CN114904493B - Ionic crosslinking beta-cyclodextrin polymer and preparation method and application thereof - Google Patents
Ionic crosslinking beta-cyclodextrin polymer and preparation method and application thereof Download PDFInfo
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- 229920000858 Cyclodextrin Polymers 0.000 title claims abstract description 131
- 239000001116 FEMA 4028 Substances 0.000 title claims abstract description 130
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 title claims abstract description 130
- 235000011175 beta-cyclodextrine Nutrition 0.000 title claims abstract description 130
- 229960004853 betadex Drugs 0.000 title claims abstract description 130
- 229920000642 polymer Polymers 0.000 title claims abstract description 49
- 238000004132 cross linking Methods 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000243 solution Substances 0.000 claims abstract description 51
- 238000003756 stirring Methods 0.000 claims abstract description 40
- 229920000554 ionomer Polymers 0.000 claims abstract description 23
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- 125000000129 anionic group Chemical group 0.000 claims abstract description 16
- 238000010992 reflux Methods 0.000 claims abstract description 13
- 125000002091 cationic group Chemical group 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 230000001105 regulatory effect Effects 0.000 claims abstract description 5
- 239000012213 gelatinous substance Substances 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 29
- 150000002500 ions Chemical class 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 15
- PUVAFTRIIUSGLK-UHFFFAOYSA-M trimethyl(oxiran-2-ylmethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1CO1 PUVAFTRIIUSGLK-UHFFFAOYSA-M 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 5
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 5
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 5
- 239000002351 wastewater Substances 0.000 claims description 5
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000975 dye Substances 0.000 claims description 4
- 229910001385 heavy metal Inorganic materials 0.000 claims description 4
- 238000010907 mechanical stirring Methods 0.000 claims description 4
- 229940068041 phytic acid Drugs 0.000 claims description 4
- 235000002949 phytic acid Nutrition 0.000 claims description 4
- 239000000467 phytic acid Substances 0.000 claims description 4
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims description 3
- 235000019743 Choline chloride Nutrition 0.000 claims description 3
- 229960003178 choline chloride Drugs 0.000 claims description 3
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- FENRSEGZMITUEF-ATTCVCFYSA-E [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].OP(=O)([O-])O[C@@H]1[C@@H](OP(=O)([O-])[O-])[C@H](OP(=O)(O)[O-])[C@H](OP(=O)([O-])[O-])[C@H](OP(=O)(O)[O-])[C@H]1OP(=O)([O-])[O-] Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].OP(=O)([O-])O[C@@H]1[C@@H](OP(=O)([O-])[O-])[C@H](OP(=O)(O)[O-])[C@H](OP(=O)([O-])[O-])[C@H](OP(=O)(O)[O-])[C@H]1OP(=O)([O-])[O-] FENRSEGZMITUEF-ATTCVCFYSA-E 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229940083982 sodium phytate Drugs 0.000 claims description 2
- 238000000707 layer-by-layer assembly Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 5
- 239000000178 monomer Substances 0.000 abstract description 5
- 239000011148 porous material Substances 0.000 abstract description 4
- 239000003463 adsorbent Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- 239000008367 deionised water Substances 0.000 description 22
- 229910021641 deionized water Inorganic materials 0.000 description 22
- 230000002378 acidificating effect Effects 0.000 description 11
- 238000001704 evaporation Methods 0.000 description 11
- 239000000706 filtrate Substances 0.000 description 11
- 238000011010 flushing procedure Methods 0.000 description 11
- 230000007935 neutral effect Effects 0.000 description 11
- 238000001291 vacuum drying Methods 0.000 description 11
- 238000001914 filtration Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000000356 contaminant Substances 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- 229920000426 Microplastic Polymers 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 229940088710 antibiotic agent Drugs 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
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- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- 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
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- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28047—Gels
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- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- 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
- Y02W10/10—Biological treatment of water, waste water, or sewage
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Abstract
The invention belongs to the technical field of preparation of functional porous materials, and discloses an ionic crosslinking beta-cyclodextrin polymer and a preparation method and application thereof. The method comprises the following steps: dissolving beta-cyclodextrin in a solvent, adding a cationic etherifying agent, carrying out reflux reaction for 4-10 hours at 50-100 ℃, regulating the pH value of the solution to terminate the reaction, removing the solvent, and drying the product to obtain cationized beta-cyclodextrin; preparation of an ionomer beta-cyclodextrin polymer: dispersing the cationized beta-cyclodextrin in an aqueous solution of an anionic crosslinking agent for ionic crosslinking, mechanically stirring at 200-600 rpm for 1-8 hours to obtain a gelatinous substance, repeatedly washing, and drying to obtain the ionic crosslinked beta-cyclodextrin polymer. The method has the advantages of easily available raw materials, mild conditions, simple operation, stronger crosslinking activity, controllable crosslinking degree, wider types of crosslinking agents and cyclodextrin monomers used in the crosslinking reaction, and can be used for preparing the adsorbent material with controllable structure and stable performance.
Description
Technical Field
The invention belongs to the field of chemical synthesis of functional porous materials, and relates to an ionic crosslinking beta-cyclodextrin polymer and a preparation method and application thereof.
Background
The problem of the rapid improvement of the production and living capacities of the human society is that the worldwide trend of resource consumption and ecological environment deterioration is continuously aggravated, a large amount of toxic and harmful wastes are discharged into the air, the water body and the soil, and if the toxic and harmful substances in the environments cannot be further managed and treated, the toxic and harmful substances in the environments are harmful to the human health, and the ecological system is more likely to be unbalanced, so that the high-quality development of the human society is restricted. Contaminants in the environment including, but not limited to, organic dyes, heavy metal ions, antibiotics, microplastic, polycyclic aromatic hydrocarbons, etc.; in terms of its existence, it is mainly dispersed in the water body such as ocean, surface water, groundwater, glacier, etc., so there is a need to develop more kinds of higher efficiency and higher performance treatment technologies and materials. Among the numerous methods for treating wastewater containing one or more of the aforementioned contaminants, the adsorption method is simple to operate, low in cost, high in adsorption separation efficiency and little in secondary pollution, and is the most widely-studied method.
Beta-cyclodextrin has special host-guest interaction and other various weak interaction synergistic effects as a supermolecule compound, and has unique advantages in the aspects of identifying and adsorbing pollutants such as organic dyes, heavy metal ions, antibiotics, microplastic, polycyclic aromatic hydrocarbon and the like. However, the scholars also have to notice that beta-cyclodextrin has a relatively good water solubility, which limits its use as an adsorbent material in actual water sample contaminant removal. Therefore, the beta-cyclodextrin needs to be chemically modified and functionalized by adopting a plurality of different methods or be compounded with other materials, so that the water-solubility defect of the beta-cyclodextrin can be overcome, and the advantages of the beta-cyclodextrin can be exerted to a greater extent.
Disclosure of Invention
In view of the above drawbacks and shortcomings of the prior art, a primary object of the present invention is to provide a process for preparing an ionomer beta-cyclodextrin polymer.
It is another object of the present invention to provide an ionomer beta-cyclodextrin polymer prepared by the above method.
It is a further object of the present invention to provide the use of the above ionomer beta-cyclodextrin polymer.
The invention provides a simple ion crosslinking method for preparing a beta-cyclodextrin-based functional porous material adsorbent, which has the following specific implementation strategy: the beta-cyclodextrin is firstly cationized by a cationic etherifying agent, and then is subjected to ionic crosslinking with an anionic crosslinking agent to prepare the beta-cyclodextrin polymer with the porous structure.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a method for preparing an ionic crosslinked beta-cyclodextrin polymer, comprising the following steps:
(1) Preparing cationized beta-cyclodextrin: dissolving beta-cyclodextrin in a solvent, adding a cationic etherifying agent, carrying out reflux reaction for 4-10 hours at 50-100 ℃, regulating the pH value of the solution to terminate the reaction, removing the solvent, and drying the product to obtain cationized beta-cyclodextrin;
(2) Preparation of an ionomer beta-cyclodextrin polymer: dispersing the cationized beta-cyclodextrin obtained in the step (1) in an aqueous solution of an anionic crosslinking agent for ionic crosslinking, mechanically stirring at 200-600 rpm for 1-8 hours to obtain a gelatinous substance, repeatedly washing, and drying to obtain the ionic crosslinked beta-cyclodextrin polymer.
Preferably, the cationic etherifying agent in the step (1) is one or two of 2, 3-epoxypropyl trimethyl ammonium chloride and choline chloride;
The solvent in the step (1) is sodium hydroxide solution, and the concentration of the solvent is 25-40 wt%;
The reagent for regulating the pH of the solution in the step (1) is one or more of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, sodium hydroxide and ammonia water, and the pH range is 4-10.
Preferably, the anionic cross-linking agent in the step (2) is one or more than two of sodium tripolyphosphate, sodium hexametaphosphate, phytic acid and sodium phytate.
Preferably, the molar ratio of the beta-cyclodextrin to the cationic etherifying agent in the step (1) is 1:1-1:7, and the mass ratio of the cationized beta-cyclodextrin to the anionic crosslinking agent in the step (2) is 1:1-12:1.
Preferably, the molar ratio of the beta-cyclodextrin to the cationic etherifying agent in the step (1) is 1:7, and the mass ratio of the cationized beta-cyclodextrin to the anionic crosslinking agent in the step (2) is 1:1.
Preferably, the mass volume concentration g/mL of the aqueous solution of the anionic crosslinking agent in the step (2) is 0.01-0.1.
Preferably, the mechanical stirring speed in the step (2) is 400rpm, the reaction time is 4 hours, and the mechanical stirring enables the positively charged cationized beta-cyclodextrin to be electrostatically self-assembled with the negatively charged anionic cross-linking agent.
The ionic crosslinking beta-cyclodextrin polymer is prepared by the preparation method.
The ionic crosslinking beta-cyclodextrin polymer is applied to the treatment of wastewater containing organic dyes and/or heavy metal ions.
The invention has the advantages that:
1. The raw materials are low in cost and low in toxicity.
2. The ionic crosslinking condition is mild, the operation is simple and convenient, and the time consumption is less.
3. The polymer formed after the cationic beta-cyclodextrin and the anionic crosslinking agent are crosslinked is in a gel state and is insoluble in water, so that the defect that the beta-cyclodextrin monomer is easy to dissolve in water is overcome, the difficulty of recycling and reutilizing the beta-cyclodextrin monomer is reduced, and the beta-cyclodextrin can be better applied to actual wastewater sample treatment.
4. The ionic crosslinking degree is controllable, and the effective control of the ionic crosslinking degree can be realized by changing the cationization degree of the beta-cyclodextrin, adjusting the proportion of the cationized beta-cyclodextrin monomer to the anionic crosslinking agent, changing the pH, time and other parameters in the ionic crosslinking process.
5. The ion crosslinking beta-cyclodextrin polymer has a loose porous structure, which is beneficial to enhancing the adsorption performance of various pollutants in wastewater.
6. The ionic crosslinking method for preparing the beta-cyclodextrin polymer has a wider applicable monomer range, and similar beneficial effects can be realized on the one-step cationization of beta-cyclodextrin serving as other nonionic substituents and the multi-step cationization of beta-cyclodextrin and the nonionic substituent beta-cyclodextrin except for the one-step cationization of beta-cyclodextrin.
Drawings
FIG. 1 is a diagram showing the mechanism of preparing an ionomer of an ionomer beta-cyclodextrin according to the present invention;
FIG. 2 is a graph showing the nitrogen adsorption and desorption curves of the ionomer beta-cyclodextrin polymer prepared in example 3 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but embodiments of the present invention are not limited thereto, and may be performed with reference to conventional techniques for process parameters that are not specifically noted.
Example 1
1. Preparing cationized beta-cyclodextrin:
11.35g of beta-cyclodextrin was dissolved in 50ml of 40wt% NaOH solution with stirring thoroughly to dissolve, 1.52g of 2, 3-epoxypropyltrimethylammonium chloride was added to the solution at 70℃under reflux for 4h, and then the pH of the solution was adjusted to be acidic with dilute hydrochloric acid to terminate the cationization reaction. Rotary evaporating at 80deg.C for 2 hr to remove most of the solvent, and vacuum drying at 60deg.C overnight to obtain cationized beta-cyclodextrin.
2. Preparation of an ionomer beta-cyclodextrin polymer:
(1) Adding 1g of sodium tripolyphosphate into 100mL of deionized water, sequentially stirring, sonicating and stirring for 5min at room temperature to completely dissolve the sodium tripolyphosphate, and then adjusting the pH to 8 (+ -0.1);
(2) 1g of the cationized beta-cyclodextrin prepared in the step 1 is added into a sodium tripolyphosphate solution, and the mixture is mechanically stirred at 400rpm for 4 hours to obtain a gel-like substance;
(3) And (3) filtering the gel substance prepared in the step (2), repeatedly flushing the gel substance with a large amount of deionized water until the filtrate is neutral, and then drying the gel substance in vacuum at 60 ℃ overnight to obtain the ion crosslinking beta-cyclodextrin polymer 1.
Example 2
1. Preparing cationized beta-cyclodextrin:
11.35g of beta-cyclodextrin was dissolved in 50ml of 40wt% NaOH solution with stirring thoroughly to dissolve, 6.08g of 2, 3-epoxypropyltrimethylammonium chloride was added to the solution at 70℃under reflux for 4 hours, and then the pH of the solution was adjusted to be acidic with dilute hydrochloric acid to terminate the cationization reaction. Rotary evaporating at 80deg.C for 2 hr to remove most of the solvent, and vacuum drying at 60deg.C overnight to obtain cationized beta-cyclodextrin.
2. Preparation of an ionomer beta-cyclodextrin polymer:
(1) Adding 1g of sodium tripolyphosphate into 100mL of deionized water, sequentially stirring, sonicating and stirring for 5min at room temperature to completely dissolve the sodium tripolyphosphate, and then adjusting the pH to 8 (+ -0.1);
(2) 1g of the cationized beta-cyclodextrin prepared in the step 1 is added into a sodium tripolyphosphate solution, and the mixture is mechanically stirred at 400rpm for 4 hours to obtain a gel-like substance;
(3) And (3) filtering the gel substance prepared in the step (2), repeatedly flushing the gel substance with a large amount of deionized water until the filtrate is neutral, and then drying the gel substance in vacuum at 60 ℃ overnight to obtain the ion crosslinking beta-cyclodextrin polymer 2.
Example 3
1. Preparing cationized beta-cyclodextrin:
11.35g of beta-cyclodextrin was dissolved in 50ml of 40wt% NaOH solution with stirring thoroughly until dissolved, 10.64g of 2, 3-epoxypropyltrimethylammonium chloride was added to the solution at 70℃under reflux for 4 hours, and then the pH of the solution was adjusted to be acidic with dilute hydrochloric acid to terminate the cationization reaction. Rotary evaporating at 80deg.C for 2 hr to remove most of the solvent, and vacuum drying at 60deg.C overnight to obtain cationized beta-cyclodextrin.
2. Preparation of an ionomer beta-cyclodextrin polymer:
(1) Adding 1g of sodium tripolyphosphate into 100mL of deionized water, sequentially stirring, sonicating and stirring for 5min at room temperature to completely dissolve the sodium tripolyphosphate, and then adjusting the pH to 8 (+ -0.1);
(2) 1g of the cationized beta-cyclodextrin prepared in the step 1 is added into a sodium tripolyphosphate solution, and the mixture is mechanically stirred at 400rpm for 4 hours to obtain a gel-like substance;
(3) And (3) filtering the gel substance prepared in the step (2), repeatedly flushing the gel substance with a large amount of deionized water until the filtrate is neutral, and then drying the gel substance in vacuum at 60 ℃ overnight to obtain the ion crosslinking beta-cyclodextrin polymer 3. The specific surface area of the ion crosslinking beta-cyclodextrin polymer 3 is 1145cm 2/g measured by a nitrogen adsorption and desorption curve, and the hysteresis loop shape and the size of the nitrogen adsorption and desorption curve indicate that the polymer structure contains a large number of uniform micropore and mesopore structures, so that the ion crosslinking beta-cyclodextrin polymer is an adsorption material with good pore performance.
Example 4
1. Preparing cationized beta-cyclodextrin:
11.35g of beta-cyclodextrin was dissolved in 50ml of 40wt% NaOH solution with stirring thoroughly to dissolve, 9.8g of choline chloride was added to the solution and refluxed at 70℃for 4 hours, followed by adjusting the pH of the solution to be acidic with dilute hydrochloric acid to terminate the cationization reaction. Rotary evaporating at 80deg.C for 2 hr to remove most of the solvent, and vacuum drying at 60deg.C overnight to obtain cationized beta-cyclodextrin.
2. Preparation of an ionomer beta-cyclodextrin polymer:
(1) Adding 1g of sodium tripolyphosphate into 100mL of deionized water, sequentially stirring, sonicating and stirring for 5min at room temperature to completely dissolve the sodium tripolyphosphate, and then adjusting the pH to 8 (+ -0.1);
(2) 1g of the cationized beta-cyclodextrin prepared in the step 1 is added into a sodium tripolyphosphate solution, and the mixture is mechanically stirred at 400rpm for 4 hours to obtain a gel-like substance;
(3) And (3) filtering the gel substance prepared in the step (2), repeatedly flushing the gel substance with a large amount of deionized water until the filtrate is neutral, and then drying the gel substance in vacuum at 60 ℃ overnight to obtain the ion crosslinking beta-cyclodextrin polymer 4.
Example 5
1. Preparing cationized beta-cyclodextrin:
11.35g of beta-cyclodextrin was dissolved in 50ml of 40wt% NaOH solution with stirring thoroughly until dissolved, 10.64g of 2, 3-epoxypropyltrimethylammonium chloride was added to the solution at 70℃under reflux for 4 hours, and then the pH of the solution was adjusted to be acidic with dilute hydrochloric acid to terminate the cationization reaction. Rotary evaporating at 80deg.C for 2 hr to remove most of the solvent, and vacuum drying at 60deg.C overnight to obtain cationized beta-cyclodextrin.
2. Preparation of an ionomer beta-cyclodextrin polymer:
(1) Adding 0.5g of sodium tripolyphosphate into 100mL of deionized water, sequentially stirring, sonicating and stirring for 5min at room temperature to completely dissolve the sodium tripolyphosphate, and then adjusting the pH to 8 (+ -0.1);
(2) 1g of the cationized beta-cyclodextrin prepared in the step 1 is added into a sodium tripolyphosphate solution, and the mixture is mechanically stirred at 400rpm for 4 hours to obtain a gel-like substance;
(3) And (3) filtering the gel substance prepared in the step (2), repeatedly flushing the gel substance with a large amount of deionized water until the filtrate is neutral, and then drying the gel substance in vacuum at 60 ℃ overnight to obtain the ion crosslinking beta-cyclodextrin polymer 5.
Example 6
1. Preparing cationized beta-cyclodextrin:
11.35g of beta-cyclodextrin was dissolved in 50ml of 40wt% NaOH solution with stirring thoroughly until dissolved, 10.64g of 2, 3-epoxypropyltrimethylammonium chloride was added to the solution at 70℃under reflux for 4 hours, and then the pH of the solution was adjusted to be acidic with dilute hydrochloric acid to terminate the cationization reaction. Rotary evaporating at 80deg.C for 2 hr to remove most of the solvent, and vacuum drying at 60deg.C overnight to obtain cationized beta-cyclodextrin.
2. Preparation of an ionomer beta-cyclodextrin polymer:
(1) Adding 1.5g of sodium tripolyphosphate into 100mL of deionized water, sequentially stirring, sonicating and stirring for 5min at room temperature to completely dissolve the sodium tripolyphosphate, and then adjusting the pH to 8 (+ -0.1);
(2) 1g of the cationized beta-cyclodextrin prepared in the step 1 is added into a sodium tripolyphosphate solution, and the mixture is mechanically stirred at 400rpm for 4 hours to obtain a gel-like substance;
(3) And (3) filtering the gel substance prepared in the step (2), repeatedly flushing the gel substance with a large amount of deionized water until the filtrate is neutral, and then drying the gel substance in vacuum at 60 ℃ overnight to obtain the ion crosslinking beta-cyclodextrin polymer 6.
Example 7
1. Preparing cationized beta-cyclodextrin:
11.35g of beta-cyclodextrin was dissolved in 50ml of 40wt% NaOH solution with stirring thoroughly until dissolved, 10.64g of 2, 3-epoxypropyltrimethylammonium chloride was added to the solution at 70℃under reflux for 4 hours, and then the pH of the solution was adjusted to be acidic with dilute hydrochloric acid to terminate the cationization reaction. Rotary evaporating at 80deg.C for 2 hr to remove most of the solvent, and vacuum drying at 60deg.C overnight to obtain cationized beta-cyclodextrin.
2. Preparation of an ionomer beta-cyclodextrin polymer:
(1) Adding 3g of sodium tripolyphosphate into 100mL of deionized water, sequentially stirring, sonicating and stirring for 5min at room temperature to completely dissolve the sodium tripolyphosphate, and then adjusting the pH to 8 (+ -0.1);
(2) 1g of the cationized beta-cyclodextrin prepared in the step 1 is added into a sodium tripolyphosphate solution, and the mixture is mechanically stirred at 400rpm for 4 hours to obtain a gel-like substance;
(3) And (3) filtering the gel substance prepared in the step (2), repeatedly flushing the gel substance with a large amount of deionized water until the filtrate is neutral, and then drying the gel substance in vacuum at 60 ℃ overnight to obtain the ion crosslinking beta-cyclodextrin polymer 7.
Example 8
1. Preparing cationized beta-cyclodextrin:
11.35g of beta-cyclodextrin was dissolved in 50ml of 40wt% NaOH solution with stirring thoroughly until dissolved, 10.64g of 2, 3-epoxypropyltrimethylammonium chloride was added to the solution at 70℃under reflux for 4 hours, and then the pH of the solution was adjusted to be acidic with dilute hydrochloric acid to terminate the cationization reaction. Rotary evaporating at 80deg.C for 2 hr to remove most of the solvent, and vacuum drying at 60deg.C overnight to obtain cationized beta-cyclodextrin.
2. Preparation of an ionomer beta-cyclodextrin polymer:
(1) Adding 1g of sodium tripolyphosphate into 100mL of deionized water, sequentially stirring, sonicating and stirring for 5min at room temperature to completely dissolve the sodium tripolyphosphate, and then adjusting the pH to 8 (+ -0.1);
(2) Adding 1g of the cationized beta-cyclodextrin prepared in the step 1 into a sodium tripolyphosphate solution, and mechanically stirring at 200rpm for 4 hours to obtain massive hard gel;
(3) And (3) repeatedly flushing the massive hard gel prepared in the step (2) with a large amount of deionized water until the filtrate is neutral, and then drying the gel in vacuum at 60 ℃ overnight to obtain the ion crosslinking beta-cyclodextrin polymer 8.
Example 9
1. Preparing cationized beta-cyclodextrin:
11.35g of beta-cyclodextrin was dissolved in 50ml of 40wt% NaOH solution with stirring thoroughly until dissolved, 10.64g of 2, 3-epoxypropyltrimethylammonium chloride was added to the solution at 70℃under reflux for 4 hours, and then the pH of the solution was adjusted to be acidic with dilute hydrochloric acid to terminate the cationization reaction. Rotary evaporating at 80deg.C for 2 hr to remove most of the solvent, and vacuum drying at 60deg.C overnight to obtain cationized beta-cyclodextrin.
2. Preparation of an ionomer beta-cyclodextrin polymer:
(1) Adding 1g of sodium tripolyphosphate into 100mL of deionized water, sequentially stirring, sonicating and stirring for 5min at room temperature to completely dissolve the sodium tripolyphosphate, and then adjusting the pH to 8 (+ -0.1);
(2) Adding 1g of the cationized beta-cyclodextrin prepared in the step 1 into a sodium tripolyphosphate solution, and mechanically stirring at 600rpm for 4 hours to obtain finely divided gel;
(3) And (3) repeatedly flushing the finely-divided gel prepared in the step (2) with a large amount of deionized water until the filtrate is neutral, and then drying the gel in vacuum at 60 ℃ overnight to obtain the ion-crosslinked beta-cyclodextrin polymer 9.
Example 10
1. Preparing cationized beta-cyclodextrin:
11.35g of beta-cyclodextrin was dissolved in 50ml of 40wt% NaOH solution with stirring thoroughly until dissolved, 10.64g of 2, 3-epoxypropyltrimethylammonium chloride was added to the solution at 70℃under reflux for 4 hours, and then the pH of the solution was adjusted to be acidic with dilute hydrochloric acid to terminate the cationization reaction. Rotary evaporating at 80deg.C for 2 hr to remove most of the solvent, and vacuum drying at 60deg.C overnight to obtain cationized beta-cyclodextrin.
2. Preparation of an ionomer beta-cyclodextrin polymer:
(1) Adding 1g of sodium hexametaphosphate into 100mL of deionized water, sequentially stirring, ultrasonically stirring at room temperature for 5min to completely dissolve the sodium hexametaphosphate, and then adjusting the pH to 8 (+ -0.1);
(2) Adding 1g of the cationized beta-cyclodextrin prepared in the step1 into a sodium hexametaphosphate solution, and mechanically stirring at 400rpm for 4 hours to obtain a gel-like substance;
(3) And (3) repeatedly flushing the gel substance prepared in the step (2) with a large amount of deionized water until the filtrate is neutral, and then drying the gel substance in vacuum at 60 ℃ overnight to obtain the ion crosslinking beta-cyclodextrin polymer 10.
Example 11
1. Preparing cationized beta-cyclodextrin:
11.35g of beta-cyclodextrin was dissolved in 50ml of 40wt% NaOH solution with stirring thoroughly until dissolved, 10.64g of 2, 3-epoxypropyltrimethylammonium chloride was added to the solution at 70℃under reflux for 4 hours, and then the pH of the solution was adjusted to be acidic with dilute hydrochloric acid to terminate the cationization reaction. Rotary evaporating at 80deg.C for 2 hr to remove most of the solvent, and vacuum drying at 60deg.C overnight to obtain cationized beta-cyclodextrin.
2. Preparation of an ionomer beta-cyclodextrin polymer:
(1) Adding 1g of phytic acid into 100mL of deionized water, sequentially stirring, ultrasonically stirring for 5min at room temperature to completely dissolve the phytic acid, and then adjusting the pH to 8 (+ -0.1);
(2) Adding 1g of the cationized beta-cyclodextrin prepared in the step 1 into a phytic acid solution, and mechanically stirring at 400rpm for 4 hours to obtain a gel-like substance;
(3) And (3) repeatedly flushing the gel substance prepared in the step (2) with a large amount of deionized water until the filtrate is neutral, and then drying the gel substance in vacuum at 60 ℃ overnight to obtain the ionic crosslinking beta-cyclodextrin polymer 11.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (7)
1. A method for preparing an ionomer beta-cyclodextrin polymer, which is characterized by comprising the following steps:
(1) Preparing cationized beta-cyclodextrin: dissolving beta-cyclodextrin in a solvent, adding a cationic etherifying agent, carrying out reflux reaction for 4-10 hours at 50-100 ℃, regulating the pH value of the solution to terminate the reaction, removing the solvent, and drying the product to obtain cationized beta-cyclodextrin;
(2) Preparation of an ionomer beta-cyclodextrin polymer: dispersing the cationized beta-cyclodextrin obtained in the step (1) in an aqueous solution of an anionic crosslinking agent for ionic crosslinking, mechanically stirring at 200-600 rpm for 1-8 hours to obtain a gelatinous substance, repeatedly washing, and drying to obtain an ionic crosslinked beta-cyclodextrin polymer;
the anionic cross-linking agent in the step (2) is one or more than two of sodium tripolyphosphate, sodium hexametaphosphate, phytic acid and sodium phytate;
The molar ratio of the beta-cyclodextrin to the cationic etherifying agent in the step (1) is 1:1-1:7, and the mass ratio of the cationized beta-cyclodextrin to the anionic crosslinking agent in the step (2) is 1:1-12:1;
And (3) carrying out electrostatic self-assembly on the positively charged cationized beta-cyclodextrin and the negatively charged anionic cross-linking agent through mechanical stirring.
2. The preparation method according to claim 1, wherein the cationic etherifying agent in the step (1) is one or two of 2, 3-epoxypropyl trimethyl ammonium chloride and choline chloride;
The solvent in the step (1) is sodium hydroxide solution, and the concentration of the solvent is 25-40 wt%;
The reagent for regulating the pH of the solution in the step (1) is one or more of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, sodium hydroxide and ammonia water, and the pH range is 4-10.
3. The method of claim 1, wherein the molar ratio of the beta-cyclodextrin to the cationic etherifying agent in step (1) is 1:7 and the mass ratio of the cationized beta-cyclodextrin to the anionic cross-linking agent in step (2) is 1:1.
4. The process according to claim 1, wherein the aqueous solution of the anionic crosslinking agent in the step (2) has a mass/volume concentration of 0.01 to 0.1g/mL.
5. The process according to claim 1, wherein the mechanical stirring rate in step (2) is 400rpm and the reaction time is 4 hours.
6. An ionomer beta-cyclodextrin polymer obtained by the process of any one of claims 1 to 5.
7. Use of the ionomer beta-cyclodextrin polymer of claim 6 for treating wastewater containing organic dyes and/or heavy metal ions.
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