CN112934198A - Cyclodextrin porous adsorption material and preparation method and application thereof - Google Patents

Cyclodextrin porous adsorption material and preparation method and application thereof Download PDF

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CN112934198A
CN112934198A CN202110134402.0A CN202110134402A CN112934198A CN 112934198 A CN112934198 A CN 112934198A CN 202110134402 A CN202110134402 A CN 202110134402A CN 112934198 A CN112934198 A CN 112934198A
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cyclodextrin
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CN112934198B (en
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刘银丽
李妮
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Zhejiang University of Technology ZJUT
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
    • B01J20/267—Cross-linked polymers
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract

The invention relates to the technical field of functional porous materials, and provides a cyclodextrin porous adsorption material and a preparation method and application thereof. The preparation method comprises the following steps: carrying out dehydration condensation reaction on cyclodextrin and acrylic anhydride, and then carrying out cross-linking polymerization reaction on the cyclodextrin and acrylic anhydride and olefin micromolecule monomers to prepare the cyclodextrin porous adsorption material. The preparation method of the invention has simple steps and mild reaction conditions; the obtained cyclodextrin porous adsorption material has a hierarchical pore structure, a high specific surface area and various active binding sites, and can be used for efficiently removing pollutants in wastewater; and the cyclic utilization can be simply realized, the cyclic adsorption is carried out for 20 times, and the cyclodextrin porous adsorption material can still keep higher adsorption effect.

Description

Cyclodextrin porous adsorption material and preparation method and application thereof
Technical Field
The invention relates to the technical field of functional porous materials, in particular to a cyclodextrin porous adsorption material and a preparation method and application thereof.
The term of art: CD refers to cyclodextrin, alpha-CD refers to alpha-cyclodextrin, beta-CD refers to beta-cyclodextrin, gamma-CD refers to gamma-cyclodextrin, DMF refers to N, N-dimethylformamide, and AIBN refers to azobisisobutyronitrile.
Background
The cyclodextrin is simple in preparation method, is a series of cyclic oligosaccharides generated by amylose under the action of cyclodextrin glucosyltransferase generated by bacillus, has a special cavity structure, can form host-guest inclusion complex with organic and inorganic molecules in the environment, and is widely applied to the fields of food, environment, medicine, polymer synthesis, cosmetics, chemical detection and the like. However, the characteristic of easy water solubility of cyclodextrin limits its application in wastewater treatment. Therefore, the preparation of water-insoluble cyclodextrin-based compounds is receiving increasing attention from researchers. In recent years, a plurality of water-insoluble cyclodextrin-based compounds not only overcome the inherent water-soluble defect of cyclodextrin, but also show a remarkable pollutant adsorption effect in the wastewater treatment process, and further expand the application range of cyclodextrin and derivatives thereof. However, the existing insoluble cyclodextrin-based compound has a small specific surface area and few types of active functional group binding sites, and the adsorption effect of the compound on pollutants in wastewater needs to be further improved.
Disclosure of Invention
The invention aims to overcome at least one of the defects in the prior art, and provides a cyclodextrin porous adsorption material, a preparation method and application thereof. The purpose of the invention is realized based on the following technical scheme:
the invention aims to provide a preparation method of a cyclodextrin porous adsorption material, which comprises the steps of carrying out dehydration condensation reaction on cyclodextrin and acrylic anhydride, and then carrying out cross-linking polymerization reaction on the cyclodextrin and an olefin micromolecule monomer to prepare the cyclodextrin porous adsorption material.
Preferably, the preparation method specifically comprises the following steps:
s1, adding a certain volume of solvent, a certain amount of cyclodextrin, acrylic anhydride and a catalyst into a reaction container in an ice bath, and stirring to perform a dehydration condensation reaction;
s2, after the reaction in the step S1 is finished, adding a certain amount of olefin micromolecule monomer and an initiator into the reaction solution obtained in the step S1, adjusting the temperature of the reaction mixed solution, and carrying out cross-linking polymerization reaction at a certain temperature to prepare a cyclodextrin cross-linked polymer;
and S3, after the reaction in the step S2 is finished, putting the reaction mixed solution into a dialysis bag, dialyzing for 24-72 hours, and freeze-drying the obtained product to obtain the cyclodextrin porous adsorbing material.
Preferably, in step S1: the solvent comprises one or more of N, N-dimethylformamide, cyclohexane, toluene, dichloromethane, tetrahydrofuran and dioxane; and/or
The cyclodextrin comprises one of alpha-cyclodextrin, beta-cyclodextrin and gamma-cyclodextrin; and/or
The acrylic anhydride comprises one of methacrylic anhydride or acrylic anhydride; and/or
The catalyst comprises one or more of diethylamine, triethylamine, sodium bicarbonate and potassium bicarbonate; and/or
The olefin small molecular monomer comprises one of sodium p-styrene sulfonate, acrylic acid, methacrylic acid, divinyl benzene, hydroxypropyl acrylate or hydroxypropyl methacrylate.
Preferably, in the step S1, the molar charge ratio of the cyclodextrin to the acrylic anhydride is 1: 1-1: 5, and the molar charge ratio of the cyclodextrin to the catalyst is 1: 1-1: 5.
Preferably, in the step S1, the stirring speed is 500-1500 rpm, the reaction temperature is-5 ℃, and the reaction time is 12-72 hours.
Preferably, the initiator in step S2 is one or more of ammonium persulfate, azobisisobutyronitrile, dibenzoyl peroxide, dicumyl peroxide, and azobisisoheptonitrile.
Preferably, the reaction temperature of the cross-linking polymerization reaction in the step S2 is 60-120 ℃, the molar charge ratio of the olefin small molecular monomer to the cyclodextrin is 2: 1-1: 3, and the molar charge ratio of the initiator to the cyclodextrin is 2: 1-1: 2.
Preferably, the temperature of the freeze drying in the step S3 is-90 ℃ to-30 ℃, and the drying time is 24-72 h.
In a second aspect of the invention, a cyclodextrin porous adsorbing material is provided, which is prepared according to the preparation method.
In a third aspect of the invention, the application of the cyclodextrin porous adsorption material in adsorbing pollutants in wastewater is provided.
The invention can obtain at least one of the following beneficial effects:
1. the invention takes Cyclodextrin (CD), acrylic anhydride and olefin micromolecule monomer as raw materials, and prepares the cyclodextrin cross-linked polymer through a step method under certain conditions, dehydration condensation reaction and cross-linking polymerization reaction. Compared with the existing cyclodextrin porous material, the cyclodextrin porous adsorption material prepared by the invention not only has a hierarchical pore structure and a higher specific surface area, but also has various active functional group binding sites, and can be used for efficiently adsorbing and removing pollutants in wastewater.
2. The cyclodextrin porous adsorption material obtained by the invention can be recycled, is used for adsorbing and removing pollutants in wastewater, can be used for adsorption for 20 times, and still can keep a high adsorption effect. The regeneration process of the adsorption material is simple, and the recovery cost is low.
3. The preparation method of the porous adsorption material has the advantages of simple steps, mild and non-harsh reaction conditions, safe process and no need of a specific reaction device.
Drawings
FIG. 1 is a schematic diagram of a reaction process of a cyclodextrin porous adsorption material.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The molecular structure and the composition of the cyclodextrin porous adsorbing material finally synthesized by the embodiment of the invention are measured by a nuclear magnetic resonance spectrometer13C NMR、1H NMR) and Fourier transform infrared spectrometer (FTIR) for test analysis; the cyclodextrin porous adsorption material was analyzed for specific surface area, pore size and distribution range by BET test.
The adsorption effect of the cyclodextrin porous adsorption material on heavy metal ions in wastewater is tested and analyzed by an atomic energy spectrometer (ICP), and the test method specifically comprises the following steps: preparing Cu with the mass concentration of 100 mg/L-1000 mg/L2+Respectively taking 20mg of cyclodextrin porous adsorption materials in the solution, respectively putting the cyclodextrin porous adsorption materials in 20ml of heavy metal ion solutions with different concentrations, stirring and adsorbing the cyclodextrin porous adsorption materials in a water bath shaking table for 24 hours at room temperature under the condition that the pH value is 5, and measuring Cu in the solution before and after adsorption by using an atomic energy spectrometer2+Concentration of (c).
Analyzing the adsorption effect of the cyclodextrin porous adsorption material on the dye in the wastewater by an ultraviolet spectrophotometer, wherein the test method specifically comprises the following steps: preparing methylene blue solutions with different concentrations (100mol/L,200mol/L,400mol/L,800mol/L and 1000mol/L), respectively taking 20mg of cyclodextrin porous adsorption materials, respectively putting the cyclodextrin porous adsorption materials into 20ml of dye solutions with different concentrations, then putting the dye solutions into a constant temperature oscillator, performing adsorption oscillation for 12 hours at room temperature to enable the dye solutions to reach adsorption balance, testing the absorbance of the dye in the solutions before and after adsorption by using an ultraviolet-visible spectrophotometer, and calculating the adsorption efficiency of the material on the dye according to a formula.
The specific cyclic regeneration process of the cyclodextrin porous adsorption material comprises the following steps: and (3) placing the adsorption material for adsorbing the pollutants in a saturated way into an acidic methanol or ethanol solution, soaking for 10 minutes, then filtering by using a circulating water pump and a Buchner funnel, collecting the solid, freezing and drying for 48 hours at the temperature of minus 60 ℃, and using the obtained solid material for circularly adsorbing the pollutants.
Example 1:
in this embodiment, the preparation method of the cyclodextrin porous adsorption material includes the following steps:
(1) placing 180ml of N, N-Dimethylformamide (DMF) into a round-bottom flask under ice bath, adding beta-cyclodextrin (beta-CD, 12g), acrylic anhydride (2.4g) and triethylamine (2g) into the round-bottom flask, and performing dehydration condensation reaction by stirring at the reaction temperature of 0 ℃ for 48h at the stirring speed of 500rpm, wherein the feeding molar ratio of the beta-CD to the acrylic anhydride is 1:2, and the adding molar ratio of the beta-CD to the triethylamine is 1: 2.
(2) After the reaction in the step (1) is finished, adding sodium p-styrenesulfonate (2g) and ammonium persulfate (2.2g) into the reaction solution, adjusting the temperature of the reaction mixed solution, and carrying out cross-linking polymerization reaction at a certain temperature to prepare a cyclodextrin cross-linked polymer, wherein the reaction temperature is 80 ℃, the feeding ratio of the sodium p-styrenesulfonate to the beta-CD is 1:1, and the feeding ratio of the ammonium persulfate to the beta-CD is 1:1.
(3) And (3) after the reaction in the step (2) is finished, putting the reaction mixture into a dialysis bag (an MWCO8000 regenerated cellulose dialysis bag, Viskease in America), putting the dialysis bag into 2000ml of ionized water, changing water every 2h, dialyzing for 48h, and then freeze-drying the obtained product at-30 ℃ for 60h to obtain the cyclodextrin porous adsorption material.
The synthesized cyclodextrin porous adsorbing material has specific surface area SBET＝278.69m2(ii) in terms of/g. The adsorption rate of the sample on methylene blue is as high as 99 percent, and the sample has heavy metal ions (Cu)2+) The adsorption rate of the adsorbent is as high as 86%. After the sample is circularly adsorbed for 20 times, the adsorption rate of the sample on methylene blue reaches 91 percent, and the adsorption rate on heavy metal ions (Cu) is high2+) The adsorption rate of the adsorbent is up to 66%.
Example 2:
in this embodiment, the preparation method of the cyclodextrin porous adsorption material includes the following steps:
(1) 200ml of cyclohexane is placed in a round-bottom flask under ice bath, then beta-cyclodextrin (beta-CD, 12g), acrylic anhydride (2.4g) and triethylamine (2g) are added into the round-bottom flask, dehydration condensation reaction is carried out by stirring, the reaction temperature is 0 ℃, the reaction time is 48h, the stirring speed is 1000rpm, the feeding molar ratio of the beta-CD to the acrylic anhydride is 1:2, and the adding molar ratio of the beta-CD to the triethylamine is 1: 2.
(2) After the reaction in the step (1) is finished, adding sodium p-styrenesulfonate (2g) and ammonium persulfate (2.2g) into the reaction solution, adjusting the temperature of the reaction mixed solution, and carrying out cross-linking polymerization reaction at a certain temperature to prepare a cyclodextrin cross-linked polymer, wherein the reaction temperature is 80 ℃, the feeding ratio of the sodium p-styrenesulfonate to the beta-CD is 1:1, and the feeding ratio of the ammonium persulfate to the beta-CD is 1:1.
(3) And (3) after the reaction in the step (2) is finished, putting the reaction mixture into a dialysis bag (an MWCO8000 regenerated cellulose dialysis bag, Viskease in America), putting the dialysis bag into 2000ml of ionized water, changing water every 2h, dialyzing for 36h, and then freeze-drying the obtained product at the temperature of 50 ℃ below zero for 48h to obtain the cyclodextrin porous adsorption material.
The synthesized cyclodextrin porous adsorbing material has specific surface area SBET＝325.67m2(ii) in terms of/g. The adsorption rate of the sample on methylene blue is as high as 99.9 percent, and the sample has heavy metal ions (Cu)2+) The adsorption rate of the adsorbent is as high as 93.6 percent. After the sample is circularly adsorbed for 20 times, the adsorption rate of the sample on methylene blue reaches 89%, and the adsorption rate on heavy metal ions (Cu) is high2+) The adsorption rate of the adsorbent is as high as 73.6 percent.
Example 3:
in this embodiment, the preparation method of the cyclodextrin porous adsorption material includes the following steps:
(1) 200ml of N, N-Dimethylformamide (DMF) is placed in a round-bottom flask under ice bath, then beta-cyclodextrin (beta-CD, 12g), acrylic anhydride (3.6g) and triethylamine (2g) are added into the round-bottom flask, dehydration condensation reaction is carried out by stirring, the reaction temperature is 0 ℃, the reaction time is 48h, the stirring speed is 800rpm, the feeding molar ratio of the beta-CD to the acrylic anhydride is 1:3, and the adding molar ratio of the beta-CD to the triethylamine is 1: 2.
(2) After the reaction in the step (1) is finished, adding sodium p-styrenesulfonate (3g) and ammonium persulfate (2.2g) into the reaction solution, adjusting the temperature of the reaction mixed solution, and carrying out cross-linking polymerization reaction at a certain temperature to prepare a cyclodextrin cross-linked polymer, wherein the reaction temperature is 80 ℃, the feeding ratio of the sodium p-styrenesulfonate to the beta-CD is 1:1.5, and the feeding ratio of the ammonium persulfate to the beta-CD is 1:1.
(3) And (3) after the reaction in the step (2) is finished, putting the reaction mixture into a dialysis bag (an MWCO8000 regenerated cellulose dialysis bag, Viskease in America), putting the dialysis bag into 2000ml of ionized water, changing water every 2h, dialyzing for 48h, and then freeze-drying the obtained product at-70 ℃ for 48h to obtain the cyclodextrin porous adsorption material.
The synthesized cyclodextrin porous adsorbing material has specific surface area SBET＝324.69m2(ii) in terms of/g. The adsorption rate of the sample on methylene blue is as high as 99.9 percent, and the sample has heavy metal ions (Cu)2+) The adsorption rate of the adsorbent is as high as 95 percent. After the sample is circularly adsorbed for 20 times, the adsorption rate of the sample on methylene blue is as high as 86.7 percent, and the heavy metal ions (Cu)2+) The adsorption rate of the adsorbent is as high as 75.6 percent.
Example 4:
in this embodiment, the preparation method of the cyclodextrin porous adsorption material includes the following steps:
(1) 180ml of N, N-Dimethylformamide (DMF) is placed in a round-bottom flask under ice bath, then beta-cyclodextrin (beta-CD, 12g), methacrylic anhydride (3.0g) and triethylamine (2g) are added into the round-bottom flask, dehydration condensation reaction is carried out by stirring, the reaction temperature is 0 ℃, the reaction time is 48h, the stirring speed is 600rpm, the feeding molar ratio of the beta-CD to the methacrylic anhydride is 1:2, and the molar ratio of the beta-CD to the addition amount of the triethylamine is 1: 2.
(2) After the reaction in the step (1) is finished, adding sodium p-styrenesulfonate (2g) and ammonium persulfate (2.2g) into the reaction solution, adjusting the temperature of the reaction mixed solution, and carrying out cross-linking polymerization reaction at a certain temperature to prepare a cyclodextrin cross-linked polymer, wherein the reaction temperature is 80 ℃, the feeding ratio of the sodium p-styrenesulfonate to the beta-CD is 1:1, and the feeding ratio of the ammonium persulfate to the beta-CD is 1:1.
(3) And (3) after the reaction in the step (2) is finished, putting the reaction mixture into a dialysis bag (an MWCO8000 regenerated cellulose dialysis bag, Viskease in America), putting the dialysis bag into 2000ml of ionized water, changing water every 2h, dialyzing for 48h, and then freeze-drying the obtained product at-80 ℃ for 36h to obtain the cyclodextrin porous adsorption material.
The synthesized cyclodextrin porous adsorbing material has specific surface area SBET＝296.98m2(ii) in terms of/g. The adsorption rate of the sample on methylene blue is as high as 99 percent, and the sample has heavy metal ions (Cu)2+) The adsorption rate of the adsorbent is as high as 93.2 percent. After the sample is circularly adsorbed for 20 times, the adsorption rate of the sample on methylene blue reaches up to 83.1 percent, and the heavy metal ions (Cu)2+) The adsorption rate of the adsorbent is as high as 70.3 percent.
Example 5:
in this embodiment, the preparation method of the cyclodextrin porous adsorption material includes the following steps:
(1) 180ml of dichloromethane is placed in a round-bottom flask under ice bath, then beta-cyclodextrin (beta-CD, 12g), methacrylic anhydride (4.5g) and diethylamine (2.2g) are added into the round-bottom flask, dehydration condensation reaction is carried out by stirring, the reaction temperature is 0 ℃, the reaction time is 48h, the stirring speed is 1200rpm, the feeding molar ratio of the beta-CD to the methacrylic anhydride is 1:3, and the molar ratio of the beta-CD to the addition amount of triethylamine is 1: 3.
(2) After the reaction in the step (1) is finished, adding sodium p-styrenesulfonate (2g) and AIBN (1.6g) into the reaction solution, adjusting the temperature of the reaction mixed solution, and carrying out cross-linking polymerization reaction at a certain temperature to prepare a cyclodextrin cross-linked polymer, wherein the reaction temperature is 80 ℃, the feeding ratio of the sodium p-styrenesulfonate to the beta-CD is 1:1, and the feeding ratio of the AIBN to the beta-CD is 1:1.
(3) And (3) after the reaction in the step (2) is finished, putting the reaction mixture into a dialysis bag (an MWCO8000 regenerated cellulose dialysis bag, Viskease in America), putting the dialysis bag into 2000ml of ionized water, changing water every 2h, dialyzing for 48h, and then freeze-drying the obtained product at the temperature of minus 90 ℃ for 30h to obtain the cyclodextrin porous adsorption material.
The synthesized cyclodextrin porous adsorbing material has specific surface area SBET＝287.32m2(ii) in terms of/g. The adsorption rate of the sample on methylene blue is up to 96 percent, and the sample has a heavy metal ion (Cu)2+) The adsorption rate of the adsorbent is as high as 83.6 percent. After the sample is circularly adsorbed for 20 times, the adsorption rate of the sample on methylene blue reaches 73.6 percent, and the adsorption rate on heavy metal ions (Cu) is high2+) The adsorption rate of the adsorbent is as high as 63.3 percent.
Example 6:
in this embodiment, the preparation method of the cyclodextrin porous adsorption material includes the following steps:
(1) 200ml of N, N-Dimethylformamide (DMF) was placed in a round-bottomed flask under ice bath, and then β -cyclodextrin (β -CD, 12g), acrylic anhydride (2.4g) and sodium bicarbonate (1.6g) were added to the round-bottomed flask, followed by dehydration condensation reaction with stirring at 0 ℃ for 48 hours at a stirring speed of 500rpm in a molar ratio of β -CD to acrylic anhydride of 1:2 to the amount of sodium bicarbonate of 1: 2.
(2) After the reaction in the step (1) is finished, adding sodium p-styrenesulfonate (2g) and ammonium persulfate (2.2g) into the reaction solution, adjusting the temperature of the reaction mixed solution, and carrying out cross-linking polymerization reaction at a certain temperature to prepare a cyclodextrin cross-linked polymer, wherein the reaction temperature is 80 ℃, the feeding ratio of the sodium p-styrenesulfonate to the beta-CD is 1:1, and the feeding ratio of the ammonium persulfate to the beta-CD is 1:1.
(3) And (3) after the reaction in the step (2) is finished, putting the reaction mixture into a dialysis bag (an MWCO8000 regenerated cellulose dialysis bag, Viskease in America), putting the dialysis bag into 2000ml of ionized water, changing water every 2h, dialyzing for 48h, and then freeze-drying the obtained product at-70 ℃ for 48h to obtain the cyclodextrin porous adsorption material.
The synthesized cyclodextrin porous adsorbing material has specific surface area SBET＝328.67m2(ii) in terms of/g. The adsorption rate of the sample on methylene blue is as high as 99 percent, and the sample has heavy metal ions (Cu)2+) The adsorption rate of (2) is as high as 93%. After the sample is circularly adsorbed for 20 times, the adsorption rate of the sample on methylene blue is up to 82.6 percent, and the adsorption rate on heavy metal ions (Cu) is up to 82.6 percent2+) The adsorption rate of the adsorbent is as high as 71.9 percent.
Example 7:
in this embodiment, the preparation method of the cyclodextrin porous adsorption material includes the following steps:
(1) putting 180ml of tetrahydrofuran in a round-bottom flask under ice bath, then adding gamma-cyclodextrin (gamma-CD, 12g), acrylic anhydride (2.4g) and triethylamine (2g) into the round-bottom flask, and carrying out dehydration condensation reaction by stirring at the reaction temperature of 0 ℃ for 48h at the stirring speed of 1400rpm, wherein the feeding molar ratio of the gamma-CD to the acrylic anhydride is 1:2, and the adding molar ratio of the gamma-CD to the triethylamine is 1: 2.
(2) After the reaction in the step (1) is finished, adding sodium p-styrenesulfonate (2g) and ammonium persulfate (2.2g) into the reaction solution, adjusting the temperature of the reaction mixed solution, and carrying out cross-linking polymerization reaction at a certain temperature to prepare a cyclodextrin cross-linked polymer, wherein the reaction temperature is 80 ℃, the feeding ratio of the sodium p-styrenesulfonate to the gamma-CD is 1:1, and the feeding ratio of the ammonium persulfate to the gamma-CD is 1:1.
(3) And (3) after the reaction in the step (2) is finished, putting the reaction mixture into a dialysis bag (an MWCO8000 regenerated cellulose dialysis bag, Viskease in America), putting the dialysis bag into 2000ml of ionized water, changing water every 2h, dialyzing for 48h, and then freeze-drying the obtained product at-70 ℃ for 48h to obtain the cyclodextrin porous adsorption material.
The synthesized cyclodextrin porous adsorbing material has specific surface area SBET＝289.56m2(ii) in terms of/g. The adsorption rate of the sample on methylene blue is as high as 99 percent, and the sample has heavy metal ions (Cu)2+) The adsorption rate of the adsorbent is up to 87 percent. After the sample is circularly adsorbed for 20 times, the adsorption rate of the sample on methylene blue is up to 79.5 percent, and the adsorption rate on heavy metal ions (Cu) is up to 79.5 percent2+) The adsorption rate of the adsorbent is as high as 60.8 percent.
Example 8:
in this embodiment, the preparation method of the cyclodextrin porous adsorption material includes the following steps:
(1) 200ml of N, N-Dimethylformamide (DMF) was placed in a round-bottomed flask under ice bath, and then gamma-cyclodextrin (gamma-CD, 12g), acrylic anhydride (2.4g) and sodium bicarbonate (1.6g) were added to the round-bottomed flask, followed by dehydration condensation reaction with stirring at 0 ℃ for 48 hours at a stirring speed of 500rpm in a molar ratio of 1:2 of gamma-CD to acrylic anhydride and 1:2 of gamma-CD to sodium bicarbonate.
(2) After the reaction in the step (1) is finished, adding sodium p-styrenesulfonate (2g) and ammonium persulfate (2.2g) into the reaction solution, adjusting the temperature of the reaction mixed solution, and carrying out cross-linking polymerization reaction at a certain temperature to prepare a cyclodextrin cross-linked polymer, wherein the reaction temperature is 80 ℃, the feeding ratio of the sodium p-styrenesulfonate to the gamma-CD is 1:1, and the feeding ratio of the ammonium persulfate to the gamma-CD is 1:1.
(3) And (3) after the reaction in the step (2) is finished, putting the reaction mixture into a dialysis bag (an MWCO8000 regenerated cellulose dialysis bag, Viskease in America), putting the dialysis bag into 2000ml of ionized water, changing water every 2h, dialyzing for 48h, and then freeze-drying the obtained product at-70 ℃ for 48h to obtain the cyclodextrin porous adsorption material.
The synthesized cyclodextrin porous adsorbing material has specific surface area SBET＝318.67m2(ii) in terms of/g. The adsorption rate of the sample on methylene blue is as high as 99 percentHeavy metal ion (Cu)2+) The adsorption rate of the adsorbent is as high as 92.8 percent. After the sample is circularly adsorbed for 20 times, the adsorption rate of the sample on methylene blue is as high as 84.2 percent, and the heavy metal ions (Cu)2+) The adsorption rate of the adsorbent is as high as 74.9 percent.
Example 9:
in this embodiment, the preparation method of the cyclodextrin porous adsorption material includes the following steps:
(1) 200ml of dioxane is placed in a round-bottom flask under ice bath, then gamma-cyclodextrin (gamma-CD, 12g), acrylic anhydride (2.4g) and triethylamine (2g) are added into the round-bottom flask, dehydration condensation reaction is carried out by stirring, the reaction temperature is 0 ℃, the reaction time is 48h, the stirring speed is 900rpm, the feeding molar ratio of the gamma-CD to the acrylic anhydride is 1:2, and the molar ratio of the gamma-CD to the addition amount of the triethylamine is 1: 2.
(2) After the reaction in the step (1) is finished, adding sodium p-styrenesulfonate (2g) and ammonium persulfate (2.2g) into the reaction solution, adjusting the temperature of the reaction mixed solution, and carrying out cross-linking polymerization reaction at a certain temperature to prepare a cyclodextrin cross-linked polymer, wherein the reaction temperature is 100 ℃, the feeding ratio of the sodium p-styrenesulfonate to the gamma-CD is 1:1, and the feeding ratio of the ammonium persulfate to the gamma-CD is 1:1.
(3) And (3) after the reaction in the step (2) is finished, putting the reaction mixture into a dialysis bag (an MWCO8000 regenerated cellulose dialysis bag, Viskease in America), putting the dialysis bag into 2000ml of ionized water, changing water every 2h, dialyzing for 48h, and then freeze-drying the obtained product at-70 ℃ for 48h to obtain the cyclodextrin porous adsorption material.
The synthesized cyclodextrin porous adsorbing material has specific surface area SBET＝328.67m2(ii) in terms of/g. The adsorption rate of the sample on methylene blue is as high as 99 percent, and the sample has heavy metal ions (Cu)2+) The adsorption rate of the adsorbent is as high as 93.8 percent. After the sample is circularly adsorbed for 20 times, the adsorption rate of the sample on methylene blue is up to 79.5 percent, and the adsorption rate on heavy metal ions (Cu) is up to 79.5 percent2+) The adsorption rate of the adsorbent is as high as 69.3 percent.
Example 10:
in this embodiment, the preparation method of the cyclodextrin porous adsorption material includes the following steps:
(1) 200ml of N, N-Dimethylformamide (DMF) was placed in a round-bottomed flask under ice bath, and then α -cyclodextrin (α -CD, 12g), acrylic anhydride (2.4g) and sodium bicarbonate (1.6g) were added to the round-bottomed flask, followed by dehydration condensation reaction with stirring at 0 ℃ for 48 hours at a stirring speed of 1100rpm in a molar ratio of α -CD to acrylic anhydride of 1:2 to sodium bicarbonate of 1: 2.
(2) After the reaction in the step (1) is finished, adding sodium p-styrenesulfonate (2g) and ammonium persulfate (2.2g) into the reaction solution, adjusting the temperature of the reaction mixed solution, and carrying out cross-linking polymerization reaction at a certain temperature to prepare a cyclodextrin cross-linked polymer, wherein the reaction temperature is 80 ℃, the feeding ratio of the sodium p-styrenesulfonate to the alpha-CD is 1:1, and the feeding ratio of the ammonium persulfate to the alpha-CD is 1:1.
(3) And (3) after the reaction in the step (2) is finished, putting the reaction mixture into a dialysis bag (an MWCO8000 regenerated cellulose dialysis bag, Viskease in America), putting the dialysis bag into 2000ml of ionized water, changing water every 2h, dialyzing for 48h, and then freeze-drying the obtained product at-70 ℃ for 48h to obtain the cyclodextrin porous adsorption material.
The synthesized cyclodextrin porous adsorbing material has specific surface area SBET＝336.67m2(ii) in terms of/g. The adsorption rate of the sample on methylene blue is as high as 99 percent, and the sample has heavy metal ions (Cu)2+) The adsorption rate of the adsorbent is as high as 98.1%. After the sample is circularly adsorbed for 20 times, the adsorption rate of the sample on methylene blue is up to 82.8 percent, and the adsorption rate on heavy metal ions (Cu) is up to 82.8 percent2+) The adsorption rate of the adsorbent is as high as 76.3 percent.
Example 11:
in this embodiment, the preparation method of the cyclodextrin porous adsorption material includes the following steps:
(1) 180ml of N, N-Dimethylformamide (DMF) was placed in a round-bottomed flask under ice bath, and then α -cyclodextrin (α -CD, 12g), acrylic anhydride (2.4g) and sodium bicarbonate (1.6g) were added to the round-bottomed flask, followed by dehydration condensation reaction with stirring at 0 ℃ for 48 hours at a stirring speed of 1000rpm in a molar ratio of α -CD to acrylic anhydride of 1:2 to sodium bicarbonate of 1: 2.
(2) After the reaction in the step (1) is finished, adding sodium p-styrenesulfonate (4g) and ammonium persulfate (2.2g) into the reaction solution, adjusting the temperature of the reaction mixed solution, and carrying out cross-linking polymerization reaction at a certain temperature to prepare a cyclodextrin cross-linked polymer, wherein the reaction temperature is 100 ℃, the feeding ratio of the sodium p-styrenesulfonate to alpha-CD is 1:2, and the feeding ratio of the ammonium persulfate to the alpha-CD is 1:1.
(3) And (3) after the reaction in the step (2) is finished, putting the reaction mixture into a dialysis bag (an MWCO8000 regenerated cellulose dialysis bag, Viskease in America), putting the dialysis bag into 2000ml of ionized water, changing water every 2h, dialyzing for 48h, and then freeze-drying the obtained product at-70 ℃ for 48h to obtain the cyclodextrin porous adsorption material.
The synthesized cyclodextrin porous adsorbing material has specific surface area SBET＝356.78m2(ii) in terms of/g. The adsorption rate of the sample on methylene blue is as high as 99.9 percent, and the sample has heavy metal ions (Cu)2+) The adsorption rate of the adsorbent is as high as 98.9 percent. After the sample is circularly adsorbed for 20 times, the adsorption rate of the sample on methylene blue reaches up to 83.6 percent, and the heavy metal ions (Cu)2+) The adsorption rate of the adsorbent is as high as 80.5 percent.
Example 12:
in this embodiment, the preparation method of the cyclodextrin porous adsorption material includes the following steps:
(1) 200ml of N, N-Dimethylformamide (DMF) was placed in a round-bottomed flask under ice bath, and then alpha-cyclodextrin (alpha-CD, 12g), acrylic anhydride (2.4g) and triethylamine (2g) were added to the round-bottomed flask, followed by dehydration condensation reaction with stirring at 0 ℃ for 48 hours at a stirring speed of 500rpm in a molar ratio of 1:2 of alpha-CD to acrylic anhydride and 1:2 of alpha-CD to triethylamine.
(2) After the reaction in the step (1) is finished, adding sodium p-styrenesulfonate (2g) and ammonium persulfate (2.2g) into the reaction solution, adjusting the temperature of the reaction mixed solution, and carrying out cross-linking polymerization reaction at a certain temperature to prepare a cyclodextrin cross-linked polymer, wherein the reaction temperature is 100 ℃, the feeding ratio of the sodium p-styrenesulfonate to the alpha-CD is 1:1, and the feeding ratio of the ammonium persulfate to the alpha-CD is 1:1.
(3) And (3) after the reaction in the step (2) is finished, putting the reaction mixture into a dialysis bag (an MWCO8000 regenerated cellulose dialysis bag, Viskease in America), putting the dialysis bag into 2000ml of ionized water, changing water every 2h, dialyzing for 48h, and then freeze-drying the obtained product at-70 ℃ for 48h to obtain the cyclodextrin porous adsorption material.
The synthesized cyclodextrin porous adsorbing material has specific surface area SBET＝336.89m2(ii) in terms of/g. The adsorption rate of the sample on methylene blue is as high as 99.9 percent, and the sample has heavy metal ions (Cu)2+) The adsorption rate of the adsorbent is as high as 97.9 percent. After the sample is circularly adsorbed for 20 times, the adsorption rate of the sample on methylene blue reaches up to 83.7 percent, and the heavy metal ions (Cu)2+) The adsorption rate of the adsorbent is as high as 71.5 percent.
Example 13:
in this example, the preparation method of the cyclodextrin porous adsorption material is basically the same as that of example 12, except that: in the step (2), the reaction temperature is 90 ℃.
The synthesized cyclodextrin porous adsorbing material has specific surface area SBET＝326.89m2(ii) in terms of/g. The adsorption rate of the sample on methylene blue is as high as 99.9 percent, and the sample has heavy metal ions (Cu)2+) The adsorption rate of the adsorbent is as high as 97.5 percent. After the sample is circularly adsorbed for 20 times, the adsorption rate of the sample on methylene blue reaches up to 83.1 percent, and the heavy metal ions (Cu)2+) The adsorption rate of the adsorbent is as high as 71.3 percent.
Example 14:
in this example, the preparation method of the cyclodextrin porous adsorbing material was substantially the same as that of example 11, except that: in the step (2), the reaction temperature was 110 ℃.
The synthesized cyclodextrin porous adsorbing material has specific surface area SBET＝338.46m2(ii) in terms of/g. The adsorption rate of the sample on methylene blue is as high as 99.9 percent, and the sample has heavy metal ions (Cu)2+) The adsorption rate of the adsorbent is as high as 98.6 percent. After the sample is circularly adsorbed for 20 times, the adsorption rate of the sample on methylene blue is up to 82.9 percent, and the heavy metal ions (Cu)2+) The adsorption rate of the adsorbent is as high as 72.1 percent.
Example 15:
in this example, the preparation method of the cyclodextrin porous adsorption material is basically the same as that of example 12, except that: in the step (1), the feeding molar ratio of the alpha-CD to the acrylic anhydride is 1:1, and the molar ratio of the alpha-CD to the addition amount of the sodium bicarbonate is 1:1.
The synthesized cyclodextrin porous adsorbing material has specific surface area SBET＝301.93m2(ii) in terms of/g. The adsorption rate of the sample on methylene blue is as high as 98.9 percent, and the sample has heavy metal ions (Cu)2+) The adsorption rate of the adsorbent is up to 91.9 percent. After the sample is circularly adsorbed for 20 times, the adsorption rate of the sample on methylene blue is up to 79.6 percent, and the adsorption rate on heavy metal ions (Cu) is up to 79.6 percent2+) The adsorption rate of the adsorbent is as high as 68.5 percent.
Example 16:
in this example, the preparation method of the cyclodextrin porous adsorbing material was substantially the same as that of example 11, except that: in the step (2), the feeding ratio of sodium p-styrene sulfonate to alpha-CD is 1:1, and the feeding ratio of ammonium persulfate to alpha-CD is 1: 1.5.
The synthesized cyclodextrin porous adsorbing material has specific surface area SBET＝316.95m2(ii) in terms of/g. The adsorption rate of the sample on methylene blue is as high as 99.9 percent, and the sample has heavy metal ions (Cu)2+) The adsorption rate of the adsorbent is as high as 97.6 percent. After the sample is circularly adsorbed for 20 times, the adsorption rate of the sample on methylene blue is up to 82.6 percent, and the adsorption rate on heavy metal ions (Cu) is up to 82.6 percent2+) The adsorption rate of the adsorbent is as high as 69.4 percent.
Example 17:
in this example, the preparation method of the cyclodextrin porous adsorbing material was substantially the same as that of example 11, except that: in the step (2), the olefin small molecular monomer is divinylbenzene, and the initiator is dibenzoyl peroxide.
The synthesized cyclodextrin porous adsorbing material has specific surface area SBET＝325.63m2(ii) in terms of/g. The adsorption rate of the sample on methylene blue is as high as 99.9 percent, and the sample has heavy metal ions (Cu)2+) The adsorption rate of the adsorbent is up to 96.7 percent. After the sample is circularly adsorbed for 20 times, the adsorption rate of the sample on methylene blue is up to 82.8 percent, and the adsorption rate on heavy metal ions (Cu) is up to 82.8 percent2+) The adsorption rate of the adsorbent is as high as 70.3 percent.
Example 18:
in this example, the preparation method of the cyclodextrin porous adsorbing material was substantially the same as that of example 11, except that: in the step (2), the olefin small molecular monomer is hydroxypropyl acrylate, and the initiator is dicumyl peroxide.
The synthesized cyclodextrin porous adsorbing material has specific surface area SBET＝311.67m2(ii) in terms of/g. The adsorption rate of the sample on methylene blue is as high as 99.9 percent, and the sample has heavy metal ions (Cu)2+) The adsorption rate of the adsorbent is up to 96.3 percent. After the sample is circularly adsorbed for 20 times, the adsorption rate of the sample on methylene blue is up to 82.7 percent, and the heavy metal ions (Cu)2+) The adsorption rate of the adsorbent is as high as 70.6 percent.
Example 19:
in this example, the preparation method of the cyclodextrin porous adsorbing material was substantially the same as that of example 11, except that: in the step (2), the olefin small molecular monomer is hydroxypropyl methacrylate, and the initiator is azobisisoheptonitrile.
The synthesized cyclodextrin porous adsorbing material has specific surface area SBET＝297.49m2(ii) in terms of/g. The adsorption rate of the sample on methylene blue is as high as 98.9 percent, and the sample has heavy metal ions (Cu)2+) The adsorption rate of the adsorbent is as high as 92.3 percent. After the sample is circularly adsorbed for 20 times, the adsorption rate of the sample on methylene blue is up to 78.9 percent, and the adsorption rate on heavy metal ions (Cu) is up to 78.9 percent2+) The adsorption rate of the adsorbent is up to 66.4 percent.
Comparative example 1:
the literature: huang W, et al, journal of the Taiwan Institute of Chemical Engineers 82(2018) 189-BET＝0.81m2(ii)/g, the adsorption rate to methylene blue is 99%, and heavy metal ion Cu2 +The adsorption rate of (2) is 58.6%, and the adsorption rate is obviously reduced after 5 times of cyclic adsorption.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments or portions thereof without departing from the spirit and scope of the invention.

Claims (10)

1. A preparation method of a cyclodextrin porous adsorption material is characterized in that cyclodextrin and acrylic anhydride are subjected to dehydration condensation reaction and then subjected to cross-linking polymerization reaction with olefin micromolecule monomers to prepare the cyclodextrin porous adsorption material.
2. The preparation method of the cyclodextrin porous adsorbing material as claimed in claim 1, which comprises the following steps:
s1, adding a certain volume of solvent, a certain amount of cyclodextrin, acrylic anhydride and a catalyst into a reaction container in an ice bath, and stirring to perform a dehydration condensation reaction;
s2, after the reaction in the step S1 is finished, adding a certain amount of olefin micromolecule monomer and an initiator into the reaction solution obtained in the step S1, adjusting the temperature of the reaction mixed solution, and carrying out cross-linking polymerization reaction at a certain temperature to prepare a cyclodextrin cross-linked polymer;
and S3, after the reaction in the step S2 is finished, putting the reaction mixed solution into a dialysis bag, dialyzing for 24-72 hours, and freeze-drying the obtained product to obtain the cyclodextrin porous adsorbing material.
3. The method for preparing a cyclodextrin porous adsorbing material according to claim 2, wherein in step S1: the solvent comprises one or more of N, N-dimethylformamide, cyclohexane, toluene, dichloromethane, tetrahydrofuran and dioxane; and/or
The cyclodextrin comprises one of alpha-cyclodextrin, beta-cyclodextrin and gamma-cyclodextrin; and/or
The acrylic anhydride comprises one of methacrylic anhydride or acrylic anhydride; and/or
The catalyst comprises one or more of diethylamine, triethylamine, sodium bicarbonate and potassium bicarbonate; and/or
The olefin small molecular monomer comprises one of sodium p-styrene sulfonate, acrylic acid, methacrylic acid, divinyl benzene, hydroxypropyl acrylate or hydroxypropyl methacrylate.
4. The preparation method of the cyclodextrin porous adsorption material according to claim 2, wherein the molar charge ratio of cyclodextrin to acrylic anhydride in step S1 is 1: 1-1: 5, and the molar charge ratio of cyclodextrin to the catalyst is 1: 1-1: 5.
5. The preparation method of the cyclodextrin porous adsorption material according to claim 2, wherein in the step S1, the stirring speed is 500-1500 rpm, the reaction temperature is-5 ℃, and the reaction time is 12-48 h.
6. The method for preparing a cyclodextrin porous adsorbing material according to claim 2, wherein the initiator in step S2 is one or more of ammonium persulfate, azobisisobutyronitrile, dibenzoyl peroxide, dicumyl peroxide and azobisisoheptonitrile.
7. The preparation method of the cyclodextrin porous adsorption material according to claim 2, wherein the reaction temperature of the cross-linking polymerization reaction in the step S2 is 60-120 ℃, the molar charge ratio of the olefin small molecular monomer to the cyclodextrin is 2: 1-1: 3, and the molar charge ratio of the initiator to the cyclodextrin is 2: 1-1: 2.
8. The preparation method of the cyclodextrin porous adsorbing material as claimed in claim 2, wherein the temperature of the freeze drying in the step S3 is-90 ℃ to-30 ℃, and the drying time is 24-72 h.
9. A cyclodextrin porous adsorption material, which is prepared by the preparation method of any one of claims 1 to 9.
10. An application of cyclodextrin porous adsorption material in adsorbing pollutants in wastewater.
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