CN109092265B - Cellulose-based adsorbent modified by polyimidazole ionic liquid and preparation method and application thereof - Google Patents

Cellulose-based adsorbent modified by polyimidazole ionic liquid and preparation method and application thereof Download PDF

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CN109092265B
CN109092265B CN201811050817.4A CN201811050817A CN109092265B CN 109092265 B CN109092265 B CN 109092265B CN 201811050817 A CN201811050817 A CN 201811050817A CN 109092265 B CN109092265 B CN 109092265B
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钱立伟
杨苗秀
许亮
刘文倩
张楠
张素风
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Shaanxi University of Science and Technology
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Abstract

The invention provides a cellulose-based adsorbent modified by polyimidazole ionic liquid and a preparation method and application thereof, wherein the preparation method comprises the following steps: step 1, preparing dialdehyde cellulose and polyimidazole ionic liquid respectively; step 2, immersing the dialdehyde cellulose in water, dissolving the polyimidazole ionic liquid in HCl solution, mixing the dialdehyde cellulose aqueous solution and the HCl solution of the polyimidazole ionic liquid, controlling the pH value within the range of 2.5-3.5, and stirring for 4-8 hours at the temperature of 20-45 ℃ to obtain a crude product of the polyimidazole ionic liquid modified cellulose; and 3, washing the crude product of the polyimidazole ionic liquid modified cellulose with ethanol and water, and drying to obtain the polyimidazole ionic liquid modified cellulose-based adsorbent. The adsorbent can effectively solve the problems of low adsorption capacity of cellulose in a water phase, few adsorption sites of a single grafted imidazole ionic liquid functional group and weak adsorption effect in the prior art, and can be used for treating dye wastewater.

Description

Cellulose-based adsorbent modified by polyimidazole ionic liquid and preparation method and application thereof
Technical Field
The invention belongs to the technical field of preparation and development of efficient adsorbents, and relates to a cellulose-based adsorbent modified by a polyimidazole ionic liquid, and a preparation method and application thereof.
Background
In recent years, due to the rapid development of the printing and dyeing, textile and paper making industries, the environmental pollution is increasingly serious, and particularly, the discharge amount of waste water containing dye and heavy metal is gradually increased year by year. Because the printing and dyeing wastewater has high toxicity and is easy to cause carcinogenesis and teratogenesis, the treatment of the printing and dyeing wastewater is a problem which needs to be solved urgently. There are many methods currently used for treating printing and dyeing wastewater, such as electrolysis, ultrafiltration, chemical flocculation, chemical oxidation, adsorption, dialysis, and anaerobic-aerobic treatment. Based on the advantages of high efficiency, low cost, easy operation and the like, the adsorption is a more practical method for treating the printing and dyeing wastewater.
Cellulose is the most abundant biopolymer resource in the world, and is expected to replace activated carbon to become an adsorbent for wastewater treatment due to unique inherent characteristics such as biodegradability, environmental friendliness and the like. However, the hydroxyl groups of cellulose are sensitive to water molecules and have weak interactions with contaminant molecules, resulting in low adsorption capacity. Therefore, the cellulose material needs to be modified, and functional groups which can generate electrostatic and pi-pi conjugation with pollutants in a water phase are introduced, so that the adsorption performance of the cellulose adsorbent can be improved to a certain extent.
The ionic liquid is a liquid composed of ions, imidazole rings are aromatic five-membered nitrogen-containing heterocyclic rings, and nitrogen atoms are subjected to alkylation reaction and then alkyl chains are introduced into the imidazole rings, so that the imidazole rings become positive ions to form the imidazole ionic liquid. The structure property is stable, the positive charges are uniformly distributed, and the imidazole ionic liquid functional group can generate multiple interactions with pollutants, so that the adsorbent material with a good adsorption effect can be obtained by introducing the imidazole ionic liquid functional group into cellulose.
However, at present, cellulose-based materials are modified by single functional groups, and the adsorption effect still cannot meet the actual requirement.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a cellulose-based adsorbent modified by a polyimidazole ionic liquid, and a preparation method and application thereof.
The invention is realized by the following technical scheme:
a cellulose-based adsorbent modified by polyimidazole ionic liquid has a structural formula shown as formula (1):
Figure BDA0001794491720000021
wherein n is 400 to 10000, and m is 25 to 100.
The preparation method of the polyimidazole ionic liquid modified cellulose-based adsorbent comprises the following steps:
step 1, preparing dialdehyde cellulose and polyimidazole ionic liquid respectively;
step 2, immersing the dialdehyde cellulose in water, dissolving the polyimidazole ionic liquid in HCl solution, mixing the dialdehyde cellulose aqueous solution and the HCl solution of the polyimidazole ionic liquid, controlling the pH value within the range of 2.5-3.5, and stirring for 4-8 hours at the temperature of 20-45 ℃ to obtain a crude product of the polyimidazole ionic liquid modified cellulose;
and 3, washing the crude product of the polyimidazole ionic liquid modified cellulose with ethanol and water, and drying to obtain the polyimidazole ionic liquid modified cellulose-based adsorbent.
Preferably, in step 1, the preparation method of the dialdehyde cellulose specifically comprises the following steps: immersing cellulose in sodium periodate aqueous solution, reacting for 3-7 hours at 30-80 ℃ in the dark, and then adding ethylene glycol for reaction to prepare a dialdehyde cellulose crude product; and repeatedly washing the crude product of the dialdehyde cellulose with water and ethanol until the supernatant is neutral to obtain the dialdehyde cellulose.
Preferably, the concentration of the sodium periodate aqueous solution is 8-32 g.L-1。
Preferably, the cellulose source is dissolved regenerated cotton cellulose, bacterial cellulose, microcrystalline cellulose or nanocellulose; the cellulose is in the form of a film, hydrogel, aerogel, paper, or powder.
Preferably, in the step 1, the preparation method of the polyimidazole ionic liquid specifically comprises the following steps:
(1) dissolving 1-vinyl imidazole and 3-bromopropylamine hydrobromide in absolute ethyl alcohol, stirring and mixing under the atmosphere of nitrogen, and carrying out reflux reaction at the temperature of 60-80 ℃ for 10-30 hours to obtain a crude product of ionic liquid 1-vinyl-3-aminopropylimidazole hydrobromide;
(2) adding ethyl acetate into the ionic liquid 1-vinyl-3-aminopropylimidazole hydrobromide crude product, precipitating and separating the ionic liquid, finally adding ethanol, and drying to obtain the ionic liquid 1-vinyl-3-aminopropylimidazole hydrobromide;
(3) dissolving ionic liquid 1-vinyl-3-aminopropylimidazole hydrobromide and azobisisobutyronitrile into N, N-dimethylformamide, stirring and mixing under the atmosphere of nitrogen, and carrying out reflux reaction at the temperature of 60-75 ℃ for 5-8 hours to obtain a crude product of the polyimidazole ionic liquid;
(4) adding ether into the crude product of the polyionic liquid for precipitation, adding N, N-dimethylformamide into the precipitate to prepare a saturated solution, dialyzing with water, and freeze-drying to obtain the polyimidazole ionic liquid.
Further, the mass ratio of the 1-vinyl imidazole to the 3-bromopropylamine hydrobromide is (1-2.5): 1.
Further, the mass ratio of the 1-vinyl-3-aminopropylimidazole hydrobromide to the azobisisobutyronitrile is 2: (0.02-0.2).
Furthermore, in the step 2, the mass ratio of the dialdehyde cellulose to the polyimidazole ionic liquid is 1 (1-7).
The application of the polyimidazole ionic liquid modified cellulose-based adsorbent in treating wastewater is characterized in that the wastewater is anionic dye wastewater or heavy metal ion wastewater.
Compared with the prior art, the invention has the following beneficial technical effects:
the polyion liquid is a polymer with anion and cation electrolyte groups on a repeating unit, combines some properties of the ionic liquid and the polymer, is used for modifying an adsorption material, increases adsorption action sites, can overcome the defects of few adsorption sites and weak adsorption action of a single grafted imidazole ionic liquid functional group, and greatly improves the adsorption capacity of cellulose. Meanwhile, by means of various interactions provided by imidazole functional groups in the imidazole ionic liquid on organic adsorbates, such as hydrophobic interaction, van der waals force, electrostatic interaction, hydrogen bonds, pi-pi conjugation and the like, the adsorption performance of the cellulose on pollutants in water is improved, and the problems that the adsorption capacity of the cellulose in a water phase is low, the function of the functional groups for modifying the cellulose in the existing modification technology on the dyes is single, the adsorption capacity does not meet requirements and the like can be effectively solved. Meanwhile, the prepared adsorbent has good degradability and biocompatibility, is beneficial to the sustainable development of the environment, and can be widely applied to the treatment of dye wastewater. Therefore, the polyimidazole ionic liquid is used for graft modification of the cellulose material, and the biomass adsorbent which is low in price, degradable and strong in adsorption capacity can be obtained.
The preparation method of the polyimidazole ionic liquid modified cellulose-based adsorbent is simple, the reaction condition is mild, the toxicity of reactants is low, the reaction process is safe, the process has economical efficiency and simplicity, and the adsorbent is degradable and is beneficial to sustainable development of the environment; and the reaction raw materials have wide sources, which is beneficial to the popularization and application of the material.
The polyimidazole ionic liquid modified cellulose-based adsorbent has high adsorption capacity on anionic dye and heavy metal ions, and can be used for treating dye wastewater.
Drawings
FIG. 1 is a comparison graph of infrared spectra of dialdehyde cellulose and cellulose before and after modification in example 1 of the invention, wherein A is cellulose before modification, B is dialdehyde cellulose, and C is cellulose-based adsorbent modified by polyimidazole ionic liquid.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
The invention discloses a cellulose-based adsorbent modified by polyimidazole ionic liquid, which has a structural formula shown as a formula (1):
Figure BDA0001794491720000051
wherein n is 400 to 10000, and m is 25 to 100.
The invention also discloses a preparation method of the polyimidazole ionic liquid modified cellulose-based adsorbent, which comprises the following steps:
s1, immersing 2g of cellulose in 25mL of sodium periodate aqueous solution with a certain concentration, placing the solution in a water bath at the temperature of 30-80 ℃, reacting for 3-7 hours in a dark place, adding 3mL of glycol, and reacting for 1 hour to prepare a dialdehyde cellulose crude product;
s2, repeatedly washing the crude product of the dialdehyde cellulose in the S1 with deionized water and ethanol, washing away unreacted sodium periodate and glycol solution on the surface of the dialdehyde cellulose until the supernatant is neutral to obtain the dialdehyde cellulose;
s3, dissolving 1-vinyl imidazole and 3-bromopropylamine hydrobromide in 20mL of absolute ethanol, stirring the mixture under the nitrogen atmosphere, and refluxing at 60-80 ℃ for 1 hour to obtain a crude product of ionic liquid 1-vinyl-3-aminopropylimidazole hydrobromide;
s4, adding ethyl acetate into the ionic liquid 1-vinyl-3-aminopropyl imidazole hydrobromide crude product in S3, and precipitating to separate the ionic liquid. Finally, 5mL of ethanol is added, and vacuum drying is carried out for 24 hours at the temperature of 60 ℃ to obtain ionic liquid 1-vinyl-3-aminopropylimidazole hydrobromide;
s5, dissolving the ionic liquid 1-vinyl-3-aminopropylimidazole hydrobromide and 0.02-0.2 g of azobisisobutyronitrile in the 2g S4 in 45mL of N, N-dimethylformamide. Stirring the mixture under the atmosphere of nitrogen, and refluxing for 5-8 hours at the temperature of 60-75 ℃ to obtain a crude product of the polyion liquid;
s6, adding diethyl ether into the crude product of the polyion liquid in the S5 for precipitation, adding 10-20 mL of N, N-dimethylformamide into the precipitate to prepare a saturated solution, dialyzing with pure water for 48 hours, and freeze-drying for 48 hours to obtain the polyion liquid;
s7, immersing dialdehyde-based cellulose in 2g S2 in 1L of deionized water, dissolving polyionic liquid in S6 in HCl solution with the concentration of 19.2g/L, mixing dialdehyde-based cellulose aqueous solution and HCl solution of polyimidazole ionic liquid, controlling the pH value to be within the range of 2.5-3.5, and stirring at 20-45 ℃ for 4-8 hours to obtain crude product of polyimidazole ionic liquid modified cellulose;
and S8, washing the crude product of the cellulose modified by the polyimidazole ionic liquid in the S7 with ethanol and deionized water, and drying to obtain the polyimidazole ionic liquid modified cellulose-based adsorbent.
The cellulose source in the S1 is dissolved and regenerated cotton cellulose, bacterial cellulose, microcrystalline cellulose or nano cellulose; the cellulose is in the form of a film, hydrogel, aerogel, paper, or powder.
The concentration of the sodium periodate aqueous solution in S1 is 8-32 g.L-1。
The mass ratio of 1-vinyl imidazole and 3-bromopropylamine hydrobromide in S3 is (2.5-1) to 1, and the mass ratio of dialdehyde cellulose in S7 to polyion liquid is 1 (1-7).
The invention also discloses application of the polyimidazole ionic liquid modified cellulose-based adsorbent in wastewater treatment.
The wastewater is anionic dye wastewater or heavy metal ion wastewater.
Specific examples are as follows.
Example 1
The preparation method of the polyimidazole ionic liquid modified cellulose-based adsorbent in the embodiment comprises the following steps:
1) 2g of the nano cellulose membrane (the structure is shown as the formula (2)) is immersed in 25mL of 32 g.L-1The solution was placed in a water bath at 50 ℃ and reacted for 4 hours in the dark, and then 3mL of ethylene glycol was added and reacted for 1 hour to prepare a crude dialdehyde-based cellulose.
Figure BDA0001794491720000071
2) And (3) after the reaction is finished, repeatedly washing with deionized water and ethanol, washing to remove unreacted sodium periodate and glycol solution on the surface of the dialdehyde cellulose, and washing until the supernatant is neutral to obtain the dialdehyde cellulose with the structure shown in the formula (3).
Figure BDA0001794491720000072
3) 1-vinyl imidazole and 3-bromopropylamine hydrobromide were added in a mass ratio of 2:1 to a vessel (e.g., 25mL round bottom flask), dissolved in 20mL of anhydrous ethanol, and the mixture was stirred under nitrogen atmosphere and refluxed at 60 ℃ for 24 hours to obtain ionic liquid 1-vinyl-3-aminopropylimidazole hydrobromide as a crude product.
4) After the reaction, ethyl acetate is added, and ionic liquid is separated by precipitation. And finally, adding 5mL of ethanol, and performing vacuum drying at 60 ℃ for 24 hours to obtain the ionic liquid 1-vinyl-3-aminopropylimidazole hydrobromide, wherein the structure is shown as the formula (4).
Figure BDA0001794491720000073
5) 2g of ionic liquid and 0.04g of azobisisobutyronitrile were dissolved in 45mL of N, N-dimethylformamide. The mixture was stirred under nitrogen and refluxed at 75 ℃ for 6 hours to give a crude polyionic liquid product.
6) After the reaction is finished, adding diethyl ether for precipitation, adding 10mL of N, N-dimethylformamide into the precipitate to prepare a saturated solution, dialyzing with pure water for 48 hours, and freeze-drying for 48 hours to obtain the polyion liquid.
7) Immersing 2g of dialdehyde cellulose in 1L of deionized water, dissolving 2g of polyionic liquid in a HCl solution with the concentration of 19.2g/L, mixing the dialdehyde cellulose aqueous solution and the HCl solution of the polyimidazole ionic liquid, controlling the pH value to be 3, and stirring at 25 ℃ for 6 hours to obtain a crude product of the polyimidazole ionic liquid modified cellulose.
8) After the reaction is finished, washing with ethanol and deionized water, and drying to obtain the cellulose-based adsorbent modified by the polyimidazole ionic liquid, wherein the structure is shown as the formula (1).
Example 2
The preparation method of the polyimidazole ionic liquid modified cellulose-based adsorbent in the embodiment comprises the following steps:
1) 2g of bacterial cellulose membrane (the structure is shown as formula (2)) is immersed in 25mL of 16 g.L-1The solution was placed in a water bath at 50 ℃ and was left to react for 5 hours in the dark, and then 3mL of ethylene glycol was added and reacted for 1 hour to prepare a crude dialdehyde-based cellulose.
2) And (3) after the reaction is finished, repeatedly washing with deionized water and ethanol, washing to remove unreacted sodium periodate and glycol solution on the surface of the dialdehyde cellulose, and washing until the supernatant is neutral to obtain the dialdehyde cellulose with the structure shown in the formula (3).
3) 1-vinyl imidazole and 3-bromopropylamine hydrobromide were added in a mass ratio of 2.1:1 to a vessel (e.g., 25mL round bottom flask), dissolved in 20mL of anhydrous ethanol, and the mixture was stirred under nitrogen atmosphere and refluxed at 80 ℃ for 24 hours to give a crude ionic liquid 1-vinyl-3-aminopropylimidazole hydrobromide.
4) After the reaction, ethyl acetate is added, and ionic liquid is separated by precipitation. And finally, adding 5mL of ethanol, and performing vacuum drying at 60 ℃ for 24 hours to obtain the ionic liquid 1-vinyl-3-aminopropylimidazole hydrobromide, wherein the structure is shown as the formula (4).
5) 2g of ionic liquid and 0.04g of azobisisobutyronitrile were dissolved in 45mL of N, N-dimethylformamide. The mixture was stirred under nitrogen and refluxed at 65 ℃ for 6 hours to give a crude polyionic liquid product.
6) After the reaction is finished, adding diethyl ether for precipitation, adding 10mL of N, N-dimethylformamide into the precipitate to prepare a saturated solution, dialyzing with pure water for 48 hours, and freeze-drying for 48 hours to obtain the polyion liquid.
7) Immersing 2g of dialdehyde cellulose in 1L of deionized water, dissolving 4g of polyionic liquid in a HCl solution with the concentration of 19.2g/L, mixing the dialdehyde cellulose aqueous solution and the HCl solution of the polyimidazole ionic liquid, controlling the pH value to be 3.3, and stirring at 25 ℃ for 5 hours to obtain a crude product of the polyimidazole ionic liquid modified cellulose.
8) After the reaction is finished, washing with ethanol and deionized water, and drying to obtain the polyimidazole ionic liquid modified cellulose-based adsorbent, wherein the structure is shown as the formula (1).
Example 3
The preparation method of the polyimidazole ionic liquid modified cellulose-based adsorbent in the embodiment comprises the following steps:
1) 2g of microcrystalline cellulose membrane (with the structure shown in formula (2)) is immersed in 25mL of 32 g.L-1The solution is put in a water bath at 60 ℃ and is protected from light for 5 hours, then 3mL of glycol is added for 1 hour, and a crude product of dialdehyde cellulose is prepared.
2) And (3) after the reaction is finished, repeatedly washing with deionized water and ethanol, washing to remove unreacted sodium periodate and glycol solution on the surface of the dialdehyde cellulose, and washing until the supernatant is neutral to obtain the dialdehyde cellulose with the structure shown in the formula (3).
3) 1-vinyl imidazole and 3-bromopropylamine hydrobromide were added in a mass ratio of 2:1 to a vessel (e.g., 25mL round bottom flask), dissolved in 20mL of anhydrous ethanol, and the mixture was stirred under nitrogen atmosphere and refluxed at 60 ℃ for 24 hours to obtain ionic liquid 1-vinyl-3-aminopropylimidazole hydrobromide as a crude product.
4) After the reaction, ethyl acetate is added, and ionic liquid is separated by precipitation. And finally, adding 5mL of ethanol, and performing vacuum drying at 60 ℃ for 24 hours to obtain the ionic liquid 1-vinyl-3-aminopropylimidazole hydrobromide, wherein the structure is shown as the formula (4).
5) 2g of ionic liquid and 0.04g of azobisisobutyronitrile were dissolved in 45mL of N, N-dimethylformamide. The mixture was stirred under nitrogen and refluxed at 75 ℃ for 6 hours to give a crude polyionic liquid product.
6) After the reaction is finished, adding diethyl ether for precipitation, adding 10mL of N, N-dimethylformamide into the precipitate to prepare a saturated solution, dialyzing with pure water for 48 hours, and freeze-drying for 48 hours to obtain the polyion liquid.
7) Immersing 2g of dialdehyde cellulose in 1L of deionized water, dissolving 6g of polyionic liquid in a HCl solution with the concentration of 19.2g/L, mixing the dialdehyde cellulose aqueous solution and the HCl solution of the polyimidazole ionic liquid, controlling the pH value to be 2.5, and stirring at 25 ℃ for 6 hours to obtain the polyimidazole ionic liquid modified cellulose.
8) After the reaction is finished, washing with ethanol and deionized water, and drying to obtain the polyimidazole ionic liquid modified cellulose-based adsorbent, wherein the structure is shown as the formula (1).
Example 4
The preparation method of the polyimidazole ionic liquid modified cellulose-based adsorbent in the embodiment comprises the following steps:
1) 2g of dissolved regenerated cotton cellulose aerogel (the structure is shown as the formula (2)) is immersed in 25mL of 16 g.L-1The solution was placed in a water bath at 50 ℃ and was left to react for 5 hours in the dark, and then 3mL of ethylene glycol was added and reacted for 1 hour to prepare a crude dialdehyde-based cellulose.
2) And (3) after the reaction is finished, repeatedly washing with deionized water and ethanol, washing to remove unreacted sodium periodate and glycol solution on the surface of the dialdehyde cellulose, and washing until the supernatant is neutral to obtain the dialdehyde cellulose with the structure shown in the formula (3).
3) 1-vinyl imidazole and 3-bromopropylamine hydrobromide were added in a mass ratio of 2.2:1 to a vessel (e.g., 25mL round bottom flask), dissolved in 20mL of anhydrous ethanol, and the mixture was stirred under nitrogen atmosphere and refluxed at 80 ℃ for 24 hours to give a crude ionic liquid 1-vinyl-3-aminopropylimidazole hydrobromide.
4) After the reaction, ethyl acetate is added, and ionic liquid is separated by precipitation. And finally, adding 5mL of ethanol, and performing vacuum drying at 60 ℃ for 24 hours to obtain the ionic liquid 1-vinyl-3-aminopropylimidazole hydrobromide, wherein the structure is shown as the formula (4).
5) 2g of ionic liquid and 0.04g of azobisisobutyronitrile were dissolved in 45mL of N, N-dimethylformamide. The mixture was stirred under nitrogen and refluxed at 65 ℃ for 7 hours to give a crude polyionic liquid product.
6) After the reaction is finished, adding diethyl ether for precipitation, adding 10mL of N, N-dimethylformamide into the precipitate to prepare a saturated solution, dialyzing with pure water for 48 hours, and freeze-drying for 48 hours to obtain the polyion liquid.
7) Immersing 2g of dialdehyde cellulose in 1L of deionized water, dissolving 6g of polyionic liquid in a HCl solution with the concentration of 19.2g/L, mixing the dialdehyde cellulose aqueous solution and the HCl solution of the polyimidazole ionic liquid, controlling the pH value to be 3, and stirring at 25 ℃ for 6 hours to obtain the polyimidazole ionic liquid modified cellulose.
8) After the reaction is finished, washing with ethanol and deionized water, and drying to obtain the polyimidazole ionic liquid modified cellulose-based adsorbent, wherein the structure is shown as the formula (1).
Example 5
The preparation method of the polyimidazole ionic liquid modified cellulose-based adsorbent in the embodiment comprises the following steps:
1) 2g of dissolved regenerated cotton cellulose aerogel (the structure is shown as the formula (2)) is immersed in 25mL of 32 g.L-1The solution was placed in a water bath at 80 ℃ and was reacted for 7 hours in the dark, and then 3mL of ethylene glycol was added and reacted for 1 hour to prepare a crude dialdehyde-based cellulose.
2) And (3) after the reaction is finished, repeatedly washing with deionized water and ethanol, washing to remove unreacted sodium periodate and glycol solution on the surface of the dialdehyde cellulose, and washing until the supernatant is neutral to obtain the dialdehyde cellulose with the structure shown in the formula (3).
3) 1-vinyl imidazole and 3-bromopropylamine hydrobromide were added in a mass ratio of 2:1 to a vessel (e.g., 25mL round bottom flask), dissolved in 20mL of anhydrous ethanol, and the mixture was stirred under nitrogen atmosphere and refluxed at 60 ℃ for 24 hours to obtain ionic liquid 1-vinyl-3-aminopropylimidazole hydrobromide as a crude product.
4) After the reaction, ethyl acetate is added, and ionic liquid is separated by precipitation. And finally, adding 5mL of ethanol, and performing vacuum drying at 60 ℃ for 24 hours to obtain the ionic liquid 1-vinyl-3-aminopropylimidazole hydrobromide, wherein the structure is shown as the formula (4).
5) 2g of ionic liquid and 0.04g of azobisisobutyronitrile were dissolved in 45mL of N, N-dimethylformamide. The mixture was stirred under nitrogen and refluxed at 65 ℃ for 7 hours to give a crude polyionic liquid product.
6) After the reaction is finished, adding diethyl ether for precipitation, adding 10mL of N, N-dimethylformamide into the precipitate to prepare a saturated solution, dialyzing with pure water for 48 hours, and freeze-drying for 48 hours to obtain the polyion liquid.
7) Immersing 2g of dialdehyde cellulose in 1L of deionized water, dissolving 6g of polyionic liquid in a HCl solution with the concentration of 19.2g/L, mixing the dialdehyde cellulose aqueous solution and the HCl solution of the polyimidazole ionic liquid, controlling the pH value to be 3, and stirring at 25 ℃ for 6 hours to obtain the polyimidazole ionic liquid modified cellulose.
8) After the reaction is finished, washing with ethanol and deionized water, and drying to obtain the polyimidazole ionic liquid modified cellulose-based adsorbent, wherein the structure is shown as the formula (1).
Example 6
The preparation method of the polyimidazole ionic liquid modified cellulose-based adsorbent in the embodiment comprises the following steps:
1) 2g of dissolved bacterial cellulose powder (the structure is shown as formula (2)) is immersed in 25mL of 8 g.L-1The solution was placed in a water bath at 30 ℃ and was reacted for 7 hours in the dark, and then 3mL of ethylene glycol was added and reacted for 1 hour to prepare a crude dialdehyde-based cellulose.
2) And (3) after the reaction is finished, repeatedly washing with deionized water and ethanol, washing to remove unreacted sodium periodate and glycol solution on the surface of the dialdehyde cellulose, and washing until the supernatant is neutral to obtain the dialdehyde cellulose with the structure shown in the formula (3).
3) 1-vinyl imidazole and 3-bromopropylamine hydrobromide were added in a mass ratio of 1:1 to a vessel (e.g., 25mL round bottom flask), dissolved in 20mL of anhydrous ethanol, and the mixture was stirred under nitrogen atmosphere and refluxed at 65 ℃ for 24 hours to obtain ionic liquid 1-vinyl-3-aminopropylimidazole hydrobromide as a crude product.
4) After the reaction, ethyl acetate is added, and ionic liquid is separated by precipitation. And finally, adding 5mL of ethanol, and performing vacuum drying at 60 ℃ for 24 hours to obtain the ionic liquid 1-vinyl-3-aminopropylimidazole hydrobromide, wherein the structure is shown as the formula (4).
5) 2g of ionic liquid and 0.04g of azobisisobutyronitrile were dissolved in 45mL of N, N-dimethylformamide. The mixture was stirred under nitrogen and refluxed at 60 ℃ for 8 hours to give a crude polyionic liquid product.
6) After the reaction is finished, adding diethyl ether for precipitation, adding 10mL of N, N-dimethylformamide into the precipitate to prepare a saturated solution, dialyzing with pure water for 48 hours, and freeze-drying for 48 hours to obtain the polyion liquid.
7) Immersing 2g of dialdehyde cellulose in 1L of deionized water, dissolving 8g of polyionic liquid in a HCl solution with the concentration of 19.2g/L, mixing the dialdehyde cellulose aqueous solution and the HCl solution of the polyimidazole ionic liquid, controlling the pH value to be 3.5, and stirring at 30 ℃ for 6 hours to obtain the polyimidazole ionic liquid modified cellulose.
8) After the reaction is finished, washing with ethanol and deionized water, and drying to obtain the polyimidazole ionic liquid modified cellulose-based adsorbent, wherein the structure is shown as the formula (1).
Example 7
The preparation method of the polyimidazole ionic liquid modified cellulose-based adsorbent in the embodiment comprises the following steps:
1) 2g of a dissolved microcrystalline cellulose hydrogel (having the structure shown in formula (2)) was immersed in 25mL of 20 g. L-1The solution was placed in a water bath at 70 ℃ and was reacted for 3 hours in the dark, and then 3mL of ethylene glycol was added and reacted for 1 hour to prepare a crude dialdehyde-based cellulose.
2) And (3) after the reaction is finished, repeatedly washing with deionized water and ethanol, washing to remove unreacted sodium periodate and glycol solution on the surface of the dialdehyde cellulose, and washing until the supernatant is neutral to obtain the dialdehyde cellulose with the structure shown in the formula (3).
3) 1-vinyl imidazole and 3-bromopropylamine hydrobromide were added in a mass ratio of 1.5:1 to a vessel (e.g., 25mL round bottom flask), dissolved in 20mL of anhydrous ethanol, and the mixture was stirred under nitrogen atmosphere and refluxed at 70 ℃ for 24 hours to give a crude ionic liquid 1-vinyl-3-aminopropylimidazole hydrobromide.
4) After the reaction, ethyl acetate is added, and ionic liquid is separated by precipitation. And finally, adding 5mL of ethanol, and performing vacuum drying at 60 ℃ for 24 hours to obtain the ionic liquid 1-vinyl-3-aminopropylimidazole hydrobromide, wherein the structure is shown as the formula (4).
5) 2g of ionic liquid and 0.04g of azobisisobutyronitrile were dissolved in 45mL of N, N-dimethylformamide. The mixture was stirred under nitrogen and refluxed at 70 ℃ for 5 hours to give a crude polyionic liquid product.
6) After the reaction is finished, adding diethyl ether for precipitation, adding 10mL of N, N-dimethylformamide into the precipitate to prepare a saturated solution, dialyzing with pure water for 48 hours, and freeze-drying for 48 hours to obtain the polyion liquid.
7) Immersing 2g of dialdehyde cellulose in 1L of deionized water, dissolving 10g of polyionic liquid in a HCl solution with the concentration of 19.2g/L, mixing the dialdehyde cellulose aqueous solution and the HCl solution of the polyimidazole ionic liquid, controlling the pH value to be 3.5, and stirring at 35 ℃ for 6 hours to obtain the polyimidazole ionic liquid modified cellulose.
8) After the reaction is finished, washing with ethanol and deionized water, and drying to obtain the polyimidazole ionic liquid modified cellulose-based adsorbent, wherein the structure is shown as the formula (1).
Example 8
The preparation method of the polyimidazole ionic liquid modified cellulose-based adsorbent in the embodiment comprises the following steps:
1) 2g of dissolved microcrystalline cellulose hydrogel (the structure is shown as formula (2)) is immersed in 25mL of 20g & L-1 sodium periodate aqueous solution, placed in a water bath at 70 ℃, and reacted for 3 hours in a dark place, and then 3mL of ethylene glycol is added for reaction for 1 hour, so as to prepare the crude product of dialdehyde cellulose.
2) And (3) after the reaction is finished, repeatedly washing with deionized water and ethanol, washing to remove unreacted sodium periodate and glycol solution on the surface of the dialdehyde cellulose, and washing until the supernatant is neutral to obtain the dialdehyde cellulose with the structure shown in the formula (3).
3) 1-vinyl imidazole and 3-bromopropylamine hydrobromide were added in a mass ratio of 2.5:1 to a vessel (e.g., 25mL round bottom flask), dissolved in 20mL of anhydrous ethanol, and the mixture was stirred under nitrogen atmosphere and refluxed at 70 ℃ for 28 hours to give a crude ionic liquid 1-vinyl-3-aminopropylimidazole hydrobromide.
4) After the reaction, ethyl acetate is added, and ionic liquid is separated by precipitation. And finally, adding 5mL of ethanol, and performing vacuum drying at 60 ℃ for 24 hours to obtain the ionic liquid 1-vinyl-3-aminopropylimidazole hydrobromide, wherein the structure is shown as the formula (4).
5) 2g of ionic liquid and 0.02g of azobisisobutyronitrile were dissolved in 45mL of N, N-dimethylformamide. The mixture was stirred under nitrogen and refluxed at 70 ℃ for 5 hours to give a crude polyionic liquid product.
6) After the reaction is finished, adding diethyl ether for precipitation, adding 10mL of N, N-dimethylformamide into the precipitate to prepare a saturated solution, dialyzing with pure water for 48 hours, and freeze-drying for 48 hours to obtain the polyion liquid.
7) Immersing 2g of dialdehyde cellulose in 1L of deionized water, dissolving 14g of polyionic liquid in a HCl solution with the concentration of 19.2g/L, mixing the dialdehyde cellulose aqueous solution and the HCl solution of the polyimidazole ionic liquid, controlling the pH value to be 3.5, and stirring at 25 ℃ for 6 hours to obtain the polyimidazole ionic liquid modified cellulose.
8) After the reaction is finished, washing with ethanol and deionized water, and drying to obtain the polyimidazole ionic liquid modified cellulose-based adsorbent, wherein the structure is shown as the formula (1).
Example 9
The preparation method of the polyimidazole ionic liquid modified cellulose-based adsorbent in the embodiment comprises the following steps:
1) 2g of bacterial cellulose membrane (the structure is shown as formula (2)) is immersed in 25mL of 16 g.L-1The solution was placed in a water bath at 50 ℃ and was left to react for 5 hours in the dark, and then 3mL of ethylene glycol was added and reacted for 1 hour to prepare a crude dialdehyde-based cellulose.
2) And (3) after the reaction is finished, repeatedly washing with deionized water and ethanol, washing to remove unreacted sodium periodate and glycol solution on the surface of the dialdehyde cellulose, and washing until the supernatant is neutral to obtain the dialdehyde cellulose with the structure shown in the formula (3).
3) 1-vinyl imidazole and 3-bromopropylamine hydrobromide were added in a mass ratio of 2.1:1 to a vessel (e.g., 25mL round bottom flask), dissolved in 20mL of anhydrous ethanol, and the mixture was stirred under nitrogen atmosphere and refluxed at 80 ℃ for 10 hours to give a crude ionic liquid 1-vinyl-3-aminopropylimidazole hydrobromide.
4) After the reaction, ethyl acetate is added, and ionic liquid is separated by precipitation. And finally, adding 5mL of ethanol, and performing vacuum drying at 60 ℃ for 24 hours to obtain the ionic liquid 1-vinyl-3-aminopropylimidazole hydrobromide, wherein the structure is shown as the formula (4).
5) 2g of ionic liquid and 0.08g of azobisisobutyronitrile were dissolved in 45mL of N, N-dimethylformamide. The mixture was stirred under nitrogen and refluxed at 65 ℃ for 6 hours to give a crude polyionic liquid product.
6) After the reaction is finished, adding diethyl ether for precipitation, adding 10mL of N, N-dimethylformamide into the precipitate to prepare a saturated solution, dialyzing with pure water for 48 hours, and freeze-drying for 48 hours to obtain the polyion liquid.
7) Immersing 2g of dialdehyde cellulose in 1L of deionized water, dissolving 4g of polyionic liquid in a HCl solution with the concentration of 19.2g/L, mixing the dialdehyde cellulose aqueous solution and the HCl solution of the polyimidazole ionic liquid, controlling the pH value to be 3.3, and stirring at 25 ℃ for 5 hours to obtain a crude product of the polyimidazole ionic liquid modified cellulose.
8) After the reaction is finished, washing with ethanol and deionized water, and drying to obtain the polyimidazole ionic liquid modified cellulose-based adsorbent, wherein the structure is shown as the formula (1).
Example 10
The preparation method of the polyimidazole ionic liquid modified cellulose-based adsorbent in the embodiment comprises the following steps:
1) 2g of bacterial cellulose membrane (the structure is shown as formula (2)) is immersed in 25mL of 16 g.L-1The solution was placed in a water bath at 50 ℃ and was left to react for 5 hours in the dark, and then 3mL of ethylene glycol was added and reacted for 1 hour to prepare a crude dialdehyde-based cellulose.
2) And (3) after the reaction is finished, repeatedly washing with deionized water and ethanol, washing to remove unreacted sodium periodate and glycol solution on the surface of the dialdehyde cellulose, and washing until the supernatant is neutral to obtain the dialdehyde cellulose with the structure shown in the formula (3).
3) 1-vinyl imidazole and 3-bromopropylamine hydrobromide were added in a mass ratio of 2.1:1 to a vessel (e.g., 25mL round bottom flask), dissolved in 20mL of anhydrous ethanol, and the mixture was stirred under nitrogen atmosphere and refluxed at 80 ℃ for 30 hours to obtain a crude ionic liquid 1-vinyl-3-aminopropylimidazole hydrobromide.
4) After the reaction, ethyl acetate is added, and ionic liquid is separated by precipitation. And finally, adding 5mL of ethanol, and performing vacuum drying at 60 ℃ for 24 hours to obtain the ionic liquid 1-vinyl-3-aminopropylimidazole hydrobromide, wherein the structure is shown as the formula (4).
5) 2g of ionic liquid and 0.10g of azobisisobutyronitrile were dissolved in 45mL of N, N-dimethylformamide. The mixture was stirred under nitrogen and refluxed at 65 ℃ for 6 hours to give a crude polyionic liquid product.
6) After the reaction is finished, adding diethyl ether for precipitation, adding 10mL of N, N-dimethylformamide into the precipitate to prepare a saturated solution, dialyzing with pure water for 48 hours, and freeze-drying for 48 hours to obtain the polyion liquid.
7) Immersing 2g of dialdehyde cellulose in 1L of deionized water, dissolving 4g of polyionic liquid in a HCl solution with the concentration of 19.2g/L, mixing the dialdehyde cellulose aqueous solution and the HCl solution of the polyimidazole ionic liquid, controlling the pH value to be 3.3, and stirring at 20 ℃ for 4 hours to obtain a crude product of the polyimidazole ionic liquid modified cellulose.
8) After the reaction is finished, washing with ethanol and deionized water, and drying to obtain the polyimidazole ionic liquid modified cellulose-based adsorbent, wherein the structure is shown as the formula (1).
Example 11
The preparation method of the polyimidazole ionic liquid modified cellulose-based adsorbent in the embodiment comprises the following steps:
1) 2g of bacterial cellulose membrane (the structure is shown as formula (2)) is immersed in 25mL of 16 g.L-1The solution was placed in a water bath at 50 ℃ and was left to react for 5 hours in the dark, and then 3mL of ethylene glycol was added and reacted for 1 hour to prepare a crude dialdehyde-based cellulose.
2) And (3) after the reaction is finished, repeatedly washing with deionized water and ethanol, washing to remove unreacted sodium periodate and glycol solution on the surface of the dialdehyde cellulose, and washing until the supernatant is neutral to obtain the dialdehyde cellulose with the structure shown in the formula (3).
3) 1-vinyl imidazole and 3-bromopropylamine hydrobromide were added in a mass ratio of 2.1:1 to a vessel (e.g., 25mL round bottom flask), dissolved in 20mL of anhydrous ethanol, and the mixture was stirred under nitrogen atmosphere and refluxed at 80 ℃ for 15 hours to give a crude ionic liquid 1-vinyl-3-aminopropylimidazole hydrobromide.
4) After the reaction, ethyl acetate is added, and ionic liquid is separated by precipitation. And finally, adding 5mL of ethanol, and performing vacuum drying at 60 ℃ for 24 hours to obtain the ionic liquid 1-vinyl-3-aminopropylimidazole hydrobromide, wherein the structure is shown as the formula (4).
5) 2g of ionic liquid and 0.15g of azobisisobutyronitrile were dissolved in 45mL of N, N-dimethylformamide. The mixture was stirred under nitrogen and refluxed at 65 ℃ for 6 hours to give a crude polyionic liquid product.
6) After the reaction is finished, adding diethyl ether for precipitation, adding 10mL of N, N-dimethylformamide into the precipitate to prepare a saturated solution, dialyzing with pure water for 48 hours, and freeze-drying for 48 hours to obtain the polyion liquid.
7) Immersing 2g of dialdehyde cellulose in 1L of deionized water, dissolving 4g of polyionic liquid in a HCl solution with the concentration of 19.2g/L, mixing the dialdehyde cellulose aqueous solution and the HCl solution of the polyimidazole ionic liquid, controlling the pH value to be 3.3, and stirring at 45 ℃ for 6 hours to obtain a crude product of the polyimidazole ionic liquid modified cellulose.
8) After the reaction is finished, washing with ethanol and deionized water, and drying to obtain the polyimidazole ionic liquid modified cellulose-based adsorbent, wherein the structure is shown as the formula (1).
Example 12
The preparation method of the polyimidazole ionic liquid modified cellulose-based adsorbent in the embodiment comprises the following steps:
1) 2g of bacterial cellulose membrane (the structure is shown as formula (2)) is immersed in 25mL of 16 g.L-1The solution was placed in a water bath at 50 ℃ and was left to react for 5 hours in the dark, and then 3mL of ethylene glycol was added and reacted for 1 hour to prepare a crude dialdehyde-based cellulose.
2) And (3) after the reaction is finished, repeatedly washing with deionized water and ethanol, washing to remove unreacted sodium periodate and glycol solution on the surface of the dialdehyde cellulose, and washing until the supernatant is neutral to obtain the dialdehyde cellulose with the structure shown in the formula (3).
3) 1-vinyl imidazole and 3-bromopropylamine hydrobromide were added in a mass ratio of 2.1:1 to a vessel (e.g., 25mL round bottom flask), dissolved in 20mL of anhydrous ethanol, and the mixture was stirred under a nitrogen atmosphere and refluxed at 80 ℃ for 20 hours to give a crude ionic liquid 1-vinyl-3-aminopropylimidazole hydrobromide.
4) After the reaction, ethyl acetate is added, and ionic liquid is separated by precipitation. And finally, adding 5mL of ethanol, and performing vacuum drying at 60 ℃ for 24 hours to obtain the ionic liquid 1-vinyl-3-aminopropylimidazole hydrobromide, wherein the structure is shown as the formula (4).
5) 2g of ionic liquid and 0.2g of azobisisobutyronitrile were dissolved in 45mL of N, N-dimethylformamide. The mixture was stirred under nitrogen and refluxed at 65 ℃ for 6 hours to give a crude polyionic liquid product.
6) After the reaction is finished, adding diethyl ether for precipitation, adding 10mL of N, N-dimethylformamide into the precipitate to prepare a saturated solution, dialyzing with pure water for 48 hours, and freeze-drying for 48 hours to obtain the polyion liquid.
7) Immersing 2g of dialdehyde cellulose in 1L of deionized water, dissolving 4g of polyionic liquid in a HCl solution with the concentration of 19.2g/L, mixing the dialdehyde cellulose aqueous solution and the HCl solution of the polyimidazole ionic liquid, controlling the pH value to be 3.3, and stirring at 20 ℃ for 8 hours to obtain a crude product of the polyimidazole ionic liquid modified cellulose.
8) After the reaction is finished, washing with ethanol and deionized water, and drying to obtain the polyimidazole ionic liquid modified cellulose-based adsorbent, wherein the structure is shown as the formula (1).
The polyimidazole ionic liquid modified cellulose-based adsorbent prepared by the invention is characterized as follows:
1) infrared spectroscopic analysis
Infrared spectroscopic analysis was performed on the polyimidazole ionic liquid-modified cellulose-based adsorbent and dialdehyde cellulose prepared in example 1 of the present invention, see fig. 1, where a in fig. 1 is cellulose before modification, B is dialdehyde cellulose, and C is the polyimidazole ionic liquid-modified cellulose-based adsorbent. By infrared spectroscopic analysis, cellulose showed only the typical absorption band of the cellulose skeleton, 3340cm-1Due to O-HA key; compared with cellulose, dialdehyde cellulose is 1740cm higher-1Peak, is C ═ O aldehyde group stretching vibration peak; the polyimidazole ionic liquid modified cellulose-based adsorbent is 1240cm-1And 1454cm-1The imidazole ionic liquid has an absorption peak which is a skeleton characteristic peak of an imidazole functional group, and the imidazole ionic liquid is proved to be successfully connected on a cellulose skeleton.
2) Nuclear magnetic resonance hydrogen spectroscopy
The hydrogen nuclear magnetic resonance spectroscopy analysis of the polyimidazole ionic liquid modified cellulose-based adsorbent prepared in the embodiment 1 of the invention is further performed to confirm that the target product is synthesized.1HNMR(D2O，298K)δ：2.15(m，2H，-C-CH2-C-)，2.97(m，2H，-NCH2)，4.12(m，2H，-Im-CH2-), 5.33(dd, 1H, -CHH), 5.70(m, 1H, -CHH), 7.06(m, ═ CH-Im), 7.48(dd, 1H, C-CH-N, Im), 7.71(m, 1H, N-CH-C, Im), 9.02(s, 1H, N-CH-N, Im), Im means the imidazole ring.
3) Adsorption Performance test
0.05g of the polyimidazole ionic liquid modified cellulose-based adsorbent prepared in examples 1 to 3 and 5 was added to 10mL of congo red solution with a concentration of 3g/L, respectively, the polyimidazole ionic liquid modified cellulose-based adsorbent prepared in example 4 was added to 10mL of heavy metal ion chromium ion solution with a concentration of 3g/L, and after each reaction (adsorption) was performed at 25 ℃ for 24 hours, the concentrations of the remaining anionic dye congo red and heavy metal ion chromium ions in the solution were measured, and the adsorption amounts of the adsorbent to the anionic dye congo red and heavy metal ion chromium ions were calculated, respectively.
The calculation formula of the adsorption amount of the polyimidazole ionic liquid modified cellulose-based adsorbent to anionic dye congo red and heavy metal ion chromium ions is as follows:
Figure BDA0001794491720000201
wherein Q represents the adsorption quantity of the adsorbent to the anionic dye Congo red or heavy metal ion chromium ion, mg.L-1；C0Indicates anionInitial concentration of the daughter dye Congo Red or heavy Metal ion chromium ion, mg. L-1；CtExpressing the concentration of the anionic dye Congo red or heavy metal ion chromium ion after adsorption, mg.L-1(ii) a V represents the volume of the anionic dye Congo red or heavy metal ion chromium ion solution, L; m represents the mass of the adsorbent, g; the results of the adsorption performance test are shown in table 1.
Table 1 adsorption performance test results
Figure BDA0001794491720000211
Test results show that the polyimidazole ionic liquid modified cellulose-based adsorbent prepared by the invention has higher adsorption capacity on anionic dye and heavy metal ions, and can be widely applied to treatment of printing and dyeing wastewater.
The invention relates to a polyimidazole ionic liquid modified cellulose-based adsorbent, which is a synthetic adsorbent prepared by two-step reaction, wherein firstly, dialdehyde cellulose is prepared, and secondly, the polyimidazole ionic liquid modified cellulose is prepared; immersing 2g of dissolved regenerated cotton cellulose, bacterial cellulose, microcrystalline cellulose or nano cellulose membrane, hydrogel, aerogel, paper or powder in 25mL of 8-32 g.L < -1 > sodium periodate aqueous solution, reacting for 3-7 hours at 30-80 ℃ in a dark place, adding 3mL of glycol, reacting for 1 hour, and repeatedly washing with deionized water and ethanol until the supernatant is neutral; dissolving 1-vinylimidazole and 3-bromopropylamine hydrobromide in a mass ratio of 2.5-1: 1 in 20mL of absolute ethanol, stirring the mixture under a nitrogen atmosphere, refluxing at 60-80 ℃ for 24 hours, adding ethyl acetate, precipitating and separating ionic liquid, adding 5mL of ethanol, and vacuum-drying at 60 ℃ for 24 hours; dissolving 2g of ionic liquid 1-vinyl-3-aminopropylimidazole hydrobromide and 0.04g of azobisisobutyronitrile in 45mL of N, N-dimethylformamide, stirring the mixture under the nitrogen atmosphere, refluxing at 60-75 ℃ for 5-8 hours, adding diethyl ether for precipitation, adding 10-20 mL of N, N-dimethylformamide into the precipitate to prepare a saturated solution, dialyzing with pure water for 48 hours, and freeze-drying for 48 hours; immersing 2g of dialdehyde-based cellulose in 1L of deionized water, dissolving polyion liquid with the mass being 1-7 times that of the dialdehyde-based cellulose in 19.2g/L HCl solution, controlling the pH value of the solution within the range of 2.5-3.5, stirring for 6 hours at 25 ℃, washing with ethanol and deionized water, and drying to obtain the polyimidazole ion liquid modified cellulose-based adsorbent.
The efficient and economic adsorbent has high adsorption capacity on pollutants through various interactions, such as hydrophobic interaction, electrostatic interaction, hydrogen bonds, pi-pi conjugation and the like, and can effectively solve the problems that the adsorption capacity of cellulose in a water phase is low, the function of a functional group for modifying the cellulose by the existing modification technology is single to dyes, the adsorption capacity does not meet requirements and the like. Compared with the single imidazole ionic liquid functional group subjected to grafting modification, the method increases adsorption action sites by utilizing the imidazole ionic liquid to modify the cellulose, and can effectively adsorb pollutants in water. The adsorbent can be widely applied to treatment of printing and dyeing wastewater, the preparation method is simple, the reaction conditions are mild, the toxicity of reactants is low, the reaction process is safe, the sources of reaction raw materials are wide, the process has economical efficiency and simplicity, and the adsorbent is degradable and is beneficial to sustainable development of the environment.

Claims (8)

1. A preparation method of a cellulose-based adsorbent modified by polyimidazole ionic liquid is disclosed, wherein the structural formula of the cellulose-based adsorbent modified by the polyimidazole ionic liquid is shown as a formula (1):
Figure FDA0002892402070000011
wherein n is 400-10000, and m is 25-100;
the method is characterized by comprising the following steps:
step 1, preparing dialdehyde cellulose and polyimidazole ionic liquid respectively;
step 2, immersing the dialdehyde cellulose in water, dissolving the polyimidazole ionic liquid in HCl solution, mixing the dialdehyde cellulose aqueous solution and the HCl solution of the polyimidazole ionic liquid, controlling the pH value within the range of 2.5-3.5, and stirring for 4-8 hours at the temperature of 20-45 ℃ to obtain a crude product of the polyimidazole ionic liquid modified cellulose;
and 3, washing the crude product of the polyimidazole ionic liquid modified cellulose with ethanol and water, and drying to obtain the polyimidazole ionic liquid modified cellulose-based adsorbent.
2. The method for preparing the polyimidazole ionic liquid-modified cellulose-based adsorbent according to claim 1, wherein in the step 1, the method for preparing dialdehyde-based cellulose specifically comprises the following steps: immersing cellulose in sodium periodate aqueous solution, reacting for 3-7 hours at 30-80 ℃ in the dark, and then adding ethylene glycol for reaction to prepare a dialdehyde cellulose crude product; and repeatedly washing the crude product of the dialdehyde cellulose with water and ethanol until the supernatant is neutral to obtain the dialdehyde cellulose.
3. The method for preparing the polyimidazole ionic liquid-modified cellulose-based adsorbent according to claim 2, wherein the concentration of the sodium periodate aqueous solution is 8-32 g-L-1。
4. The method for preparing the polyimidazole ionic liquid-modified cellulose-based adsorbent according to claim 2, wherein the cellulose source is dissolved regenerated cotton cellulose, bacterial cellulose, microcrystalline cellulose or nanocellulose; the cellulose is in the form of a film, hydrogel, aerogel, paper, or powder.
5. The method for preparing the polyimidazole ionic liquid-modified cellulose-based adsorbent according to claim 1, wherein in the step 1, the method for preparing the polyimidazole ionic liquid specifically comprises:
(1) dissolving 1-vinyl imidazole and 3-bromopropylamine hydrobromide in absolute ethyl alcohol, stirring and mixing under the atmosphere of nitrogen, and carrying out reflux reaction at the temperature of 60-80 ℃ for 10-30 hours to obtain a crude product of ionic liquid 1-vinyl-3-aminopropylimidazole hydrobromide;
(2) adding ethyl acetate into the ionic liquid 1-vinyl-3-aminopropylimidazole hydrobromide crude product, precipitating and separating the ionic liquid, finally adding ethanol, and drying to obtain the ionic liquid 1-vinyl-3-aminopropylimidazole hydrobromide;
(3) dissolving ionic liquid 1-vinyl-3-aminopropylimidazole hydrobromide and azobisisobutyronitrile into N, N-dimethylformamide, stirring and mixing under the atmosphere of nitrogen, and carrying out reflux reaction at the temperature of 60-75 ℃ for 5-8 hours to obtain a crude product of the polyimidazole ionic liquid;
(4) adding ether into the crude product of the polyionic liquid for precipitation, adding N, N-dimethylformamide into the precipitate to prepare a saturated solution, dialyzing with water, and freeze-drying to obtain the polyimidazole ionic liquid.
6. The method for preparing the polyimidazole ionic liquid-modified cellulose-based adsorbent according to claim 5, wherein the mass ratio of 1-vinylimidazole to 3-bromopropylamine hydrobromide is (1-2.5): 1.
7. The method for preparing a polyimidazole ionic liquid-modified cellulose-based adsorbent according to claim 5, wherein the mass ratio of 1-vinyl-3-aminopropylimidazole hydrobromide to azobisisobutyronitrile is 2: (0.02-0.2).
8. The preparation method of the polyimidazole ionic liquid modified cellulose-based adsorbent according to claim 1, wherein in the step 2, the mass ratio of the dialdehyde cellulose to the polyimidazole ionic liquid is 1 (1-7).
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