CN112934198B - Cyclodextrin porous adsorption material and preparation method and application thereof - Google Patents

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

Info

Publication number
CN112934198B
CN112934198B CN202110134402.0A CN202110134402A CN112934198B CN 112934198 B CN112934198 B CN 112934198B CN 202110134402 A CN202110134402 A CN 202110134402A CN 112934198 B CN112934198 B CN 112934198B
Authority
CN
China
Prior art keywords
cyclodextrin
reaction
percent
adsorption
sample
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202110134402.0A
Other languages
Chinese (zh)
Other versions
CN112934198A (en
Inventor
刘银丽
李妮
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang Sci Tech University ZSTU
Original Assignee
Zhejiang Sci Tech University ZSTU
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhejiang Sci Tech University ZSTU filed Critical Zhejiang Sci Tech University ZSTU
Priority to CN202110134402.0A priority Critical patent/CN112934198B/en
Publication of CN112934198A publication Critical patent/CN112934198A/en
Application granted granted Critical
Publication of CN112934198B publication Critical patent/CN112934198B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

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 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 "professional: 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 at providing 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, under ice bath, adding a certain volume of solvent, a certain amount of cyclodextrin, acrylic anhydride and a catalyst into a reaction container, and stirring for 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 cyclically adsorbed for 20 times, and still can keep a higher 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 accompanying 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 obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to 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 a 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 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 (A) is as high as 93.2%. 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 20 times of cyclic adsorption, 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 percent, and the sample has heavy metal ions (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 a 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 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 reaches up to 99 percent, and the adsorption rate is high for heavy metal ions (Cu)2+) The adsorption rate of the adsorbent is as high as 93.8 percent. After 20 times of cyclic adsorption, the adsorption rate of the sample on methylene blue reaches 79.5 percent, and the adsorption rate on heavy metal ions (Cu) is high2+) 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(iv) 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 20 times of cyclic adsorption, the adsorption rate of the sample on methylene blue reaches up to 82.8 percent, and the adsorption rate on heavy metal ions (Cu) is high2+) 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 (a cellulose regeneration dialysis bag MWCO8000, Viskase in America), putting the dialysis bag into 2000ml of ionized water, changing the water every 2 hours, dialyzing for 48 hours, and then freeze-drying the obtained product at the temperature of-70 ℃ for 48 hours to obtain the cyclodextrin porous adsorbing 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 (2) is as high as 80.5%.
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 (a cellulose regeneration dialysis bag MWCO8000, Viskase in America), putting the dialysis bag into 2000ml of ionized water, changing the water every 2 hours, dialyzing for 48 hours, and then freeze-drying the obtained product at the temperature of-70 ℃ for 48 hours to obtain the cyclodextrin porous adsorbing 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 sample has high adsorption rate to methylene blueUp to 99.9% of heavy metal ion (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(iv) 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 (A) is as high as 72.1%.
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 alpha-CD to acrylic anhydride is 1:1, and the molar ratio of the alpha-CD to the addition amount of 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+) Adsorption rate of (2)Up to 97.6%. 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. Circulation typeAfter ring adsorption for 20 times, the adsorption rate of the sample on methylene blue is as high as 78.9 percent, and the heavy metal ions (Cu)2+) The adsorption rate of the adsorbent is up to 66.4 percent.
Comparative example 1:
the literature is as follows: huang W, et al, journal of the Taiwan Institute of Chemical Engineers 82(2018) 189-197 preparation of a water-insoluble polymer of beta-cyclodextrin by citric acid Cross-linking polymerization of beta-cyclodextrin, resulting in a porous adsorbent material having a specific surface area SBET＝0.81m2(ii)/g, the adsorption rate of methylene blue is 99%, and the heavy metal ion Cu is2 +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 (7)

1. A preparation method of a cyclodextrin porous adsorption material is characterized by comprising 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; 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;
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; the reaction temperature of the cross-linking polymerization reaction is 60-120 ℃, the molar charge ratio of the olefin micromolecule 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;
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.
2. The method according to claim 1, 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.
3. The method according to claim 1, wherein the stirring speed in step S1 is 500-1500 rpm, the reaction temperature is-5 ℃, and the reaction time is 12-48 h.
4. The method of claim 1, wherein the initiator in step S2 is one or more of ammonium persulfate, azobisisobutyronitrile, dibenzoyl peroxide, dicumyl peroxide, and azobisisoheptonitrile.
5. The method according to claim 1, wherein the freeze-drying temperature in step S3 is-90 ℃ to-30 ℃, and the drying time is 24 to 72 hours.
6. A cyclodextrin porous adsorption material, which is prepared by the preparation method of any one of claims 1 to 5.
7. Use of the cyclodextrin porous adsorbent material of claim 6 for adsorbing contaminants in wastewater.
CN202110134402.0A 2021-01-29 2021-01-29 Cyclodextrin porous adsorption material and preparation method and application thereof Active CN112934198B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110134402.0A CN112934198B (en) 2021-01-29 2021-01-29 Cyclodextrin porous adsorption material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110134402.0A CN112934198B (en) 2021-01-29 2021-01-29 Cyclodextrin porous adsorption material and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN112934198A CN112934198A (en) 2021-06-11
CN112934198B true CN112934198B (en) 2022-07-08

Family

ID=76240982

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110134402.0A Active CN112934198B (en) 2021-01-29 2021-01-29 Cyclodextrin porous adsorption material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN112934198B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114602434B (en) * 2022-03-08 2023-03-28 中国地质大学（武汉） Cyclodextrin-based adsorption material and preparation method and application thereof
CN114768773A (en) * 2022-03-24 2022-07-22 宁波职业技术学院 Heavy metal adsorption material for edible liquid and preparation method and application thereof
CN114849660A (en) * 2022-05-20 2022-08-05 浙江理工大学绍兴柯桥研究院有限公司 Cyclodextrin-based nano-porous composite adsorption material and preparation method thereof
CN115445584B (en) * 2022-09-29 2023-09-22 西安交通大学 Preparation method and application of polyvinyl alcohol polymer adsorbent

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19548038A1 (en) * 1995-12-21 1997-06-26 Basf Ag Process for the preparation of polymers by emulsion polymerization
CA2481491A1 (en) * 2004-09-14 2006-03-14 Le Groupe Lysac Inc. Amidinated or guanidinated polysaccharides, their use as absorbents and a process for producing same
EP2295480A1 (en) * 2009-09-10 2011-03-16 Occlugel Implantable bio-resorbable polymer
CN101812159B (en) * 2010-05-05 2012-12-19 东北林业大学 Preparation method of Beta-cyclodextrin-based superabsorbent resin
CN109806851B (en) * 2019-03-25 2022-08-09 东华大学 Cyclodextrin porous material and preparation method thereof
CN110760033B (en) * 2019-11-06 2022-06-28 岭南师范学院 Functional high-adsorption resin and simple preparation method and application thereof

Also Published As

Publication number Publication date
CN112934198A (en) 2021-06-11

Similar Documents

Publication Publication Date Title
CN112934198B (en) Cyclodextrin porous adsorption material and preparation method and application thereof
Desmet et al. Cellulose functionalization via high-energy irradiation-initiated grafting of glycidyl methacrylate and cyclodextrin immobilization
Amiel et al. Association between amphiphilic poly (ethylene oxide) and β-cyclodextrin polymers: aggregation and phase separation
Harada et al. Preparation and characterization of inclusion complexes of poly (propylene glycol) with cyclodextrins
Wang et al. Synthesis of chitosan molecularly imprinted polymers for solid-phase extraction of methandrostenolone
Yang et al. Molecularly imprinted polymer using β-cyclodextrin as functional monomer for the efficient recognition of bilirubin
Reis et al. Synthesis and characterization of pH-responsive hydrogels based on chemically modified Arabic gum polysaccharide
Yavuz et al. Synthesis of cholesterol imprinted polymeric particles
CN109772178B (en) Preparation method and application of pyrimethamine molecularly imprinted composite membrane based on click chemistry double-sided loading
Bakhshpour et al. Surface imprinted bacterial cellulose nanofibers for hemoglobin purification
Oz et al. Magnetic glyconanoparticles for selective lectin separation and purification
Sreenivasan Synthesis and evaluation of a beta cyclodextrin‐based molecularly imprinted copolymer
CN108948231B (en) Water-soluble polyrotaxane crosslinking agent and preparation method thereof
Samatya et al. Comparative boron removal performance of monodisperse-porous particles with molecular brushes via “click chemistry” and direct coupling
Cui et al. Molecularly imprinted electrospun nanofibre membrane assisted stir bar sorptive extraction for trace analysis of sulfonamides from animal feeds
Wu et al. Efficient one-pot synthesis of artemisinin-imprinted membrane by direct surface-initiated AGET-ATRP
Phillips et al. Cyclodextrin-derived polymer networks for selective molecular adsorption
Gao et al. Fabrication of a novel surface molecularly imprinted polymer based on zeolitic imidazolate framework-7 for selective extraction of phthalates
Karoyo et al. Preparation and Characterization of a polymer-based “Molecular Accordion”
CN111704693B (en) Pseudo template molecularly imprinted polymer and application thereof
CN112110861B (en) Carbendazim virtual template molecularly imprinted polymer and preparation method thereof
CN108047380A (en) A kind of preparation method of beta-cyclodextrin imprinted polymer
CN115368498A (en) Preparation method and application of eutectic solvent type molecularly imprinted polymer based on magnetic metal organic framework material carrier
Rachkov et al. Molecularly imprinted polymers selective for β-estradiol
CN107570125B (en) EDTA-Ni molecularly imprinted material, and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant