CN111760560A - Polyacrylic acid-beta-cyclodextrin composite hydrogel magnetic adsorption material and preparation method thereof - Google Patents

Polyacrylic acid-beta-cyclodextrin composite hydrogel magnetic adsorption material and preparation method thereof Download PDF

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CN111760560A
CN111760560A CN202010651302.0A CN202010651302A CN111760560A CN 111760560 A CN111760560 A CN 111760560A CN 202010651302 A CN202010651302 A CN 202010651302A CN 111760560 A CN111760560 A CN 111760560A
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李金妹
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Abstract

The invention relates to the field of adsorption materials, and discloses a polyacrylic acid- β -cyclodextrin composite hydrogel magnetic adsorption material, petal-shaped nano Fe3O4Has super high specific surface area and excellent magnetism, and a great amount of hydroxyl on the surface reacts with 3-aminopropyl triethoxysilane to obtain amino nano Fe with high grafting rate3O4With-bromoisobutyrylamide nano-Fe3O4As a macroinitiator, acrylic acid and maleic anhydride are initiated in petal-shaped nano Fe through a single electron transfer living radical polymerization method3O4Surface in-situ polymerization, and carrying out ring-opening reaction on maleic anhydride and β -cyclodextrin to obtain nano Fe3O4Grafted polyacrylic acid- β -cyclodextrin composite hydrogel, nano Fe3O4Chemical covalent bond is tightly connected in the group of hydrogel, so that nano Fe is reduced3O4The phenomenon of magnetic attraction agglomeration among particles is avoided, and the nano Fe is avoided3O4The phase separation is carried out with the hydrogel matrix, and the excellent magnetic adsorption and magnetic recovery performances are endowed to the hydrogel material.

Description

Polyacrylic acid-beta-cyclodextrin composite hydrogel magnetic adsorption material and preparation method thereof
Technical Field
The invention relates to the field of adsorption materials, in particular to a polyacrylic acid-beta-cyclodextrin composite hydrogel magnetic adsorption material and a preparation method thereof.
Background
The water pollution problem in China is very serious, the current treatment method for pollutants mainly comprises the current heavy metal wastewater treatment methods such as a chemical precipitation method, an ion exchange method, a membrane separation method, a biological method, an adsorption method and the like, wherein the adsorption method has the advantages of being simple in operation, low in raw materials, large in adsorption capacity and the like, and the adsorption materials can be divided into inorganic material adsorbents, organic material adsorbents and organic-inorganic composite adsorption materials such as activated carbon, carbon molecular sieves, acrylamide and the like, wherein the organic-inorganic composite adsorption materials have the best adsorption performance.
The acrylic hydrogel is a three-dimensional network structure gel, has excellent hydrophilicity and water absorbability, can endow the hydrogel material with rich functional groups such as carboxyl, amino, hydroxyl and the like through reasonable network structure design and monomer selection, and can not only treat Cu2+，Cd2+、Cr3+The method is characterized in that heavy metal ions are subjected to complexation adsorption, organic dye pollutants such as methylene blue and the like can be adsorbed, but the traditional acrylic hydrogel is limited in adsorption capacity and low in adsorption efficiency, a hydrogel material and magnetic substances such as ferroferric oxide can be compounded to obtain an organic-inorganic composite adsorption material with complexation, magnetic adsorption performance and magnetic recovery performance, but at present, the hydrogel material and the magnetic substances such as ferroferric oxide are generally subjected to physical mixing, so that the hydrogel matrix and the ferroferric oxide are not tightly combined, the ferroferric oxide falls off and is separated, the magnetic performance of the composite adsorption material is reduced, and pollution is caused.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a polyacrylic acid-beta-cyclodextrin composite hydrogel magnetic adsorption material and a preparation method thereof, which solve the problem of limited adsorption performance of acrylic hydrogel and solve the problem that an acrylic hydrogel matrix and ferroferric oxide are easy to fall off and separate.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a polyacrylic acid-beta-cyclodextrin composite hydrogel magnetic adsorption material is prepared by the following steps:
(1) adding a glycol solvent, ferric chloride, urea and tetrabutylammonium bromide into a reaction bottle, uniformly stirring, placing the mixture into an oil bath reaction kettle, heating the mixture to 180 ℃ plus one temperature of 200 ℃, uniformly stirring and refluxing the mixture for reaction for 30-60min, centrifugally separating, washing and drying the mixture by using ethanol, placing the obtained solid precursor product into an atmosphere furnace, heating the product to 450 ℃ plus one temperature of 500 ℃, and carrying out heat preservation and calcination for 2-3h to prepare petal-shaped nano Fe3O4。
(2) Adding a mixed solvent of distilled water and ethanol with the volume ratio of 10:40-60 into a reaction bottle, and adding petal-shaped nano Fe3O4Performing ultrasonic dispersion treatment, adding 3-aminopropyltriethoxysilane, heating to 70-90 deg.C, stirring at uniform speed, refluxing for 2-5 hr, centrifuging with ethanol, washing, and drying to obtain amino nanometer Fe3O4。
(3) Under the nitrogen atmosphere, adding a toluene solvent and amino petal-shaped nano Fe into a reaction bottle3O4Performing ultrasonic dispersion treatment, slowly adding pyridine and 2-bromine isobutyryl bromide into ice water bath, stirring at constant speed for reaction for 2-5h, heating to 30-50 ℃, stirring at constant speed for reaction for 12-24h, centrifugally separating with toluene, washing and drying to obtain 2-bromine isobutyrylamide nano Fe3O4。
(4) Adding distilled water solvent and 2-bromoisobutyramide nano Fe into a reaction bottle in the nitrogen atmosphere3O4Performing ultrasonic dispersion treatment, adding acrylic acid, maleic anhydride, β -cyclodextrin, N-methylene bisacrylamide and 2, 2' bipyridyl, uniformly stirring, rapidly freezing by liquid nitrogen, adding cuprous chloride and copper chloride, thawing at room temperature in nitrogen atmosphere, heating to 40-80 ℃, uniformly stirring for reaction for 2-6h, centrifugally separating by using distilled water, washing and drying to prepare the polyacrylic acid- β -cyclodextrin complexAnd (3) synthesizing the hydrogel magnetic adsorption material.
Preferably, the oil bath reaction pot in the step (1) comprises a magnetic heating stirring device, a heating ring is arranged above the magnetic heating stirring device, a clamping groove is fixedly connected with the clamping ring, a clamping block is movably connected inside the clamping groove, an oil bath pot is fixedly connected with the clamping block, and a reaction bottle is arranged inside the oil bath pot.
Preferably, the mass ratio of the ferric chloride to the urea to the tetrabutylammonium bromide in the step (1) is 1:10-20: 4.5-5.5.
Preferably, the petal-shaped nano Fe in the step (2)3O4And 3-aminopropyltriethoxysilane at a mass ratio of 100: 30-60.
Preferably, the amino petal-shaped nano Fe in the step (3)3O4The mass ratio of the pyridine to the 2-bromine isobutyryl bromide is 10:100-200: 20-30.
Preferably, the 2-bromoisobutyramidine nano Fe in the step (4)3O4Acrylic acid, maleic anhydride, β -cyclodextrin, N-methylene bisacrylamide, 2' bipyridyl, cuprous chloride and copper chloride in a mass ratio of 20-40:100:10-20:4-8:0.5-1:25-35:5-10: 1-2.
(III) advantageous technical effects
Compared with the prior art, the invention has the following experimental principles and beneficial technical effects:
the polyacrylic acid- β -cyclodextrin composite hydrogel magnetic adsorption material is petal-shaped nano Fe obtained by a hot solvent method3O4Compared with common nano Fe3O4The magnetic material has ultrahigh specific surface area and more excellent magnetism, and in the hydrothermal process, urea is hydrolyzed to generate rich hydroxyl groups so that petal-shaped nano Fe3O4A large amount of hydroxyl is formed on the surface, and the reaction of the large amount of hydroxyl and 3-aminopropyl triethoxysilane is further accelerated to obtain the amino nano Fe with high grafting rate3O4Under the action of pyridine, amino reacts with acyl bromide group of 2-bromine isobutyryl bromide to obtain 2-bromine isobutyryl amidation nanometer Fe3O4By which it is madeIs a macromolecular initiator, bromine atom is used as a single electron transfer active site, and acrylic acid and maleic anhydride are initiated in petal-shaped nano Fe through a single electron transfer active free radical polymerization method3O4Surface in-situ polymerization, simultaneously carrying out ring-opening reaction on maleic anhydride and β -cyclodextrin, and then obtaining nano Fe through the crosslinking action of N, N-methylene-bisacrylamide3O4Grafted polyacrylic acid- β -cyclodextrin composite hydrogel.
The polyacrylic acid- β -cyclodextrin composite hydrogel magnetic adsorption material is petal-shaped nano Fe3O4Chemical covalent bonds are tightly connected in the groups of the hydrogel, and not only is the nano Fe reduced under the bridging action of the chemical covalent bonds3O4The phenomenon of magnetic attraction agglomeration among particles is avoided, and the nano Fe is also avoided3O4The nano Fe is separated from the hydrogel matrix3O4The polyacrylic acid- β -cyclodextrin is uniformly dispersed in a hydrogel matrix, so that the hydrogel material has excellent magnetic adsorption and magnetic recovery performances, contains rich carboxyl and hydroxyl, and can be used for treating Cd2+The heavy metal ions and the methylene blue and other ionic dyes have the adsorption effect, and the excellent sewage treatment effect is achieved.
Drawings
FIG. 1 is a schematic front view of a magnetically heated stirring apparatus;
FIG. 2 is an enlarged schematic view of the oil bath pan;
FIG. 3 is a schematic top view of the oil bath pan;
FIG. 4 is a schematic top view of a fixture block;
fig. 5 is a schematic top view of a card slot.
1-magnetic heating stirring device; 2-heating a ring; 3-a snap ring; 4-a card slot; 5-clamping blocks; 6-oil bath pan; 7-reaction flask.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: a polyacrylic acid-beta-cyclodextrin composite hydrogel magnetic adsorption material is prepared by the following steps:
(1) adding into a reaction flaskUniformly stirring ethylene glycol solvent, ferric chloride, urea and tetrabutylammonium bromide in a mass ratio of 1:10-20:4.5-5.5, placing the mixture into an oil bath reaction pot, wherein the oil bath reaction pot comprises a magnetic heating stirring device, a heating ring is arranged above the magnetic heating stirring device, a clamping ring is arranged above the magnetic heating stirring device, the clamping ring is fixedly connected with a clamping groove, a clamping block is movably connected inside the clamping groove, the clamping block is fixedly connected with an oil bath pot, a reaction bottle is arranged inside the oil bath pot, heating is carried out to 180-degree heat-storage-type 200 ℃, carrying out uniform stirring reflux reaction for 30-60min, carrying out centrifugal separation, washing and drying by using ethanol, placing the obtained solid precursor product into an atmosphere furnace, heating to 450-degree heat-storage-type 500 ℃, carrying out heat preservation and calcining for 2-3h3O4。
(2) Adding a mixed solvent of distilled water and ethanol with the volume ratio of 10:40-60 into a reaction bottle, and adding petal-shaped nano Fe3O4Performing ultrasonic dispersion treatment, adding 3-aminopropyltriethoxysilane at a mass ratio of 100:30-60, heating to 70-90 deg.C, stirring at constant speed, refluxing for 2-5h, centrifuging with ethanol, washing, and drying to obtain amino nanometer Fe3O4。
(3) Under the nitrogen atmosphere, adding a toluene solvent and amino petal-shaped nano Fe into a reaction bottle3O4Performing ultrasonic dispersion treatment, slowly adding pyridine and 2-bromoisobutyryl bromide into ice water bath according to the mass ratio of 10:100-3O4。
(4) Adding distilled water solvent and 2-bromoisobutyramide nano Fe into a reaction bottle in the nitrogen atmosphere3O4Performing ultrasonic dispersion treatment, adding acrylic acid, maleic anhydride, β -cyclodextrin, N-methylene bisacrylamide and 2, 2' bipyridyl, uniformly stirring, rapidly freezing by liquid nitrogen, adding cuprous chloride and copper chloride, and controlling 2-bromoisobutyrylamide nano Fe3O4Acrylic acid, maleic anhydride, β -cyclodextrin, N-methylene-bisacrylamide, 2' -bipyridineAnd the mass ratio of the cuprous chloride to the copper chloride is 20-40:100:10-20:4-8:0.5-1:25-35:5-10:1-2, then unfreezing at room temperature in the nitrogen atmosphere, finally heating to 40-80 ℃, stirring at a constant speed for reaction for 2-6h, centrifugally separating by using distilled water, washing and drying to prepare the polyacrylic acid- β -cyclodextrin composite hydrogel magnetic adsorbing material.
Example 1
(1) Adding ethylene glycol solvent, ferric chloride, urea and tetrabutylammonium bromide with the mass ratio of 1:10:4.5 into a reaction bottle, uniformly stirring, placing the mixture into an oil bath reaction pot, wherein the oil bath reaction pot comprises a magnetic heating stirring device, a heating ring is arranged above the magnetic heating stirring device, a clamping ring is arranged above the magnetic heating stirring device, the clamping ring is fixedly connected with a clamping groove, a clamping block is movably connected inside the clamping groove, the clamping block is fixedly connected with an oil bath pot, the reaction bottle is arranged inside the oil bath pot, heating is carried out to 180 ℃, stirring at constant speed is carried out for reflux reaction for 30min, carrying out centrifugal separation by using ethanol, washing and drying, placing the obtained solid precursor product into an atmosphere furnace, heating to 450 ℃, carrying out heat preservation and calcination for 2h, and preparing the petal-shaped3O4。
(2) Adding a mixed solvent of distilled water and ethanol with the volume ratio of 10:40 into a reaction bottle, and adding petal-shaped nano Fe3O4Performing ultrasonic dispersion treatment, adding 3-aminopropyltriethoxysilane at a mass ratio of 100:30, heating to 70 deg.C, stirring at uniform speed, refluxing for 2h, centrifuging with ethanol, washing, and drying to obtain amino nanometer Fe3O4。
(3) Under the nitrogen atmosphere, adding a toluene solvent and amino petal-shaped nano Fe into a reaction bottle3O4Performing ultrasonic dispersion treatment, slowly adding pyridine and 2-bromoisobutyryl bromide in an ice water bath at a mass ratio of 10:100:20, stirring at a constant speed for reaction for 2h, heating to 30 ℃, stirring at a constant speed for reaction for 12h, centrifugally separating by using toluene, washing and drying to obtain 2-bromoisobutyrylamide nano Fe3O4。
(4) Adding distilled water solvent and 2-bromoisobutyramide nano Fe into a reaction bottle in the nitrogen atmosphere3O4Performing ultrasonic dispersion treatment, adding acrylic acid, maleic anhydride, β -cyclodextrin, N-methylene bisacrylamide and 2, 2' bipyridyl, uniformly stirring, rapidly freezing by liquid nitrogen, adding cuprous chloride and copper chloride, and controlling 2-bromoisobutyrylamide nano Fe3O4The polyacrylic acid- β -cyclodextrin composite hydrogel magnetic adsorbing material 1 is prepared by the following steps of thawing acrylic acid, maleic anhydride, β -cyclodextrin, N-methylenebisacrylamide, 2' -bipyridine, cuprous chloride and copper chloride at room temperature in a nitrogen atmosphere at a mass ratio of 20:100:10:4:0.5:25:5:1, heating to 40 ℃, uniformly stirring for reaction for 2 hours, centrifugally separating by using distilled water, washing and drying.
Example 2
(1) Adding ethylene glycol solvent, ferric chloride, urea and tetrabutylammonium bromide with the mass ratio of 1:14:4.8 into a reaction bottle, uniformly stirring, placing the mixture into an oil bath reaction pot, wherein the oil bath reaction pot comprises a magnetic heating stirring device, a heating ring is arranged above the magnetic heating stirring device, a clamping ring is arranged above the magnetic heating stirring device, the clamping ring is fixedly connected with a clamping groove, a clamping block is movably connected inside the clamping groove, the clamping block is fixedly connected with an oil bath pot, the reaction bottle is arranged inside the oil bath pot, heating is carried out to 190 ℃, stirring at constant speed is carried out for reflux reaction for 60min, carrying out centrifugal separation by using ethanol, washing and drying, placing the obtained solid precursor product into an atmosphere furnace, heating to 500 ℃, carrying out heat preservation and calcination for 2h, and preparing the petal-shaped3O4。
(2) Adding a mixed solvent of distilled water and ethanol with the volume ratio of 10:45 into a reaction bottle, and adding petal-shaped nano Fe3O4Performing ultrasonic dispersion treatment, adding 3-aminopropyltriethoxysilane at a mass ratio of 100:40, heating to 90 deg.C, stirring at constant speed, refluxing for 2h, centrifuging with ethanol, washing, and drying to obtain amino nanometer Fe3O4。
(3) Under the nitrogen atmosphere, adding a toluene solvent and amino petal-shaped nano Fe into a reaction bottle3O4Performing ultrasonic dispersion treatment, slowly adding pyridine and 2-bromine isobutyryl bromide in an ice water bath according to the mass ratio of the pyridine to the 2-bromine isobutyryl bromide10:140:23, heating to 50 ℃, stirring at constant speed for reaction for 3h, heating to 50 ℃, stirring at constant speed for reaction for 24h, centrifugally separating by using toluene, washing and drying to prepare the 2-bromoisobutyrylamide nano Fe3O4。
(4) Adding distilled water solvent and 2-bromoisobutyramide nano Fe into a reaction bottle in the nitrogen atmosphere3O4Performing ultrasonic dispersion treatment, adding acrylic acid, maleic anhydride, β -cyclodextrin, N-methylene bisacrylamide and 2, 2' bipyridyl, uniformly stirring, rapidly freezing by liquid nitrogen, adding cuprous chloride and copper chloride, and controlling 2-bromoisobutyrylamide nano Fe3O4The polyacrylic acid- β -cyclodextrin composite hydrogel magnetic adsorption material 2 is prepared by the following steps of thawing acrylic acid, maleic anhydride, β -cyclodextrin, N-methylene bisacrylamide, 2' bipyridyl, cuprous chloride and copper chloride at the mass ratio of 25:100:13:5:0.6:28:6:1.4 at room temperature in a nitrogen atmosphere, heating to 80 ℃, stirring at a constant speed for reaction for 2 hours, centrifugally separating with distilled water, washing and drying.
Example 3
(1) Adding ethylene glycol solvent, ferric chloride, urea and tetrabutylammonium bromide with the mass ratio of 1:16:5.1 into a reaction bottle, uniformly stirring, placing the mixture into an oil bath reaction pot, wherein the oil bath reaction pot comprises a magnetic heating stirring device, a heating ring is arranged above the magnetic heating stirring device, a clamping ring is arranged above the magnetic heating stirring device, the clamping ring is fixedly connected with a clamping groove, a clamping block is movably connected inside the clamping groove, the clamping block is fixedly connected with an oil bath pot, the reaction bottle is arranged inside the oil bath pot, heating is carried out to 200 ℃, stirring at constant speed is carried out for reflux reaction for 60min, carrying out centrifugal separation by using ethanol, washing and drying, placing the obtained solid precursor product into an atmosphere furnace, heating to 500 ℃, carrying out heat preservation and calcination for 2h, and preparing the petal-shaped3O4。
(2) Adding a mixed solvent of distilled water and ethanol with the volume ratio of 10:52 into a reaction bottle, and adding petal-shaped nano Fe3O4Performing ultrasonic dispersion treatment, adding 3-aminopropyltriethoxysilane at a mass ratio of 100:50, heating to 80 deg.C, stirring at constant speed, refluxing for 4 hr, and reacting with ethylAlcohol centrifugal separation, washing and drying are carried out to prepare amino nano Fe3O4。
(3) Under the nitrogen atmosphere, adding a toluene solvent and amino petal-shaped nano Fe into a reaction bottle3O4Performing ultrasonic dispersion treatment, slowly adding pyridine and 2-bromoisobutyryl bromide in an ice water bath at a mass ratio of 10:160:27, stirring at a constant speed for reaction for 4 hours, heating to 40 ℃, stirring at a constant speed for reaction for 18 hours, centrifugally separating by using toluene, washing and drying to prepare the 2-bromoisobutyrylamide nano Fe3O4。
(4) Adding distilled water solvent and 2-bromoisobutyramide nano Fe into a reaction bottle in the nitrogen atmosphere3O4Performing ultrasonic dispersion treatment, adding acrylic acid, maleic anhydride, β -cyclodextrin, N-methylene bisacrylamide and 2, 2' bipyridyl, uniformly stirring, rapidly freezing by liquid nitrogen, adding cuprous chloride and copper chloride, and controlling 2-bromoisobutyrylamide nano Fe3O4The polyacrylic acid- β -cyclodextrin composite hydrogel magnetic adsorption material 3 is prepared by the following steps of thawing acrylic acid, maleic anhydride, β -cyclodextrin, N-methylene bisacrylamide, 2' bipyridine, cuprous chloride and copper chloride at the mass ratio of 35:100:18:7:0.8:32:8:1.7 at room temperature in a nitrogen atmosphere, heating to 60 ℃, uniformly stirring for reacting for 4 hours, centrifugally separating by using distilled water, washing and drying.
Example 4
(1) Adding ethylene glycol solvent, ferric chloride, urea and tetrabutylammonium bromide with the mass ratio of 1:20:5.5 into a reaction bottle, uniformly stirring, placing the mixture into an oil bath reaction pot, wherein the oil bath reaction pot comprises a magnetic heating stirring device, a heating ring is arranged above the magnetic heating stirring device, a clamping ring is arranged above the magnetic heating stirring device, the clamping ring is fixedly connected with a clamping groove, a clamping block is movably connected inside the clamping groove, the clamping block is fixedly connected with an oil bath pot, the reaction bottle is arranged inside the oil bath pot, heating is carried out to 200 ℃, stirring at constant speed and carrying out reflux reaction for 60min, centrifugally separating, washing and drying by using ethanol, placing the obtained solid precursor product into an atmosphere furnace, heating to 500 ℃, carrying out heat preservation and calcination for 3h, and preparing the petal-shaped nano Fe3O4。
(2) Adding a mixed solvent of distilled water and ethanol with the volume ratio of 10:60 into a reaction bottle, and adding petal-shaped nano Fe3O4Performing ultrasonic dispersion treatment, adding 3-aminopropyltriethoxysilane at a mass ratio of 100:60, heating to 90 deg.C, stirring at constant speed, refluxing for 5h, centrifuging with ethanol, washing, and drying to obtain amino nanometer Fe3O4。
(3) Under the nitrogen atmosphere, adding a toluene solvent and amino petal-shaped nano Fe into a reaction bottle3O4Performing ultrasonic dispersion treatment, slowly adding pyridine and 2-bromoisobutyryl bromide into an ice water bath at a mass ratio of 10:200:30, stirring at a constant speed for reaction for 5 hours, heating to 50 ℃, stirring at a constant speed for reaction for 24 hours, centrifugally separating by using toluene, washing and drying to obtain the 2-bromoisobutyrylamide nano Fe3O4。
(4) Adding distilled water solvent and 2-bromoisobutyramide nano Fe into a reaction bottle in the nitrogen atmosphere3O4Performing ultrasonic dispersion treatment, adding acrylic acid, maleic anhydride, β -cyclodextrin, N-methylene bisacrylamide and 2, 2' bipyridyl, uniformly stirring, rapidly freezing by liquid nitrogen, adding cuprous chloride and copper chloride, and controlling 2-bromoisobutyrylamide nano Fe3O4The polyacrylic acid- β -cyclodextrin composite hydrogel magnetic adsorbing material 4 is prepared by the following steps of thawing acrylic acid, maleic anhydride, β -cyclodextrin, N-methylene bisacrylamide, 2' bipyridyl, cuprous chloride and copper chloride at room temperature in a nitrogen atmosphere at a mass ratio of 40:100:20:8:1:35:10:2, heating to 80 ℃, stirring at a constant speed for reaction for 6 hours, and performing centrifugal separation, washing and drying by using distilled water.
Comparative example 1
(1) Adding ethylene glycol solvent, ferric chloride, urea and tetrabutylammonium bromide in a mass ratio of 1:8:4 into a reaction bottle, uniformly stirring, and placing into an oil bath reaction pot, wherein the oil bath reaction pot comprises a magnetic heating stirring device, a heating ring is arranged above the magnetic heating stirring device, a clamping ring is arranged above the magnetic heating stirring device, and the clamping ring is fixedly connected with the magnetic heating stirring deviceClamping grooves, clamping blocks are movably connected inside the clamping grooves, the clamping blocks are fixedly connected with an oil bath pot, a reaction bottle is arranged inside the oil bath pot, the oil bath pot is heated to 200 ℃, stirred at a constant speed and subjected to reflux reaction for 60min, ethanol is used for centrifugal separation, washing and drying, the obtained solid precursor product is placed in an atmosphere furnace, the temperature is raised to 450 ℃, heat preservation and calcination are carried out for 3h, and the petal-shaped nano Fe is prepared3O4。
(2) Adding a mixed solvent of distilled water and ethanol with the volume ratio of 10:30 into a reaction bottle, and adding petal-shaped nano Fe3O4Performing ultrasonic dispersion treatment, adding 3-aminopropyltriethoxysilane at a mass ratio of 100:30, heating to 90 deg.C, stirring at constant speed, refluxing for 5h, centrifuging with ethanol, washing, and drying to obtain amino nanometer Fe3O4。
(3) Under the nitrogen atmosphere, adding a toluene solvent and amino petal-shaped nano Fe into a reaction bottle3O4Performing ultrasonic dispersion treatment, slowly adding pyridine and 2-bromoisobutyryl bromide into an ice water bath at a mass ratio of 10:80:15, stirring at a constant speed for reaction for 5 hours, heating to 40 ℃, stirring at a constant speed for reaction for 24 hours, centrifugally separating by using toluene, washing and drying to obtain 2-bromoisobutyrylamide nano Fe3O4。
(4) Adding distilled water solvent and 2-bromoisobutyramide nano Fe into a reaction bottle in the nitrogen atmosphere3O4Performing ultrasonic dispersion treatment, adding acrylic acid, maleic anhydride, β -cyclodextrin, N-methylene bisacrylamide and 2, 2' bipyridyl, uniformly stirring, rapidly freezing by liquid nitrogen, adding cuprous chloride and copper chloride, and controlling 2-bromoisobutyrylamide nano Fe3O4The polyacrylic acid- β -cyclodextrin composite hydrogel magnetic adsorption material is prepared by the following steps of thawing acrylic acid, maleic anhydride, β -cyclodextrin, N-methylene bisacrylamide, 2' bipyridine, cuprous chloride and copper chloride at the mass ratio of 15:100:8:3:0.4:22:4:0.6 at room temperature in a nitrogen atmosphere, heating to 80 ℃, uniformly stirring for reacting for 6 hours, centrifugally separating by using distilled water, washing and drying, and then the polyacrylic acid- β -cyclodextrin composite hydrogel magnetic adsorption material is obtained by comparison 1.
Respectively have mass fractions of0.5 percent of cadmium nitrate solution is added with polyacrylic acid- β -cyclodextrin composite hydrogel magnetic adsorbing material in the examples and the comparative examples, the mass fraction is 2 percent, the pH value of the solution is adjusted to 3, and a 00S double-beam ultraviolet-visible spectrophotometer is used for detecting Cr6+Residual concentration and adsorption rate, and the test standard is GB/T10533-.
Figure BDA0002575074820000101

Claims (6)

1. A polyacrylic acid-beta-cyclodextrin composite hydrogel magnetic adsorption material is characterized in that: the preparation method of the polyacrylic acid-beta-cyclodextrin composite hydrogel magnetic adsorption material comprises the following steps:
(1) adding ferric chloride, urea and tetrabutylammonium bromide into an ethylene glycol solvent, placing the mixture into an oil bath reaction kettle, heating the mixture to the temperature of 180 ℃ plus one year of 200 ℃, carrying out reflux reaction for 30-60min, carrying out centrifugal separation, washing and drying, placing a solid precursor product into an atmosphere furnace, heating the product to the temperature of 450 ℃ plus one year of 500 ℃, carrying out heat preservation and calcination for 2-3h, and preparing the petal-shaped nano Fe3O4；
(2) Adding petal-shaped nano Fe into a mixed solvent of distilled water and ethanol with the volume ratio of 10:40-603O4Performing ultrasonic dispersion treatment, adding 3-aminopropyltriethoxysilane, heating to 70-90 deg.C, reflux reacting for 2-5h, centrifuging, washing and drying to obtain amino nanometer Fe3O4；
(3) Adding amino petal-shaped nano Fe into a toluene solvent in a nitrogen atmosphere3O4Performing ultrasonic dispersion treatment, slowly adding pyridine and 2-bromoisobutyryl bromide into ice water bath, stirring for reaction for 2-5h, heating to 30-50 ℃, stirring for reaction for 12-24h, centrifugally separating, washing and drying to obtain 2-bromoisobutyrylamide nano Fe3O4；
(4) Adding 2-bromoisobutyrylamide nano Fe into distilled water solvent under the atmosphere of nitrogen3O4Ultrasonic dispersing treatment is carried out, and then acrylic acid, maleic anhydride, β -cyclodextrin, N-methylene-bisacrylamide anduniformly stirring an activator 2, 2' bipyridyl, rapidly freezing the bipyridyl by liquid nitrogen, adding a catalyst cuprous chloride and a cocatalyst cupric chloride, unfreezing the cuprous chloride and the cocatalyst cupric chloride at room temperature in a nitrogen atmosphere, finally heating the cuprous chloride and the cocatalyst copper chloride to 40-80 ℃, stirring the mixture for reaction for 2-6 hours, and performing centrifugal separation, washing and drying to prepare the polyacrylic acid- β -cyclodextrin composite hydrogel magnetic adsorbing material.
2. The polyacrylic acid-beta-cyclodextrin composite hydrogel magnetic adsorption material according to claim 1, characterized in that: the oil bath reaction pot in the step (1) comprises a magnetic heating stirring device, a heating ring is arranged above the magnetic heating stirring device, a clamping groove is fixedly connected with the clamping ring, a clamping block is movably connected inside the clamping groove, the clamping block is fixedly connected with the oil bath pot, and a reaction bottle is arranged inside the oil bath pot.
3. The polyacrylic acid-beta-cyclodextrin composite hydrogel magnetic adsorption material according to claim 1, characterized in that: the mass ratio of the ferric chloride to the urea to the tetrabutylammonium bromide in the step (1) is 1:10-20: 4.5-5.5.
4. The polyacrylic acid- β -cyclodextrin composite hydrogel magnetic adsorption material of claim 1, wherein the petal-shaped nano Fe in step (2)3O4And 3-aminopropyltriethoxysilane at a mass ratio of 100: 30-60.
5. The polyacrylic acid- β -cyclodextrin composite hydrogel magnetic adsorption material of claim 1, wherein the amino petal-shaped nano Fe in step (3)3O4The mass ratio of the pyridine to the 2-bromine isobutyryl bromide is 10:100-200: 20-30.
6. The polyacrylic acid- β -cyclodextrin composite hydrogel magnetic adsorption material as claimed in claim 1, wherein the 2-bromoisobutyramide nano Fe in step (4)3O4C, CThe mass ratio of the olefine acid to the maleic anhydride to the β -cyclodextrin to the N, N-methylene-bisacrylamide to the 2, 2' -bipyridine to the cuprous chloride to the cupric chloride is 20-40:100:10-20:4-8:0.5-1:25-35:5-10: 1-2.
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