CN112973647B - Magnetic 3D polymer micro-nano dye adsorbent coated with polytannic acid-phosphazene, and preparation method and application thereof - Google Patents

Magnetic 3D polymer micro-nano dye adsorbent coated with polytannic acid-phosphazene, and preparation method and application thereof Download PDF

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CN112973647B
CN112973647B CN202011389377.2A CN202011389377A CN112973647B CN 112973647 B CN112973647 B CN 112973647B CN 202011389377 A CN202011389377 A CN 202011389377A CN 112973647 B CN112973647 B CN 112973647B
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谢煜彬
黄锦涛
谢钢禹
魏榕笙
张笑晴
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Guangdong University of Technology
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Abstract

The invention belongs to the field of environment-friendly materials, and discloses a magnetic 3D polymer micro-nano dye adsorbent coated with polytannic acid-phosphazene, and a preparation method and application thereof. The novel magnetic 3D polymer micro-nano dye adsorbent is obtained by taking a 3D polymer nano material as an adsorbent carrier and directly coating the surface layer of the polymer nano flower MCA with a polyphosphazene coating layer of BPS/TA/HCCP through in-situ polycondensation. The novel magnetic 3D polymer micro-nano dye adsorbent prepared by the invention has larger adsorption capacity to cationic dyes in a shorter time, can effectively reduce the using amount of the adsorbent and shorten the adsorption time, has stable property, and can effectively improve the pollution of cationic dye wastewater to the environment.

Description

Polytannic acid-phosphazene coated magnetic 3D polymer micro-nano dye adsorbent and preparation method and application thereof
Technical Field
The invention belongs to the field of environmental protection materials, and particularly relates to a magnetic 3D polymer micro-nano dye adsorbent coated with polytannic acid-phosphazene, and a preparation method and application thereof.
Background
In the printing and dyeing and textile industry, 1 ton of dye wastewater can pollute 20 tons of water, and the harmfulness is serious: (1) The chromaticity of the dye wastewater seriously deteriorates the appearance of a water body, and the dye in the wastewater can absorb illumination, reduce the transparency of the water body, influence the growth of aquatic organisms and microorganisms and destroy the ecological balance; (2) After the dye-polluted underground water is absorbed by a human body, the health can be seriously threatened, allergy and dermatitis are caused, and canceration is seriously even induced; (3) The molecular structure of the dye in the wastewater is developing towards photolysis resistance, oxidation resistance and biodegradation resistance, and the dye is likely to be difficult to biodegrade and chemically decompose. Therefore, proper regeneration and purification treatment is urgently needed before the wastewater is discharged so as to reach the industrial discharge standard.
There are many technical methods for regenerating, purifying and treating dye wastewater, and the method can be simply divided into two main categories: biochemical and physicochemical methods. Most of the organic dyes currently on the market are polyphenyl ring-substituted compounds such as aromatic amine compounds, aromatic nitro compounds, aromatic halides, and biphenyls. They usually have a complex aromatic structure, are difficult to biodegrade and chemically decompose, and also have the properties of acid and alkali resistance, photolysis resistance and oxidation resistance. Especially, printing and dyeing wastewater containing a mixture of various dyes (mainly takes aromatic groups such as anthracene, quinone, benzene, naphthalene and the like as precursors and carries specific colored groups), so that it is difficult to find an effective chemical decomposition or biodegradation method for removing the dyes in the wastewater. While the chemical decomposition is usually carried out by destroying the chemical structure of the dye, small molecules with toxicity are often generated, secondary pollution is caused, and the cost is high. The physical and chemical method comprises an adsorption method, a coagulation flocculation method, an oxidation method, a membrane separation technology, an ion exchange method and the like, and the aim of purifying the wastewater is achieved by enriching, separating and removing the dye or destroying the structure of the organic dye.
The adsorption method is an important dye wastewater treatment technology, has the advantages of simple and convenient operation, large dye adsorption capacity, high adsorption efficiency, less time consumption, low cost, no secondary pollution and the like, is widely applied to the aspect of printing and dyeing industry wastewater treatment, and is a dye wastewater treatment technology with the greatest development prospect. The conventional adsorbents commonly used in the adsorption method are carbon adsorbents (activated carbon, graphene and derivatives thereof), alumina, silica gel, natural materials, agricultural and industrial wastes, biomass adsorbents, and the like. In recent decades, polymeric adsorbents have become an important class of adsorbing materials that can potentially replace activated carbon materials due to their excellent designability (adjustable surface chemistry and pore size of the adsorbent), and the adsorption process of such adsorbing materials is usually a reversible process. Recently, a large number of synthetic polymer nanomaterials have been used for the treatment of dye wastewater, such as poly (N-vinyl-2-pyrrolidone), poly (1-naphthylamine). Researchers also have synthesized polyaniline nanotube/silica composites that can be used as excellent adsorbents to remove the cationic dye methylene blue from aqueous solutions.
At present, the polymer nano material also exists in the field of dye wastewater treatment: (1) low adsorption efficiency. Although the specific surface area of the traditional polymer nano material is large, the adsorption efficiency is low, and the specific surface area cannot be fully utilized; and (2) the recovery is difficult, and secondary pollution is easily caused. The traditional polymer nano material still exists in a water body after adsorbing fuel, is difficult to separate, cannot be degraded or recycled, and is easy to cause secondary pollution.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention mainly aims to provide a preparation method of a magnetic 3D polymer micro-nano dye adsorbent coated with polytannic acid-phosphazene. The preparation method is simple to operate, and the used solvent and the used drug materials do not cause toxicity to the environment and the human body.
The invention also aims to provide the magnetic 3D polymer micro-nano dye adsorbent coated with the polytannic acid-phosphazene prepared by the preparation method. Compared with the traditional polymer nano material, the poly-tannic acid-phosphazene coated magnetic micro-nano dye adsorbent material has higher adsorption efficiency, and tannic acid with high content of phenolic hydroxyl is introduced as one component to be matched with a polymer nanoflower 3D structure, so that the specific surface area and the adsorption efficiency of the material are greatly improved; the magnetic particles introduced by the magnetic material are adhered to the surface of the nano material, so that the magnetic material can be recovered and removed by a magnet, and secondary pollution caused by polymer nano material residue is avoided
The invention further aims to provide an application of the magnetic 3D polymer micro-nano dye adsorbent coated with the poly-tannic acid-phosphazene.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a magnetic 3D polymer micro-nano dye adsorbent coated by poly-tannic acid-phosphazene comprises the following steps:
(1) Preparation of 3D polymer nanomaterials: melamine and cyanuric acid are taken as raw materials, and are respectively added into two groups of dimethyl sulfoxide for ultrasonic dissolution; after complete dissolution, dropwise adding a dimethyl sulfoxide solution of Cyanuric Acid (CA) into a dimethyl sulfoxide solution of Melamine (MA), magnetically stirring, reacting for 1h, performing suction filtration, and washing off the dimethyl sulfoxide by using 1' 4-dioxane to obtain polymer nanoflower MCA;
(2) Preparing a 3D polymer micro-nano material coated by the poly-tannic acid-phosphazene: dissolving Hexachlorocyclotriphosphazene (HCCP) in an organic solvent to obtain a solvent containing Hexachlorocyclotriphosphazene (HCCP); ultrasonic dissolving Tannic Acid (TA) and alkaline substance in organic solvent, dissolving 4' 4-dihydroxy benzene sulfone (BPS) therein, and filtering to remove alkaline substance to obtain mixed solution; adding an organic solvent into MCA, and stirring to obtain a solution group containing MCA (MCA group); adding the mixed solution into the MCA-containing solution group, stirring, dropwise adding a solvent containing Hexachlorocyclotriphosphazene (HCCP), finally adding 27 drops of triethylamine, reacting for 24 hours, and performing suction filtration and freeze drying after the reaction is finished to obtain the 3D polymer micro-nano material coated by the poly-tannic acid-phosphazene;
(3) Preparing a magnetic 3D polymer micro-nano dye adsorbent coated by poly-tannic acid-phosphazene:
placing 2g of the 3D polymer micro-nano material coated by the poly-tannic acid-phosphazene obtained in the step (2) into a 250mL three-necked flask, adding 100mL of water, placing the mixture into a constant-temperature magnetic stirrer, stirring and dispersing, and meanwhile, introducing nitrogen to remove air in the flask;
weighing 0.8g FeCl 3 ·6H 2 O and 0.536g FeCl 2 ·4H 2 O, respectively dissolving the O in 10mL of water to obtain a ferric chloride solution and a ferrous chloride solution; adding a ferrous chloride solution into a ferric chloride solution for mixing, dropwise adding the mixed solution into the solution in the three-neck flask at a constant speed, and stirring for 20min on a constant-temperature magnetic stirrer after dropwise adding;
then heating the solution to 85 ℃, installing a constant pressure funnel, adding 25mL of ammonia water into the funnel, then dropwise adding the ammonia water into the flask at a constant speed, reacting for 1h in a closed environment after dropwise adding, stopping heating, and cooling to room temperature;
and then filtering the solution, washing the filtered substances with 0.1M hydrochloric acid solution and water respectively, and freeze-drying the filtered products to obtain black powdery products, namely the magnetic 3D polymer micro-nano dye adsorbent coated with the poly-tannic acid-phosphazene.
In the step (1), the mass ratio of melamine to cyanuric acid is 1.
The organic solvent in the step (2) is at least one of acetone, 1' 4-dioxane and glycerol; the alkaline substance is one of sodium hydroxide, potassium hydroxide and potassium carbonate; the mass ratio of the tannic acid to the alkaline substance is 1:15; the mass percentages of the tannic acid and the 4,4' -dihydroxy diphenyl sulfone are respectively 30% and 70%; the freeze-drying time was 24 hours.
More preferably, the organic solvent is 1' 4-dioxane; the alkaline substance is potassium carbonate.
The magnetic 3D polymer micro-nano dye adsorbent coated with the poly-tannic acid-phosphazene is prepared according to the preparation method.
The application of the magnetic 3D polymer micro-nano dye adsorbent coated with the polytannic acid-phosphazene in dye adsorption is characterized in that the dye is a cationic dye, particularly, methylene Blue (MB) is preferred, and the adsorbent has an excellent removal rate on the Methylene Blue (MB).
The principle of the invention is as follows:
the invention relates to a novel adsorbing material with high specific surface area, which is constructed by taking a polymer nanoflower (3D structure) with micron scale as a carrier and coating an adsorbing material poly tannic acid-phosphazene thin layer on the surface of the polymer nanoflower in situ by adopting a precipitation polycondensation method. The polymer nanoflower is adsorbed with cationic dye by forming hydrogen bonds, and has high cationic adsorption capacity. The dosage of the adsorbent can be effectively reduced, the adsorption time can be shortened, and the adsorption efficiency can be improved; the chemical property of the nano-material is stable, the nano-material in the water can be efficiently recycled by the magnetic particles coated in the polymer nanoflower while the tannin/BPS is efficiently utilized, the secondary pollution is effectively avoided, and the pollution of the dye wastewater to the environment can be effectively improved.
In the preparation method, MCA is used as an adsorbent carrier, and the surface layer of the polymer nanoflower MCA is directly coated with a polyphosphazene coating layer of BPS/TA/HCCP through in-situ polycondensation reaction to obtain the novel magnetic 3D polymer micro-nano dye adsorbent. The novel magnetic 3D polymer micro-nano dye adsorbent prepared by the invention has larger adsorption capacity to cationic dyes in a shorter time, can effectively reduce the using amount of the adsorbent and shorten the adsorption time, has stable property, and can effectively improve the pollution of cationic dye wastewater to the environment.
Compared with the prior art, the invention has the following advantages and effects:
(1) Compared with the micro-nano adsorbent, the polymer nanoflower (3D structure) with the micron scale is constructed, so that the specific surface area of the adsorbent is greatly increased, the coating is favorably carried out, and the adsorption efficiency is greatly improved.
(2) The raw material tannic acid used in the invention has wide source, low cost and simple and convenient preparation process, and is suitable for industrial production and application.
(3) The 3D polymer micro-nano dye adsorbent provided by the invention has a good removal effect on cationic dyes (especially methylene blue), and is quick in effect and high in adsorption efficiency.
(4) The reaction condition is simple, and the production cost is low;
(5) The magnetic particles adhered by the invention are beneficial to the recovery of the polymer nano material in water body, and the secondary pollution is prevented.
Drawings
Fig. 1 is a SEM image of polymer nanoflower MCA.
FIG. 2 is an SEM image of the polytannic acid-phosphazene coated polymeric nanoflower MCA obtained in example 1 by using 5% by mass of TA and 95% by mass of BPS.
FIG. 3 is an SEM photograph of the polytannic acid-phosphazene coated polymeric nanoflower MCA obtained in example 2 by using 10% by mass TA and 90% by mass BPS.
FIG. 4 is an SEM photograph of the polytannic acid-phosphazene coated polymeric nanoflower MCA obtained in example 3 using 20% by mass TA and 80% by mass BPS.
FIG. 5 is an SEM image of the polytannic acid-phosphazene coated polymer nanoflower MCA obtained in example 4 by 30% by mass TA and 70% by mass BPS.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1 (tannic acid substitution 5% BPS, concentration 0.01 mol/mL)
(1) Preparation of 3D polymer nanomaterials: dissolving 1.9991g of melamine in 80mL of dimethyl sulfoxide to obtain an MA group solution, dissolving 2.0501g of cyanuric acid in 40mL of dimethyl sulfoxide to obtain a CA group solution, dropwise adding the CA group solution into the MA group solution after complete dissolution, magnetically stirring during the period, and reacting for 1h; then, the mixture is filtered by suction, and dimethyl sulfoxide is washed by 1' 4-dioxane to obtain the polymer nanoflower MCA.
(2) Preparing a 3D polymer micro-nano material coated by the poly tannic acid-phosphazene: dissolving HCCP 0.3853g in 40mL of 1' 4-dioxane to obtain a solvent containing HCCP; weighing 0.7875g of 4 '4-dihydroxybenzene sulfone (BPS), 0.0435g of Tannic Acid (TA) and 0.0362g of potassium carbonate, dissolving tannic acid and potassium carbonate in 250mL1' 4-dioxane for 30min by heating and stirring, dissolving BPS in the solution, and filtering to remove the potassium carbonate to obtain a solution containing BPS and TA; and adding MCA into the residual solvent, stirring (the total amount of 1' 4-dioxane in the step is 315.4 mL), finally adding the solution containing BPS and TA, stirring, dropwise adding the solvent containing HCCP, stirring for reaction for 10min, finally adding 27 drops of triethylamine, reacting for 24h, and performing suction filtration, cooling and drying after the reaction is finished to obtain the 3D polymer micro-nano material coated with the poly-tannic acid-phosphazene.
(3) Preparing a magnetic 3D polymer micro-nano dye adsorbent coated by the poly-tannic acid-phosphazene:
adding 2.0010g of the 3D polymer micro-nano material coated by the poly tannic acid-phosphazene obtained in the step (2) into a 250mL three-neck flask, adding 100mL of water, placing the mixture into a constant-temperature magnetic stirrer, stirring and dispersing, and discharging the air in the flask under the condition of introducing nitrogen.
Weigh 0.800g FeCl 3 ·6H 2 O and 0.536g FeCl 2 ·4H 2 O, dissolving them in10mL of water to obtain a ferric chloride solution and a ferrous chloride solution; adding ferrous chloride into ferric chloride, mixing, adding the mixed solution into the three-neck flask solution at a constant speed, and stirring for 20min on a magnetic stirrer after the addition;
then heating the solution to 85 ℃, installing a constant pressure funnel, adding 25mL of ammonia water into the funnel, then dropwise adding the ammonia water into the flask at a constant speed, reacting for 1h in a closed environment after dropwise adding, stopping heating, and cooling to room temperature;
filtering the solution, washing the filtrate with 0.1M HCl and water respectively, and freeze-drying the filtered product to obtain a black powdery product, namely the magnetic 3D polymer micro-nano dye adsorbent coated with the poly-tannic acid-phosphazene.
The obtained 3D polymer micro-nano dye adsorbent has an excellent adsorption effect on cationic dyes (methylene blue), and the clarity can be improved to a certain extent by comparing the front effect with the back effect, so that the light transmittance is enhanced.
Example 2 (tannic acid substitution 10% BPS, concentration 0.01 mol/mL)
(1) Preparation of 3D polymer nanomaterials: dissolving 2.0022g of melamine in 80mL of dimethyl sulfoxide to obtain an MA group solution, dissolving 2.0499g of cyanuric acid in 40mL of dimethyl sulfoxide to obtain a CA group solution, dropwise adding the CA group solution into the MA group solution after complete dissolution, magnetically stirring during the period, and reacting for 1h; and then, performing suction filtration, and washing the dimethyl sulfoxide by using 1' 4-dioxane to obtain the polymer nano flower MCA.
(2) Preparing a 3D polymer micro-nano material coated by the poly tannic acid-phosphazene: dissolving HCCP 0.3865g in 40mL of 1' 4-dioxane to obtain a solvent containing HCCP; weighing 4 '4-dihydroxy benzene sulfone (BPS) 0.7466g, tannic Acid (TA) 0.0845g and potassium carbonate 0.0666g, ultrasonically dissolving in 258.8mL1' 4-dioxane, and filtering to remove the potassium carbonate to obtain a solution containing BPS and TA; and adding MCA into the solution, stirring, dropwise adding the solvent containing HCCP, stirring, reacting for 10min, finally adding 27 drops of triethylamine, reacting for 24h, filtering, cooling and drying after the reaction is finished, and obtaining the 3D polymer micro-nano material coated with the polytannic acid-phosphazene.
(3) Preparing a magnetic 3D polymer micro-nano dye adsorbent coated by the poly-tannic acid-phosphazene:
adding 2.008g of the 3D polymer micro-nano material coated with the poly tannic acid-phosphazene obtained in the step (2) into a 250mL three-neck flask, adding 100mL of water, placing the mixture into a constant-temperature magnetic stirrer, stirring and dispersing, and discharging air in the flask under the condition of introducing nitrogen gas;
weigh 0.801gFeCl 3 ·6H 2 O and 0.537g FeCl 2 ·4H 2 O, respectively dissolving the O in 10mL of water to obtain a ferric chloride solution and a ferrous chloride solution; adding the ferrous chloride solution into the ferric chloride solution for mixing, dropwise adding the mixed solution into the three-neck flask solution at a constant speed, and stirring on a magnetic stirrer for 20min after dropwise adding;
then heating the solution to 85 ℃, installing a constant-pressure funnel, adding 25mL of ammonia water into the funnel, then dropwise adding the ammonia water into the flask at a constant speed, reacting for 1h in a closed environment after dropwise adding, stopping heating, and cooling to room temperature;
filtering the solution, washing the filtrate with 0.1M hydrochloric acid and water respectively, and freeze-drying the filtered product to obtain a black powdery product, namely the magnetic 3D polymer micro-nano dye adsorbent coated with the polytannic acid-phosphazene.
The obtained 3D polymer micro-nano dye adsorbent has an excellent adsorption effect on cationic dyes (methylene blue), and the clarity degree of the adsorbent is improved by nearly 10% compared with that of the adsorbent in example 1.
Example 3 (tannic acid replacement of 20% BPS, concentration 0.01 mol/mL)
(1) Preparation of 3D polymer nanomaterials: dissolving 2.0078g of melamine in dimethyl sulfoxide 80mL to obtain an MA group solution, dissolving 2.0530g of cyanuric acid in dimethyl sulfoxide 40mL to obtain a CA group solution, dropwise adding the CA group solution into the MA group solution after complete dissolution, magnetically stirring during the period, and reacting for 1h. And then filtering, and washing the dimethyl sulfoxide by using 1' 4-dioxane to obtain the polymer nanoflower MCA.
(2) Preparing a 3D polymer micro-nano material coated by the poly tannic acid-phosphazene: dissolving HCCP 0.3838g in 40mL of 1' 4-dioxane to obtain a solvent containing HCCP; weighing 0.6644g of 4 '4-dihydroxy benzene sulfone (BPS), 0.1674g of Tannic Acid (TA) and 0.1347g of potassium carbonate, carrying out ultrasonic treatment on the tannic acid and the potassium carbonate for 30min, dissolving in 200mL1' 4-dioxane, dissolving the BPS in the solution, and filtering to remove the potassium carbonate to obtain a solution containing the BPS and the TA; adding MCA into the rest solvent (total solvent is 265.6 mL) and stirring for dissolving; and then adding a solution containing BPS and TA into the solution, stirring, dropwise adding the solvent containing HCCP, stirring for reacting for 10min, finally adding 27 drops of triethylamine, reacting for 24h, filtering, cooling and drying after the reaction is finished, thus obtaining the 3D polymer micro-nano material coated with the poly-tannic acid-phosphazene.
(3) Preparing a magnetic 3D polymer micro-nano dye adsorbent coated by the poly-tannic acid-phosphazene:
adding 2.007g of the 3D polymer micro-nano material coated by the poly-tannic acid-phosphazene obtained in the step (2) into a 250mL three-neck flask, adding 100mL of water, placing the mixture into a constant-temperature magnetic stirrer, stirring and dispersing, and discharging air in the flask under the condition of introducing nitrogen gas;
weigh 0.802g FeCl 3 ·6H 2 O and 0.538gFeCl 2 ·4H 2 O, respectively dissolving the O in 10mL of water to obtain a ferric chloride solution and a ferrous chloride solution; adding the ferrous chloride solution into the ferric chloride solution for mixing, dropwise adding the mixed solution into the three-neck flask solution at a constant speed, and stirring on a magnetic stirrer for 20min after dropwise adding;
and then heating the solution to 85 ℃, installing a constant-pressure funnel, adding 25mL of ammonia water into the funnel, dropwise adding the ammonia water into the flask at a constant speed, reacting for 1h in a closed environment after dropwise adding, stopping heating, and cooling to room temperature.
Filtering the solution, washing the filtrate with 0.1M HCl and water respectively, and freeze-drying the filtered product to obtain a black powdery product, namely the magnetic 3D polymer micro-nano dye adsorbent coated with the polytannic acid-phosphazene.
The obtained 3D polymer micro-nano dye adsorbent has an excellent adsorption effect on cationic dyes (methylene blue), and compared with example 1, the clarity of the adsorbent is improved again and is close to 50%.
Example 4 (tannic acid substitution 30% BPS, concentration 0.01 mol/mL)
(1) Preparation of 3D polymer nanomaterials: dissolving 2.0015g of melamine in 80mL of dimethyl sulfoxide to obtain an MA group solution, dissolving 2.0506g of cyanuric acid in 40mL of dimethyl sulfoxide to obtain a CA group solution, dropwise adding the CA group solution into the MA group solution after complete dissolution, magnetically stirring during the period, and reacting for 1h. And then filtering, and washing the dimethyl sulfoxide by using 1' 4-dioxane to obtain the polymer nanoflower MCA.
(2) Preparing a 3D polymer micro-nano material coated by the poly-tannic acid-phosphazene: then HCCP 0.3870g was dissolved in 30mL 1' 4-dioxane to give a HCCP-containing solvent; weighing 0.5825g of 4 '4-dihydroxybenzene sulfone (BPS), 0.2475g of Tannic Acid (TA) and 0.2042g of potassium carbonate, dissolving tannic acid and potassium carbonate in 160mL1' 4-dioxane under heating and stirring for 30min, dissolving BPS in the solution, and filtering to remove potassium carbonate to obtain a solution containing BPS and TA; adding MCA into the rest solvent (the total amount of the solvent is 232.4 mL) and stirring for dissolving; and then adding a solution containing BPS and TA into the solution, stirring, dropwise adding the solvent containing HCCP, stirring for reacting for 10min, finally adding 27 drops of triethylamine, reacting for 24h, filtering, cooling and drying after the reaction is finished, thus obtaining the 3D polymer micro-nano material coated with the poly-tannic acid-phosphazene.
(3) Preparing a magnetic 3D polymer micro-nano dye adsorbent coated by poly-tannic acid-phosphazene:
adding 2.009g of the 3D polymer micro-nano material coated by the poly tannin-phosphazene obtained in the step (2) into a 250mL three-neck flask, adding 100mL of water, placing the mixture into a constant-temperature magnetic stirrer, stirring and dispersing, and discharging the air in the flask under the condition of introducing nitrogen gas;
weighing 0.802gFeCl 3 ·6H 2 O and 0.536gFeCl 2 ·4H 2 O, respectively dissolving the materials in 10mL of water to obtain a ferric chloride solution and a ferrous chloride solution; adding the ferrous chloride solution into the ferric chloride solution for mixing, dropwise adding the mixed solution into the three-neck flask solution at a constant speed, and stirring on a magnetic stirrer for 20min after dropwise adding;
then heating the solution to 85 ℃, installing a constant pressure funnel, adding 25mL of ammonia water into the funnel, then dropwise adding the ammonia water into the flask at a constant speed, reacting for 1h in a closed environment after dropwise adding, stopping heating, and cooling to room temperature.
Filtering the solution, washing the filtrate with 0.1M HCl and water respectively, and freeze-drying the filtered product to obtain a black powdery product, namely the magnetic 3D polymer micro-nano dye adsorbent coated with the polytannic acid-phosphazene.
The obtained 3D polymer micro-nano dye adsorbent has excellent adsorption effect on cationic dye (methylene blue), the front and back comparison adsorption effects are the best, the clarity is greatly improved compared with that of example 1, the improvement is nearly 1.5 times, and the light transmittance is nearly improved by 2 times.
The experimental conclusion is that: the tannin-substituted mass ratio of 30% bps in example 4 was most effective, and the adsorption capacity of the polytannin-phosphazene coated polymer nanoflower MCA obtained by 30% ta and 70% bps was the strongest.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (7)

1. A preparation method of a magnetic 3D polymer micro-nano dye adsorbent coated by poly tannic acid-phosphazene is characterized by comprising the following steps:
(1) Preparation of 3D polymer nanomaterials: melamine and cyanuric acid are taken as raw materials, and are respectively added into two groups of dimethyl sulfoxide for ultrasonic dissolution; after the cyanuric acid is completely dissolved, dropwise adding the dimethyl sulfoxide solution of cyanuric acid into the dimethyl sulfoxide solution of melamine, magnetically stirring during the process, reacting for 1h, then performing suction filtration, and washing away the dimethyl sulfoxide by using 1, 4-dioxane to obtain polymer nanoflower MCA;
(2) Preparing a 3D polymer micro-nano material coated by the poly-tannic acid-phosphazene: dissolving hexachlorocyclotriphosphazene in an organic solvent to obtain a solvent containing hexachlorocyclotriphosphazene; ultrasonically dissolving tannic acid and alkaline substances into the organic solvent, dissolving 4,4' -dihydroxydiphenyl sulfone into the organic solvent, and filtering to remove the alkaline substances to obtain a mixed solution; adding MCA into the organic solvent and stirring to obtain a solution group containing MCA; adding the mixed solution into the MCA-containing solution group, stirring, dropwise adding a solvent containing hexachlorocyclotriphosphazene, finally adding 27 drops of triethylamine, reacting for 24 hours, and performing suction filtration, freeze drying after the reaction is finished to obtain the 3D polymer micro-nano material coated with the polytannic acid-phosphazene;
(3) Preparing a magnetic 3D polymer micro-nano dye adsorbent coated by poly-tannic acid-phosphazene:
placing 2g of the 3D polymer micro-nano material coated with the poly-tannic acid-phosphazene obtained in the step (2) into a 250mL three-neck flask, adding 100mL of water, placing the mixture into a constant-temperature magnetic stirrer, stirring and dispersing, and introducing nitrogen to remove air in the flask;
weighing 0.8g FeCl 3 ·6H 2 O and 0.536g FeCl 2 ·4H 2 O, respectively dissolving the O in 10mL of water to obtain a ferric chloride solution and a ferrous chloride solution; adding a ferrous chloride solution into a ferric chloride solution for mixing, dropwise adding the mixed solution into the solution in the three-neck flask at a constant speed, and stirring for 20min on a constant-temperature magnetic stirrer after dropwise adding;
then heating the obtained solution to 85 ℃, installing a constant-pressure funnel, adding 25mL of ammonia water into the funnel, then dropwise adding the ammonia water into the three-neck flask at a constant speed, reacting for 1h in a closed environment after dropwise adding, stopping heating, and cooling to room temperature;
and then filtering the obtained solution, respectively washing the filtered product by using a 0.1M hydrochloric acid solution and water, and freeze-drying the filtered product to obtain a black powdery product, namely the magnetic 3D polymer micro-nano dye adsorbent coated by the poly-tannic acid-phosphazene.
2. The production method according to claim 1, characterized in that: the mass ratio of the melamine to the cyanuric acid in the step (1) is 1.
3. The method of claim 1, wherein: the organic solvent in the step (2) is at least one of acetone, 1, 4-dioxane and glycerol; the alkaline substance is one of sodium hydroxide, potassium hydroxide and potassium carbonate; the mass ratio of the tannic acid to the alkaline substance is 1:15; the mass ratio of the tannic acid to the 4,4' -dihydroxydiphenyl sulfone is 3; the freeze drying time in the step (2) is 24 hours.
4. The production method according to claim 3, characterized in that: the organic solvent is 1, 4-dioxane; the alkaline substance is potassium carbonate.
5. The magnetic 3D polymer micro-nano dye adsorbent coated with the poly-tannic acid-phosphazene prepared by the preparation method of claim 1.
6. The application of the magnetic 3D polymer micro-nano dye adsorbent coated with the polytannic acid-phosphazene according to claim 5 in dye adsorption.
7. Use according to claim 6, characterized in that: the dye is methylene blue.
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