution, a naphthalene-containing group is modified on the cyclodextrin, a cyclodextrin cavity and benzene ring pi-pi action basic adsorption system is constructed, and then an appropriate cross-linking agent is selected to cross-link the modified cyclodextrin derivative, so that the water-insoluble cyclodextrin-based hydrogel adsorbent is prepared, and the prepared cyclodextrin hydrogel adsorbent is effectively applied to adsorbing benzene-containing cyclic pollutants in water.

Compared with the prior art, the invention has the following beneficial technical effects:

(1) the beta-cyclodextrin gel adsorbent generated by the invention is green and pollution-free, low in price and simple to synthesize;

(2) the naphthalene modified crosslinked beta-cyclodextrin gel has good adsorption effect, is insoluble in water, is convenient to recover and is beneficial to reuse;

(3) the naphthalene modified crosslinked beta-cyclodextrin gel can specifically adsorb polycyclic aromatic hydrocarbons and has stable adsorption.

(4) The specific surface area of the naphthalene modified beta-cyclodextrin gel adsorbent is 1.3893m²The swelling ratio was 75% per gram.

Drawings

The invention is further described below with reference to the accompanying drawings:

FIG. 1 is a schematic diagram of the modification process of naphthalene-modified beta-cyclodextrin gel of the present invention;

FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of a naphthalene modified beta-cyclodextrin gel of the present invention;

FIG. 3 is a schematic illustration of the cross-linking process of the naphthalene modified beta-cyclodextrin gel of the present invention;

FIG. 4 is a scanning electron microscope test chart of the naphthalene modified beta-cyclodextrin gel adsorbent of the present invention;

FIG. 5 is a TEM (transmission electron microscopy) test chart of the naphthalene-modified beta-cyclodextrin gel adsorbent of the present invention;

FIG. 6 is a nitrogen adsorption and desorption test chart of the naphthalene modified beta-cyclodextrin gel adsorbent of the present invention;

FIG. 7 is an isothermal adsorption curve of naphthalene modified beta-cyclodextrin gel adsorbents of the present invention for bisphenol A;

FIG. 8 is a graph of temperature-dependent data for adsorption of bisphenol A by a naphthalene-modified beta-cyclodextrin gel adsorbent of the present invention;

FIG. 9 is a graph of pH-dependent data for adsorption of bisphenol A by a naphthalene modified beta-cyclodextrin gel adsorbent of the present invention;

FIG. 10 is a graph showing the regeneration performance of the naphthalene-modified beta-cyclodextrin gel adsorbent of the present invention;

FIG. 11 is a synthetic roadmap for 6-Ts-CD;

FIG. 12 is a synthetic scheme for anthraquinone-modified β -cyclodextrin derivatives;

FIG. 13 is a nuclear magnetic resonance spectrum of 6-Ts-CD;

FIG. 14 is a NMR spectrum of 6-EDA-CD;

FIG. 15 is a nuclear magnetic resonance spectrum of anthraquinone-modified β -cyclodextrin derivatives;

fig. 16 (a) and (b) show nuclear magnetic resonance spectra of the anthraquinone-modified β -cyclodextrin gel adsorbent, respectively;

fig. 17(a) and (b) show nitrogen adsorption/desorption test charts of the anthraquinone-modified β -cyclodextrin gel adsorbent, respectively;

FIG. 18 is an isothermal adsorption test plot of anthraquinone-modified beta-cyclodextrin gel adsorbents;

FIG. 19 is a graph of maximum adsorption measurements of anthraquinone-modified beta-cyclodextrin gel adsorbents at different temperatures;

FIG. 20 is a graph of maximum adsorption measurements of anthraquinone-modified beta-cyclodextrin gel adsorbents at different pH;

FIG. 21 is a graph showing the regeneration performance test of anthraquinone-modified beta-cyclodextrin gel adsorbents.

Detailed Description

The invention provides a naphthalene modified cross-linked beta-cyclodextrin gel, a preparation method and application thereof, and the invention is described in detail below by combining specific embodiments in order to make the advantages and technical scheme of the invention clearer and clearer.

The raw materials required by the invention can be purchased from commercial sources.

The N-CD is a naphthalene modified beta-cyclodextrin derivative.

The DFB-N-CD is a beta-cyclodextrin gel adsorbent modified by naphthalene.

The invention discloses a preparation method of naphthalene modified cross-linked beta-cyclodextrin gel, which specifically comprises the following steps:

step 1, 11.928g of beta-CD was added to a 150mL single-neck flask, and 99mL of deionized water was injected into the flask while the solution system was stirred continuously. Aqueous NaOH (1.31g, 4mL) was then slowly added dropwise to the β -CD suspension using a constant pressure funnel, the solution was stirred continuously while the addition was ongoing, the solution became clear, and the pH of the solution was measured using a pH meter to be about 13. After the dropwise addition is finished, when the beta-CD is completely dissolved, the reaction system is placed in a low-temperature reaction bath at 0 ℃ and stirred and cooled for 20min until the temperature of the solution measured by a thermometer is stabilized at 0 ℃. Weighing 1.58mL (0.01mol) of 1-naphthoyl chloride, dissolving in 6mL of acetonitrile, stirring for dissolving, slowly injecting the acetonitrile solution dissolved with the 1-naphthoyl chloride into the system through a constant-pressure dropping funnel, ensuring that the dropwise addition of the solution is finished within 1h, and separating out white precipitate and generating foam in the reaction system along with the continuous injection of the 1-naphthoyl chloride, wherein the characteristic is the typical characteristic of cyclodextrin reaction. After the dropwise addition is finished, sealing the reaction system and continuing to react in a low-temperature bath for 2 hours until the turbidity degree of the solution is obviously reduced, filtering to obtain the reacted solution, measuring the pH value of the solution to be about 12 at the moment, indicating that the beta-cyclodextrin reacts with the 1-naphthoyl chloride, adjusting the supernatant to be about 6.5 by using 1mol/L diluted hydrochloric acid, placing the mixture in a refrigerator for overnight, and keeping the temperature of the refrigerator at 4 ℃. Standing for a period of time to find that precipitate is continuously separated out in the solution, performing suction filtration on the system after 24 hours to obtain solid precipitate, performing vacuum drying at 80 ℃ to obtain naphthalene-modified beta-cyclodextrin (N-beta-CD), and recrystallizing twice with water to remove unreacted cyclodextrin and naphthoyl chloride impurities to obtain pure N-beta-CD. The schematic diagram of the modification process of the naphthalene-modified beta-cyclodextrin gel is shown in fig. 1, and the nuclear magnetic resonance hydrogen spectrogram of the naphthalene-modified beta-cyclodextrin gel is shown in fig. 2.

Step 2, 1.36g of dried naphthalene modified beta-cyclodextrin (N-beta-CD), 1.06g of decafluorobiphenyl and 1.83g of anhydrous K₂CO₃Adding into a 100mL three-neck flask, sealing and adding N₂Purge 5 minutes. Then injecting 30mL of the solution into the syringeGrade molecular sieve dried anhydrous DMSO while introducing N₂Bubbling for 10-15 min, removing the gas injection port after gas injection, sealing the system, and mechanically stirring at 85 ℃ for 12 h. A schematic of the cross-linking process of naphthalene modified beta-cyclodextrin gels is shown in figure 3.

Step 3, after the reaction is finished, cooling the product, taking out the product, filtering, washing the product on filter paper by using 1mol/L diluted hydrochloric acid solution until no bubbles are generated, and respectively soaking the product in H₂15 min in O (2X 50mL), 30 min in THF (2X 50mL) and CH₂Cl₂(1X 60mL) for 15 minutes for washing and activation. Wrapping with filter paper tube, placing in Soxhlet extractor, and purifying with water (30h) and acetone (24h), respectively. And after the reaction is finished, drying the product in a vacuum drying oven at 80 ℃ for 24h along with a filter paper cylinder, and then drying the product for 24h at normal temperature to obtain a light yellow solid product. Scanning electron microscopy of the naphthalene-modified beta-cyclodextrin gel adsorbent is shown in fig. 4, and transmission electron microscopy of the naphthalene-modified beta-cyclodextrin gel adsorbent is shown in fig. 4, wherein (a) and (b) show different particle sizes, respectively. Naphthalene modified beta-a transmission electron microscope test pattern of the cyclodextrin gel adsorbent is shown in fig. 5(a) and (b), and a nitrogen adsorption/desorption test pattern of the naphthalene-modified β -cyclodextrin gel adsorbent is shown in fig. 6(a) and (b).

The naphthalene modified cross-linked beta-cyclodextrin gel prepared by the preparation method can be used as an adsorbent in the technical field of water treatment, and the specific application method of the beta-cyclodextrin gel is explained in detail below.

Preparing bisphenol A solutions with the concentrations of 30mg/L, 90mg/L, 150mg/L, 210mg/L, 240mg/L and 300mg/L, respectively taking 10mL of the bisphenol A solutions, injecting the solutions into 20mL of transparent vials, adding 10mg of TFN-N-CD adsorbent, shaking the solution for a certain time at normal temperature and normal pressure, filtering the solution after complete adsorption by using a 0.22-micrometer aqueous micro-filtration head to obtain an adsorbed solution, analyzing the adsorption concentration by using UV-Vis, calculating the adsorption amount, and fitting the adsorption model curve of the TFN-N-CD adsorbent to obtain the adsorption model curve of the TFN-N-CD adsorbent. As shown in fig. 7, fig. 7 shows the isothermal adsorption curve of naphthalene modified beta-cyclodextrin gel adsorbent for bisphenol a.

And secondly, weighing 50mg of each adsorbent in a 150mL beaker, placing the system in a high-low temperature test box at 25 ℃ and under normal pressure, wetting and soaking the adsorbent with water for 12 hours to fully swell the gel, preparing 100mL of each bisphenol A solution with the concentration of 300mg/L, respectively injecting the solutions into the adsorption system, violently stirring, absorbing a small amount of solution liquid according to a certain time gradient, injecting the solution back after calculating the real-time concentration by using UV-Vis measurement, and continuously repeating the operation until the concentration of the solution is stable.

Thirdly, as shown in fig. 8, the adsorption performance of the gel on bisphenol a is tested at 5 ℃, 10 ℃, 25 ℃ and 40 ℃ respectively, and the test is repeated three times at each temperature to obtain the influence of the temperature on the adsorption of pollutants by the gel; as shown in fig. 9, bisphenol a solutions with corresponding pH values were prepared in standard buffer solutions with pH values of 1, 7, and 13, respectively, gels were tested for their adsorption capacities for contaminants in solutions with different pH values at room temperature, and the optimal adsorption pH value was found; and then filtering and drying the gel adsorbed to saturation, washing for 2 times by using 1mol/L diluted hydrochloric acid solution, washing for 2 times by using acetone solution, washing for 2 times by using ethanol solution and washing for 2 times by using deionized water, filtering to obtain filtrate, detecting the filtrate by using UV-Vis, and if the filtrate does not contain bisphenol A and still contains pollutant components, continuously repeating the steps until the components are completely removed. The dried gel was subjected to the adsorption test in step 5, compared with the properties of the unused gel, and the regeneration performance was calculated by repeating the test five times. As shown in fig. 10, fig. 10 shows a graph of the regeneration performance test of the naphthalene modified β -cyclodextrin gel adsorbent.

The specific surface area of the naphthalene modified beta-cyclodextrin gel adsorbent is 1.3893m²The swelling ratio was 75% per gram.

The naphthalene modified beta-cyclodextrin gel adsorbent can be applied to the field of sewage pollution rich in polycyclic aromatic hydrocarbon: the adsorbent is put into sewage rich in polycyclic aromatic hydrocarbon, and adsorbs the polycyclic aromatic hydrocarbon in water through the interaction of a host and an object in a beta-cyclodextrin cavity and the pi-pi interaction force of naphthalene and a cross-linking agent, and because the adsorbent is insoluble in water, the adsorbent is easy to recover and reuse, and the adsorbent is low in manufacturing cost and economical.

Comparative example 1:

preparation of anthraquinone-modified beta-cyclodextrin gel

Other modifying agents are adopted to modify the beta-cyclodextrin,

the same crosslinker was used as in example 1.

The preparation method comprises the following steps:

the preparation process of the naphthalene modified beta-cyclodextrin gel is the same as that of the naphthalene modified beta-cyclodextrin gel except the following contents.

The preparation steps of the anthraquinone-modified beta-cyclodextrin gel are as follows:

a: taking beta-cyclodextrin as a core unit, modifying with p-toluenesulfonyl chloride, and performing nucleophilic substitution to obtain a p-toluenesulfonyl chloride modified beta-cyclodextrin derivative (6-Ts-CD) substituted at the 6 th position, wherein the synthetic route diagram is shown in FIG. 11, and drying the beta-cyclodextrin derivative;

b: beta-cyclodextrin gel modified by tosyl chloride is taken as a core unit, ethylene diamine is used for modification to obtain beta-cyclodextrin derivatives modified by ethylene diamine, and the beta-cyclodextrin derivatives are dried;

c: the beta-cyclodextrin modified by ethylenediamine is used as a core unit, and is modified by anthraquinone-2-carboxylic acid in the presence of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC.HCl) and aminoxysuccinimide (NHS) to obtain the anthraquinone-modified beta-cyclodextrin derivative. The synthetic route of the anthraquinone-modified beta-cyclodextrin derivative is shown in figure 12.

The method comprises the following specific steps:

the method comprises the following steps: 36g of beta-CD was placed in a 500mL single neck flask and 300mL of deionized water was added thereto while stirring the solution system. Aqueous NaOH (3.94g, 12mL) was then slowly added dropwise to the β -CD suspension using a constant pressure funnel, the solution was stirred continuously while the addition was ongoing, the solution became clear, and the pH of the solution was measured using a pH meter to be about 13. After the dropwise addition is finished, when the beta-CD is completely dissolved, the reaction system is placed in a low-temperature reaction bath at 0 ℃ and stirred and cooled for 20min until the temperature of the solution measured by a thermometer is stabilized at 0 ℃. Weighing 9.08g of p-toluenesulfonyl chloride, dissolving the p-toluenesulfonyl chloride in 27mL of acetonitrile, stirring and dissolving, slowly injecting the acetonitrile solution dissolved with the p-toluenesulfonyl chloride into the system through a constant-pressure dropping funnel, ensuring that the dropwise addition of the solution is completed within 2h, and separating out white precipitate and foaming simultaneously in the reaction system along with the continuous injection of Ts-Cl, wherein the characteristic is the typical characteristic of cyclodextrin reaction. After the dropwise addition is finished, sealing the reaction system and continuing to react in a low-temperature bath for 3 hours, filtering to obtain the reacted solution until the turbidity degree of the solution is obviously reduced, measuring the pH value of the solution to be about 12 at the moment, indicating that the beta-cyclodextrin reacts with Ts-Cl, adjusting the supernatant to be about 6.5 by using 1mol/L diluted hydrochloric acid, placing the mixture in a refrigerator for overnight, and keeping the temperature of the refrigerator at 4 ℃. Standing for a period of time to find precipitate in the solution, vacuum filtering the system after 24 hours to obtain solid precipitate, vacuum drying at 80 deg.C to obtain crude product of 6-Ts-CD, recrystallizing with water twice to remove unreacted cyclodextrin and Ts-Cl impurities to obtain pure 6-Ts-CD, wherein the nuclear magnetic resonance spectrogram is shown in FIG. 13.

Step two: 3.6g of 6-Ts-CD were weighed into a 150mL single-neck flask in N₂Under protection, slowly injecting into the system60mL of ethylenediamine, stirring was continued until the 6-Ts-CD was completely dissolved. Then the system is stirred and reacted for 6 hours under the condition of 80 ℃, the solution is changed from colorless to light yellow, the reaction is smoothly carried out, and after the system is cooled to the room temperature, the concentrated liquid is evaporated by a rotary evaporator to remove the unreacted ethylenediamine. After the system is completely cooled, the concentrated solution is slowly dripped into a large amount of acetone by using a constant pressure dropping funnel and is continuously stirred, a large amount of precipitates are separated out along with the dripping of the concentrated solution into the acetone, then the precipitates are filtered, dried and collected, the precipitates are dissolved by using deionized water, the acetone is repeatedly used for precipitating solids to achieve the purification effect, the purification effect is repeatedly carried out for three times, and finally, the pure 6-EDA-CD is obtained, and the nuclear magnetic resonance spectrogram of the 6-EDA-CD is shown in figure 14.

Step three: anthraquinone-2-carboxylic acid, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (edc. hcl), aminoxysuccinimide (NHS) was dissolved in dry DMF at 0 ℃, and then ethylenediamine modified β -CD was dissolved in dry DMF and added dropwise to the above solution. The system was then transferred to a low temperature bath and after the temperature had dropped to 0 ℃, stirred for 1h, then stirred at room temperature for 18h, concentrated in vacuo and dropped into acetone to precipitate a pale yellow color, thus precipitating the crude product. The crude product was further purified by column chromatography and the product was lyophilized to give a pale yellow powder. The nuclear magnetic resonance spectrum of the anthraquinone-modified beta-cyclodextrin derivative is shown in figure 15. The nuclear magnetic resonance spectrum of the anthraquinone-modified beta-cyclodextrin gel adsorbent is shown in fig. 16, wherein (a) and (b) respectively show the nuclear magnetic resonance spectrum measured under different particle sizes; the nitrogen adsorption and desorption test patterns of the anthraquinone modified beta-cyclodextrin gel adsorbent are respectively shown in fig. 17(a) and fig. 17 (b). The isothermal adsorption test pattern of the anthraquinone-modified beta-cyclodextrin gel adsorbent is shown in fig. 18. Maximum adsorption measurements of anthraquinone-modified beta-cyclodextrin gel adsorbents at different temperatures were attempted as shown in fig. 19. Maximum adsorption measurements of anthraquinone-modified beta-cyclodextrin gel adsorbents at different pH were attempted as shown in fig. 20. The regeneration performance test chart of the anthraquinone-modified beta-cyclodextrin gel adsorbent is shown in figure 21.

The specific surface area of the anthraquinone modified beta-cyclodextrin gel adsorbent is determined to be 0.4260m²The swelling ratio was 7.31% per gram.

The parts which are not described in the invention can be realized by taking the prior art as reference.

It should be noted that: any equivalents or obvious modifications thereof which may occur to persons skilled in the art and which are given the benefit of this description are deemed to be within the scope of the invention.