CN111495336A - Chitosan-acrylic acid-based magnetic hydrogel adsorption material and preparation method thereof - Google Patents

Chitosan-acrylic acid-based magnetic hydrogel adsorption material and preparation method thereof Download PDF

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CN111495336A
CN111495336A CN202010394618.6A CN202010394618A CN111495336A CN 111495336 A CN111495336 A CN 111495336A CN 202010394618 A CN202010394618 A CN 202010394618A CN 111495336 A CN111495336 A CN 111495336A
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易少华
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Abstract

The invention relates toThe technical field of hydrogel adsorption materials, and discloses a chitosan-acrylic acid based magnetic hydrogel adsorption material, which comprises the following formula raw materials and components: nano Fe3O4Grafted chitosan, a cross-linking agent, an initiator, acrylamide, acrylic acid and NN-methylene bisacrylamide. The chitosan-acrylic acid based magnetic hydrogel adsorbing material is porous nano Fe3O4The surface area is large, the modification with oleic acid is easy to carry out, and the carboxylated nano Fe is obtained by the oxidation of sodium periodate3O4Reacting with thionyl chloride and chitosan in sequence, and combining the nano Fe through chemical covalent bonds3O4Successfully grafting chitosan and glutaraldehyde as a cross-linking agent to obtain nano Fe3O4The method of grafting alkenyl chitosan and crosslinking chitosan-acrylic acid based magnetic hydrogel adsorption material through chemical bonds improves the nanometer Fe3O4The compatibility with the acrylic acid-based hydrogel endows the material with excellent magnetic adsorption capacity.

Description

Chitosan-acrylic acid-based magnetic hydrogel adsorption material and preparation method thereof
Technical Field
The invention relates to the technical field of hydrogel adsorption materials, in particular to a chitosan-acrylic acid-based magnetic hydrogel adsorption material and a preparation method thereof.
Background
The water pollution caused by the reduction of the use value of water due to the pollution of the water environment by chemical harmful substances is reduced, and the pollutants mainly comprise heavy metal ions such as acid, alkali, copper, cadmium and the like and inorganic pollutants such as compounds of the heavy metal ions; and organic pollutants such as phenol, dichloroethane, methylene blue and the like, when the content of the pollutants in the water body is too high, the quality of a drinking water source can be directly influenced, when microorganisms decompose organic matters in the sewage, dissolved oxygen in the water can be consumed, the life of aquatic organisms is influenced, and after the dissolved oxygen is exhausted, the organic matters are subjected to anaerobic decomposition to generate hydrogen sulfide and mercaptan toxic gases, so that the water quality is further deteriorated.
The existing methods for treating sewage and water pollution mainly comprise a chemical precipitation method, a redox method, a material adsorption method and the like, the hydrogel has a three-dimensional network gel structure with strong hydrophilicity, can rapidly swell in water and can keep a large volume of water in a swelling state without dissolving, and the acrylic acid-based hydrogel contains a large amount of functional groups such as amino, carboxyl, amide and the like, and can be matched with Cu2+、Cd2+The method comprises the steps of performing coordination and complexation reaction on heavy metal ions, adsorbing the heavy metal ions, having good adsorption effect on cationic dyes such as methylene blue and the like, and playing a role in purifying sewage, adding magnetic substances such as ferroferric oxide and magnetic nano-iron into a hydrogel material to enhance the magnetic adsorption capacity of the hydrogel material, and recovering the hydrogel adsorption material through an external magnetic field, but most of the existing magnetic hydrogel materials are prepared by mechanically blending the magnetic substances such as ferroferric oxide and the like with the hydrogel material and physically mixing the magnetic substances with the hydrogel material, so that the compatibility between the ferroferric oxide and the hydrogel material is poor, the combination is not tight, and when the hydrogel material is adsorbed in the sewage, the two substances are easy to phase separate, the magnetic adsorption capacity of the hydrogel material is reduced, and the adsorption effect of the hydrogel material isAnd secondary pollution is caused.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a chitosan-acrylic acid based magnetic hydrogel adsorption material and a preparation method thereof, and solves the problem of Fe3O4The compatibility with the acrylic hydrogel material is poor, the combination is not tight, and the two materials are easy to have the problem of phase separation.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a chitosan-acrylic acid based magnetic hydrogel adsorption material comprises the following formula raw materials and components: 18-22 parts of nano Fe3O4Grafted chitosan, 6-10 parts of cross-linking agent, 15-20 parts of initiator, 15-20 parts of acrylamide, 23-43 parts of acrylic acid and 3-5 parts of NN-methylene bisacrylamide.
Preferably, the cross-linking agent is glutaraldehyde and the initiator is potassium persulfate.
Preferably, the nano Fe3O4The preparation method of the grafted chitosan comprises the following steps:
(1) adding glycol solvent and FeCl into a reaction bottle3Tetrabutylammonium bromide and urea are placed in a constant-temperature water bath kettle, the solution is heated to 40-60 ℃, stirred at a constant speed for 20-40min, the solution is transferred into a full-automatic reaction kettle, the solution is heated to 190-220 ℃, stirred at a constant speed for reaction for 1-2h, the solution is cooled to room temperature, the solvent is removed by filtration, distilled water and ethanol are used for washing a solid product, the solid product is placed in an atmosphere resistance furnace, nitrogen is introduced, the heating rate is 5-10 ℃/min, the solution is subjected to heat preservation and calcination at 480-520 ℃ for 2-4h, and the calcination product is porous nano Fe3O4。
(2) Adding octadecylene serving as a surfactant and a solvent and porous nano Fe into a reaction bottle3O4And oleic acid, after being dispersed uniformly by ultrasonic, transferring the solution into a full-automatic reaction kettle, heating to 280-340 ℃, stirring at constant speed for reaction for 2-6h, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product by using ethanol and acetone, placing the solid product in a mixed solvent of ethyl acetate and acetone, after being dispersed uniformly by ultrasonic, adding sodium periodateStirring at 40-60 deg.C for 3-6h, distilling the solution under reduced pressure to remove solvent, washing the solid product with distilled water and ethanol, and drying to obtain carboxylated nano Fe3O4。
(3) Adding ethanol solvent and carboxylated nano Fe into a reaction bottle3O4Adding thionyl chloride after uniform ultrasonic dispersion, placing the mixture into a constant-temperature water bath kettle, heating the mixture to 75-95 ℃, uniformly stirring the mixture for reaction for 10-18 hours, distilling the solution under reduced pressure to remove the solvent, washing the solid product by using ethanol, fully drying the solid product, and preparing the acyl chloride nano Fe3O4。
(4) Adding ethanol solvent and chitosan into a reaction bottle, adding glacial acetic acid with the mass fraction of more than or equal to 99.5%, stirring at a constant speed to dissolve the chitosan, and adding acyl chloride nano Fe3O4Placing in a constant temperature water bath kettle, heating to 60-90 deg.C, stirring at uniform speed for reaction for 15-25h, vacuum drying the solution to remove solvent, washing the solid product with distilled water and ethanol, and drying thoroughly to obtain nanometer Fe3O4And (3) grafting chitosan.
Preferably, the FeCl3The mass ratio of tetrabutylammonium bromide to urea is 1:2.8-3.5: 5-12.
Preferably, the carboxylated nano Fe3O4And the mass ratio of the thionyl chloride is 1: 45-75.
Preferably, the chitosan and the acyl chloride nano Fe3O4The mass ratio of (A) to (B) is 6-10: 1.
Preferably, the full-automatic reaction kettle comprises a reaction tank, a feed hole is arranged at the upper left of the reaction tank and is movably connected with a feed valve, a stirring heater is fixedly connected above the reaction tank and is movably connected with a stirring rod, a stirring fan is fixedly connected below the stirring rod, a heating rod is arranged inside the stirring rod, a discharge hole is arranged at the lower side of the reaction tank, a filtrate tank is fixedly connected below the reaction tank, a baffle is movably connected between the reaction tank and the filtrate tank, a filter membrane is fixedly connected above the filtrate tank, a filtrate outlet is arranged at the lower side of the filtrate tank, an air inlet pipe is fixedly connected at the left side of the reaction tank and is movably connected with an air inlet valve, an air inlet pump is movably connected below the air inlet pipe, the reaction tank is fixedly connected with an air outlet pipe on one side, the air outlet pipe is movably connected with an air outlet valve, and an air collecting pump is movably connected below the air outlet pipe.
Preferably, the preparation method of the chitosan-acrylic acid based magnetic hydrogel adsorption material comprises the following steps:
(1) introducing nitrogen into the reaction bottle to exhaust air, adding distilled water solvent and 18-22 parts of nano Fe3O4Grafting chitosan and 7-12 parts of acrylamide, placing a reaction bottle in a constant-temperature water bath, heating to 90-110 ℃, uniformly stirring, adding 6-10 parts of cross-linking agent glutaraldehyde, uniformly stirring for reaction for 10-18h, reducing the temperature to 70-80 ℃, adding 23-43 parts of acrylic acid, 3-5 parts of NN-methylene bisacrylamide, 15-20 parts of initiator potassium persulfate and the remaining 8 parts of acrylamide, uniformly stirring for reaction for 6-10h, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to prepare the chitosan-acrylic acid-based magnetic hydrogel adsorbing material.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the chitosan-acrylic acid based magnetic hydrogel adsorption material is prepared by introducing high-temperature solvent method and thermal cracking calcination into urea serving as a nucleating agent and tetrabutylammonium bromide serving as an accelerating agent to obtain porous nano Fe3O4The surface area is large, the modified nano Fe is easily modified with oleic acid through a hydrothermal synthesis method, and the carboxylated nano Fe is prepared through oxidation of sodium periodate3O4Then using thionyl chloride and nano Fe3O4The carboxyl group is reacted to obtain the acyl chloride nano Fe with high activity3O4The acyl chloride group is condensed with hydroxyl in the chitosan, and the nano Fe is bonded by chemical covalent bond3O4Chitosan was grafted successfully.
The chitosan-acrylic acid based magnetic hydrogel adsorption material uses glutaraldehyde as a cross-linking agent to enable amino groups and propyl groups in chitosan to be crosslinkedCarrying out condensation reaction on amino in the enamide to obtain nano Fe3O4Grafting alkenyl chitosan, and performing free radical polymerization reaction on the alkenyl group of the grafted alkenyl chitosan, acrylamide, acrylic acid and NN-methylene bisacrylamide to obtain the chitosan-acrylic acid-based magnetic hydrogel adsorbing material and nano Fe3O4The covalent grafting of chitosan greatly improves the nanometer Fe through a chemical bond crosslinking method3O4Compatibility with acrylic acid-based hydrogel and uniformly dispersed nano Fe3O4Endows the hydrogel material with excellent magnetic adsorption capacity, can recover the hydrogel material through an external magnetic field, avoids secondary pollution, and has the chitosan-acrylic acid based magnetic hydrogel adsorption material containing a large amount of amino and carboxyl, and chitosan also containing a large amount of hydroxyl which can be added into Cu2+、Cd2+The coordination complex reaction is carried out on the heavy metal ions, the heavy metal ions are absorbed, and the methylene blue cationic dye also has good absorption performance.
Drawings
FIG. 1 is a schematic front view of a reaction tank;
1. a reaction tank; 2. a feed port; 3. a feed valve; 4. a stirring heater; 5. a stirring rod; 6. stirring fan blades; 7. a heating rod; 8. a discharge port; 9. a filtrate tank; 10. a baffle plate; 11. filtering the membrane; 12. a filtrate outlet; 13. an air inlet pipe; 14. an intake valve; 15. an intake pump; 16. an air outlet pipe; 17. an air outlet valve; 18. air collecting pump.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: a chitosan-acrylic acid based magnetic hydrogel adsorption material comprises the following formula raw materials and components: 18-22 parts of nano Fe3O4Grafted chitosan, 6-10 parts of cross-linking agent, 15-20 parts of initiator, 15-20 parts of acrylamide, 23-43 parts of acrylic acid and 3-5 parts of NN-methylene bisacrylamide, wherein the cross-linking agent is glutaraldehyde and the initiator is potassium persulfate.
Nano Fe3O4The preparation method of the grafted chitosan comprises the following steps:
(1) adding glycol solvent, FeCl into a reaction bottle3Tetrabutylammonium bromide and urea with the mass ratio of 1:2.8-3.5:5-12, placing the materials in a constant temperature water bath kettle, heating the materials to 40-60 ℃, stirring the materials at a constant speed for 20-40min, transferring the solution into a full-automatic reaction kettle, wherein the full-automatic reaction kettle comprises a reaction tank, a feed hole is arranged at the upper left of the reaction tank, the feed hole is movably connected with a feed valve, a stirring heater is fixedly connected above the reaction tank, the stirring heater is movably connected with a stirring rod, a stirring fan sheet is fixedly connected below the stirring rod, a heating rod is arranged inside the stirring rod, a discharge hole is arranged at the lower side of the reaction tank, a filtrate tank is fixedly connected below the reaction tank, a baffle is movably connected between the reaction tank and the filtrate tank, a filter membrane is fixedly connected above the filtrate tank, a filtrate outlet is arranged at the lower side of the filtrate tank, and an air inlet pipe is, an air inlet pipe is movably connected with an air inlet valve, an air inlet pump is movably connected below the air inlet pipe, an air outlet pipe is fixedly connected on one side of a reaction tank, the air outlet pipe is movably connected with the air outlet valve, an air collecting pump is movably connected below the air outlet pipe, the reaction tank is heated to 190-3O4。
(2) Adding octadecylene serving as a surfactant and a solvent and porous nano Fe into a reaction bottle3O4And oleic acid, after being uniformly dispersed by ultrasonic, transferring the solution into a full-automatic reaction kettle, heating to 280-340 ℃, uniformly stirring for reaction for 2-6h, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product by using ethanol and acetone, placing the solid product in a mixed solvent of ethyl acetate and acetone, after being uniformly dispersed by ultrasonic, adding sodium periodate, uniformly stirring for reaction for 3-6h at 40-60 ℃, distilling the solution under reduced pressure to remove the solvent, washing the solid product by using distilled water and ethanol, and fully drying to prepare the carboxylated nano Fe3O4。
(3) Into a reaction flaskAdding ethanol solvent and carboxylated nano Fe3O4Adding thionyl chloride with the mass ratio of 1:45-75 after ultrasonic dispersion is uniform, placing the mixture into a constant-temperature water bath kettle, heating the mixture to 75-95 ℃, stirring the mixture at a constant speed for reaction for 10-18 hours, distilling the solution under reduced pressure to remove the solvent, washing the solid product with ethanol, fully drying the solid product, and preparing the acyl chloride nano Fe3O4。
(4) Adding ethanol solvent and chitosan into a reaction bottle, adding glacial acetic acid with the mass fraction of more than or equal to 99.5%, stirring at a constant speed to dissolve the chitosan, and adding acyl chloride nano Fe3O4Placing the two into a constant-temperature water bath kettle with the mass ratio of 6-10:1, heating to 60-90 ℃, uniformly stirring for reaction for 15-25h, carrying out vacuum drying on the solution to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to obtain the nano Fe3O4And (3) grafting chitosan.
The preparation method of the chitosan-acrylic acid based magnetic hydrogel adsorption material comprises the following steps:
(1) introducing nitrogen into the reaction bottle to exhaust air, adding distilled water solvent and 18-22 parts of nano Fe3O4Grafting chitosan and 7-12 parts of acrylamide, placing a reaction bottle in a constant-temperature water bath, heating to 90-110 ℃, uniformly stirring, adding 6-10 parts of cross-linking agent glutaraldehyde, uniformly stirring for reaction for 10-18h, reducing the temperature to 70-80 ℃, adding 23-43 parts of acrylic acid, 3-5 parts of NN-methylene bisacrylamide, 15-20 parts of initiator potassium persulfate and the remaining 8 parts of acrylamide, uniformly stirring for reaction for 6-10h, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to prepare the chitosan-acrylic acid-based magnetic hydrogel adsorbing material.
Example 1
(1) Preparation of porous Nano Fe3O4Component 1: adding glycol solvent, FeCl into a reaction bottle3Tetrabutylammonium bromide and urea with the mass ratio of 1:2.8:5, placing the three into a constant-temperature water bath kettle, heating to 40 ℃, uniformly stirring for 20min, transferring the solution into a full-automatic reaction kettle, wherein the full-automatic reaction kettle comprises a reaction tank, and the upper left part of the reaction tank is provided with a reaction tankA feeding hole, the feeding hole is movably connected with a feeding valve, a stirring heater is fixedly connected above the reaction tank, the stirring heater is movably connected with a stirring rod, a stirring fan blade is fixedly connected below the stirring rod, a heating rod is arranged inside the stirring rod, a discharge hole is arranged on the lower side of the reaction tank, a filtrate tank is fixedly connected below the reaction tank, a baffle is movably connected between the reaction tank and the filtrate tank, a filter membrane is fixedly connected above the filtrate tank, a filtrate outlet is arranged on the lower side of the filtrate tank, an air inlet pipe is fixedly connected on the left side of the reaction tank and movably connected with an air inlet valve, an air inlet pump is movably connected below the air inlet pipe, an air outlet pipe is fixedly connected on the air outlet side of the reaction tank and movably connected with the air outlet valve, an air collecting pump is movably connected below the air outlet pipe and heated to 190 ℃, the reaction tank is, filtering to remove the solvent, washing the solid product with distilled water and ethanol, placing the solid product in an atmosphere resistance furnace, introducing nitrogen, heating at a rate of 5 ℃/min, and calcining at 480 ℃ for 2h to obtain the calcined product, i.e. the porous nano Fe3O4And (3) component 1.
(2) Preparation of carboxylated Nano Fe3O4Component 1: adding octadecylene serving as a surfactant and a solvent and porous nano Fe into a reaction bottle3O4Uniformly dispersing a component 1 and oleic acid by ultrasonic, transferring the solution into a full-automatic reaction kettle, heating to 280 ℃, uniformly stirring for reaction for 2 hours, cooling the solution to room temperature, filtering to remove the solvent, washing a solid product by using ethanol and acetone, placing the solid product into a mixed solvent of ethyl acetate and acetone, uniformly dispersing by ultrasonic, adding sodium periodate, uniformly stirring for reaction for 3 hours at 40 ℃, distilling the solution under reduced pressure to remove the solvent, washing the solid product by using distilled water and ethanol, fully drying, and preparing the carboxylated nano Fe3O4And (3) component 1.
(3) Preparation of acylchlorinated Nano Fe3O4Component 1: adding ethanol solvent and carboxylated nano Fe into a reaction bottle3O4Adding thionyl chloride into the component 1 after ultrasonic dispersion is uniform, placing the component 1 and the thionyl chloride in a mass ratio of 1:45 in a constant-temperature water bath kettle, heating to 75 ℃, and stirring at a constant speed for reaction 10h, distilling the solution under reduced pressure to remove the solvent, washing the solid product by using ethanol, and fully drying to prepare the acyl chloride nano Fe3O4And (3) component 1.
(4) Preparation of Nano Fe3O4Grafted chitosan component 1: adding ethanol solvent and chitosan into a reaction bottle, adding glacial acetic acid with the mass fraction of more than or equal to 99.5%, stirring at a constant speed to dissolve the chitosan, and adding acyl chloride nano Fe3O4Placing the component 1 in a constant-temperature water bath kettle with the mass ratio of 6:1, heating to 60 ℃, uniformly stirring for reaction for 15h, carrying out vacuum drying on the solution to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to obtain the nano Fe3O4 Grafting chitosan component 1.
(5) Preparing a chitosan-acrylic acid-based magnetic hydrogel adsorbing material 1: introducing nitrogen into the reaction bottle to exhaust air, adding distilled water solvent and 18 parts of nano Fe3O4 Grafting chitosan component 1 and 7 parts of acrylamide, placing a reaction bottle in a constant-temperature water bath kettle, heating to 90 ℃, uniformly stirring, adding 6 parts of cross-linking agent glutaraldehyde, uniformly stirring for reaction for 10 hours, reducing the temperature to 70 ℃, adding 43 parts of acrylic acid, 3 parts of NN-methylene bisacrylamide, 15 parts of initiator potassium persulfate and the remaining 8 parts of acrylamide, uniformly stirring for reaction for 6 hours, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to prepare the chitosan-acrylic acid-based magnetic hydrogel adsorbing material 1.
Example 2
(1) Preparation of porous Nano Fe3O4And (2) component: adding glycol solvent, FeCl into a reaction bottle3Tetrabutylammonium bromide and urea with the mass ratio of 1:3.5:5, heating the mixture in a constant-temperature water bath kettle to 60 ℃, stirring the mixture at a constant speed for 20min, transferring the solution into a full-automatic reaction kettle, wherein the full-automatic reaction kettle comprises a reaction tank, a feed hole is arranged at the upper left of the reaction tank, the feed hole is movably connected with a feed valve, a stirring heater is fixedly connected to the upper part of the reaction tank, the stirring heater is movably connected with a stirring rod, a stirring fan blade is fixedly connected to the lower part of the stirring rod, and the stirring rod is internally provided with a stirring bladeA heating rod is arranged, a discharge hole is arranged at the lower side of the reaction tank, a filtrate tank is fixedly connected below the reaction tank, a baffle is movably connected between the reaction tank and the filtrate tank, a filter membrane is fixedly connected above the filtrate tank, a filtrate outlet is arranged at the lower side of the filtrate tank, an air inlet pipe is fixedly connected at the left side of the reaction tank and is movably connected with an air inlet valve, an air inlet pump is movably connected below the air inlet pipe, an air outlet pipe is fixedly connected at the side of the reaction tank and is movably connected with the air outlet valve, an air collecting pump is movably connected below the air outlet pipe and is heated to 220 ℃, the solution is stirred at a constant speed for reaction for 1h and is cooled to room temperature, a solvent is removed by filtration, the solid product is washed by, and introducing nitrogen, heating at the rate of 5 ℃/min, and calcining at 520 ℃ for 4h to obtain the porous nano Fe.3O4And (3) component 2.
(2) Preparation of carboxylated Nano Fe3O4And (2) component: adding octadecylene serving as a surfactant and a solvent and porous nano Fe into a reaction bottle3O4Uniformly dispersing the component 2 and oleic acid by ultrasonic, transferring the solution into a full-automatic reaction kettle, heating to 280 ℃, uniformly stirring for reaction for 6 hours, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product by using ethanol and acetone, placing the solid product into a mixed solvent of ethyl acetate and acetone, uniformly dispersing by ultrasonic, adding sodium periodate, uniformly stirring for reaction for 6 hours at 60 ℃, distilling the solution under reduced pressure to remove the solvent, washing the solid product by using distilled water and ethanol, fully drying, and preparing the carboxylated nano Fe3O4And (3) component 2.
(3) Preparation of acylchlorinated Nano Fe3O4And (2) component: adding ethanol solvent and carboxylated nano Fe into a reaction bottle3O4Adding thionyl chloride with the mass ratio of 1:45 into the component 2 after ultrasonic dispersion, placing the mixture in a constant-temperature water bath kettle, heating the mixture to 75 ℃, stirring the mixture at a constant speed for reacting for 18 hours, distilling the solution under reduced pressure to remove the solvent, washing the solid product with ethanol, fully drying the solid product, and preparing the acyl chloride nano Fe3O4And (3) component 2.
(4) Preparation of Nano Fe3O4Grafted chitosan component 2: adding ethanol solvent and chitosan into a reaction bottle, adding glacial acetic acid with the mass fraction of more than or equal to 99.5%, stirring at a constant speed to dissolve the chitosan, and adding acyl chloride nano Fe3O4Placing the component 2 with the mass ratio of 10:1 in a constant-temperature water bath kettle, heating to 90 ℃, uniformly stirring for reaction for 15h, carrying out vacuum drying on the solution to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to obtain the nano Fe3O4 Grafting chitosan component 2.
(5) Preparing a chitosan-acrylic acid based magnetic hydrogel adsorbing material 2: introducing nitrogen into the reaction bottle to exhaust air, adding distilled water solvent and 19 parts of nano Fe3O4 Grafting chitosan component 2 and 8.5 parts of acrylamide, placing a reaction bottle in a constant-temperature water bath kettle, heating to 110 ℃, uniformly stirring, adding 7 parts of cross-linking agent glutaraldehyde, uniformly stirring for reaction for 10 hours, reducing the temperature to 80 ℃, adding 38 parts of acrylic acid, 3.5 parts of NN-methylene bisacrylamide, 16 parts of initiator potassium persulfate and the remaining 8 parts of acrylamide, uniformly stirring for reaction for 10 hours, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to prepare the chitosan-acrylic acid-based magnetic hydrogel adsorbing material 2.
Example 3
(1) Preparation of porous Nano Fe3O4And (3) component: adding glycol solvent, FeCl into a reaction bottle3Tetrabutylammonium bromide and urea with the mass ratio of 1:3.2:8, heating the solution to 50 ℃ in a constant-temperature water bath kettle, stirring the solution at a constant speed for 30min, transferring the solution into a full-automatic reaction kettle, wherein the full-automatic reaction kettle comprises a reaction tank, a feed hole is formed in the upper left of the reaction tank and movably connected with a feed valve, a stirring heater is fixedly connected to the upper part of the reaction tank and movably connected with a stirring rod, a stirring fan sheet is fixedly connected to the lower part of the stirring rod, a heating rod is arranged in the stirring rod, a discharge hole is formed in the lower side of the reaction tank, a filtrate tank is fixedly connected to the lower part of the reaction tank, a baffle is movably connected between the reaction tank and the filtrate tank, a filter membrane is fixedly connected to the upper part of the filtrate tankThe lower side of the reaction tank is provided with a filtrate outlet, the left side of the reaction tank is fixedly connected with an air inlet pipe, the air inlet pipe is movably connected with an air inlet valve, the lower part of the air inlet pipe is movably connected with an air inlet pump, the reaction tank is fixedly connected with an air outlet pipe on the side, the air outlet pipe is movably connected with the air outlet valve, the lower part of the air outlet pipe is movably connected with an air collecting pump, the reaction tank is heated to 200 ℃, the reaction tank is stirred at a constant speed for reaction for 1.5 hours, the solution is cooled to the room temperature, the solvent is filtered and removed, the solid product is washed by using distilled water and ethanol, the solid product is placed in an atmosphere resistance furnace and is3O4And (3) component.
(2) Preparation of carboxylated Nano Fe3O4And (3) component: adding octadecylene serving as a surfactant and a solvent and porous nano Fe into a reaction bottle3O4Uniformly dispersing a component 3 and oleic acid by ultrasonic, transferring the solution into a full-automatic reaction kettle, heating to 310 ℃, uniformly stirring for reaction for 4 hours, cooling the solution to room temperature, filtering to remove the solvent, washing a solid product by using ethanol and acetone, placing the solid product into a mixed solvent of ethyl acetate and acetone, uniformly dispersing by ultrasonic, adding sodium periodate, uniformly stirring for reaction for 5 hours at 50 ℃, distilling the solution under reduced pressure to remove the solvent, washing the solid product by using distilled water and ethanol, fully drying, and preparing the carboxylated nano Fe3O4And (3) component.
(3) Preparation of acylchlorinated Nano Fe3O4And (3) component: adding ethanol solvent and carboxylated nano Fe into a reaction bottle3O4Adding thionyl chloride with the mass ratio of 1:60 into the component 3 after ultrasonic dispersion, placing the mixture in a constant-temperature water bath kettle, heating the mixture to 85 ℃, stirring the mixture at a constant speed for reaction for 14 hours, distilling the solution under reduced pressure to remove the solvent, washing the solid product with ethanol, fully drying the solid product, and preparing the acyl chloride nano Fe3O4And (3) component.
(4) Preparation of Nano Fe3O4Grafted chitosan component 3: adding ethanol solvent and chitosan into a reaction bottle, adding glacial acetic acid with the mass fraction of more than or equal to 99.5%, stirring at a constant speed to dissolve the chitosan, and adding acyl chloride nano Fe3O4Placing the component 3 with the mass ratio of 8:1 in a constant-temperature water bath kettle, heating to 75 ℃, uniformly stirring for reaction for 20 hours, carrying out vacuum drying on the solution to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to obtain the nano Fe3O4 Grafting chitosan component 3.
(5) Preparing a chitosan-acrylic acid based magnetic hydrogel adsorbing material 3: introducing nitrogen into the reaction bottle to discharge air, adding distilled water solvent and 20 parts of nano Fe3O4 Grafting chitosan component 3 and 9 parts of acrylamide, placing a reaction bottle in a constant-temperature water bath kettle, heating to 100 ℃, uniformly stirring, adding 8 parts of cross-linking agent glutaraldehyde, uniformly stirring for reaction for 14 hours, reducing the temperature to 75 ℃, adding 34 parts of acrylic acid, 4 parts of NN-methylene bisacrylamide, 17 parts of initiator potassium persulfate and the remaining 8 parts of acrylamide, uniformly stirring for reaction for 80 hours, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to prepare the chitosan-acrylic acid-based magnetic hydrogel adsorbing material 3.
Example 4
(1) Preparation of porous Nano Fe3O4And (4) component: adding glycol solvent, FeCl into a reaction bottle3Tetrabutylammonium bromide and urea with the mass ratio of 1:2.8:5, placing the three components in a constant-temperature water bath kettle, heating the components to 60 ℃, stirring the components at a constant speed for 40min, transferring the solution into a full-automatic reaction kettle, wherein the full-automatic reaction kettle comprises a reaction tank, a feed hole is arranged at the upper left of the reaction tank, the feed hole is movably connected with a feed valve, a stirring heater is fixedly connected above the reaction tank, the stirring heater is movably connected with a stirring rod, a stirring fan sheet is fixedly connected below the stirring rod, a heating rod is arranged inside the stirring rod, a discharge hole is arranged at the lower side of the reaction tank, a filtrate tank is fixedly connected below the reaction tank, a baffle is movably connected between the reaction tank and the filtrate tank, a filter membrane is fixedly connected above the filtrate tank, a filtrate outlet is arranged at the lower side of the filtrate tank, an air inlet pipe is fixedly connected at the left side, an air inlet pump is movably connected below the air inlet pipe, an air outlet pipe is fixedly connected on the side of the reaction tank,an air outlet pipe is movably connected with an air outlet valve, an air collecting pump is movably connected below the air outlet pipe, the mixture is heated to 190 ℃, stirred at a constant speed for reaction for 2 hours, the solution is cooled to room temperature, the solvent is removed by filtration, distilled water and ethanol are used for washing a solid product, the solid product is placed in an atmosphere resistance furnace, nitrogen is introduced, the heating rate is 10 ℃/min, the mixture is subjected to heat preservation and calcination at 480 ℃ for 2 hours, and the calcination product is porous nano Fe3O4And (4) component.
(2) Preparation of carboxylated Nano Fe3O4And (4) component: adding octadecylene serving as a surfactant and a solvent and porous nano Fe into a reaction bottle3O4Uniformly dispersing a component 4 and oleic acid by ultrasonic, transferring the solution into a full-automatic reaction kettle, heating to 280 ℃, uniformly stirring for reaction for 6 hours, cooling the solution to room temperature, filtering to remove the solvent, washing a solid product by using ethanol and acetone, placing the solid product into a mixed solvent of ethyl acetate and acetone, uniformly dispersing by ultrasonic, adding sodium periodate, uniformly stirring for reaction for 6 hours at 60 ℃, distilling the solution under reduced pressure to remove the solvent, washing the solid product by using distilled water and ethanol, fully drying, and preparing the carboxylated nano Fe3O4And (4) component.
(3) Preparation of acylchlorinated Nano Fe3O4And (4) component: adding ethanol solvent and carboxylated nano Fe into a reaction bottle3O4Adding thionyl chloride with the mass ratio of 1:45 into the component 4 after ultrasonic dispersion, placing the mixture in a constant-temperature water bath kettle, heating the mixture to 75 ℃, stirring the mixture at a constant speed for reacting for 18 hours, distilling the solution under reduced pressure to remove the solvent, washing the solid product with ethanol, fully drying the solid product, and preparing the acyl chloride nano Fe3O4And (4) component.
(4) Preparation of Nano Fe3O4Grafted chitosan component 4: adding ethanol solvent and chitosan into a reaction bottle, adding glacial acetic acid with the mass fraction of more than or equal to 99.5%, stirring at a constant speed to dissolve the chitosan, and adding acyl chloride nano Fe3O4Placing the component 4 with the mass ratio of 10:1 in a constant-temperature water bath kettle, heating to 60 ℃, uniformly stirring for reaction for 25h, vacuum-drying the solution to remove the solvent, washing the solid product with distilled water and ethanol, and fully washingDrying to obtain the nano Fe3O4 Grafting chitosan component 4.
(5) Preparing a chitosan-acrylic acid based magnetic hydrogel adsorbing material 4: introducing nitrogen into the reaction bottle to exhaust air, adding distilled water solvent and 21 parts of nano Fe3O4 Grafting chitosan component 4 and 10.5 parts of acrylamide, placing a reaction bottle in a constant-temperature water bath kettle, heating to 90 ℃, uniformly stirring, adding 9 parts of cross-linking agent glutaraldehyde, uniformly stirring for reaction for 10 hours, reducing the temperature to 80 ℃, adding 28 parts of acrylic acid, 4.5 parts of NN-methylene bisacrylamide, 19 parts of initiator potassium persulfate and the remaining 8 parts of acrylamide, uniformly stirring for reaction for 6 hours, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to prepare the chitosan-acrylic acid-based magnetic hydrogel adsorbing material 4.
Example 5
(1) Preparation of porous Nano Fe3O4And (5) component: adding glycol solvent, FeCl into a reaction bottle3Tetrabutylammonium bromide and urea with the mass ratio of 1:3.5:12, placing the three components in a constant-temperature water bath kettle, heating the components to 60 ℃, stirring the components at a constant speed for 40min, transferring the solution into a full-automatic reaction kettle, wherein the full-automatic reaction kettle comprises a reaction tank, a feed hole is arranged at the upper left of the reaction tank, the feed hole is movably connected with a feed valve, a stirring heater is fixedly connected above the reaction tank, the stirring heater is movably connected with a stirring rod, a stirring fan sheet is fixedly connected below the stirring rod, a heating rod is arranged inside the stirring rod, a discharge hole is arranged at the lower side of the reaction tank, a filtrate tank is fixedly connected below the reaction tank, a baffle is movably connected between the reaction tank and the filtrate tank, a filter membrane is fixedly connected above the filtrate tank, a filtrate outlet is arranged at the lower side of the filtrate tank, an air inlet pipe is fixedly connected at the left side, an air inlet pump is movably connected below the air inlet pipe, an air outlet pipe is fixedly connected with the side of the reaction tank, the air outlet pipe is movably connected with an air outlet valve, an air collecting pump is movably connected below the air outlet pipe, the temperature is increased to 220 ℃, the reaction is carried out for 2 hours under uniform stirring, the solution is cooled to the room temperature, the solvent is removed by filtration, and the solution is washed by distilled water and ethanolPutting the solid product in an atmosphere resistance furnace, introducing nitrogen, heating at the rate of 10 ℃/min, and calcining at 520 ℃ for 4h to obtain the calcined product, namely the porous nano Fe3O4And (5) component.
(2) Preparation of carboxylated Nano Fe3O4And (5) component: adding octadecylene serving as a surfactant and a solvent and porous nano Fe into a reaction bottle3O4Uniformly dispersing the component 5 and oleic acid by ultrasonic, transferring the solution into a full-automatic reaction kettle, heating to 340 ℃, uniformly stirring for reaction for 6 hours, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product by using ethanol and acetone, placing the solid product into a mixed solvent of ethyl acetate and acetone, uniformly dispersing by ultrasonic, adding sodium periodate, uniformly stirring for reaction for 6 hours at 60 ℃, distilling the solution under reduced pressure to remove the solvent, washing the solid product by using distilled water and ethanol, fully drying, and preparing the carboxylated nano Fe3O4And (5) component.
(3) Preparation of acylchlorinated Nano Fe3O4And (5) component: adding ethanol solvent and carboxylated nano Fe into a reaction bottle3O4Adding thionyl chloride with the mass ratio of 1:75 into the component 5 after ultrasonic dispersion, placing the mixture in a constant-temperature water bath kettle, heating the mixture to 95 ℃, stirring the mixture at a constant speed for reacting for 18 hours, distilling the solution under reduced pressure to remove the solvent, washing the solid product with ethanol, fully drying the solid product, and preparing the acyl chloride nano Fe3O4And (5) component.
(4) Preparation of Nano Fe3O4Grafted chitosan component 5: adding ethanol solvent and chitosan into a reaction bottle, adding glacial acetic acid with the mass fraction of more than or equal to 99.5%, stirring at a constant speed to dissolve the chitosan, and adding acyl chloride nano Fe3O4Placing the component 5 with the mass ratio of 10:1 into a constant-temperature water bath kettle, heating to 90 ℃, uniformly stirring for reaction for 25h, carrying out vacuum drying on the solution to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to obtain the nano Fe3O4 Grafted chitosan component 5.
(5) Preparing the chitosan-acrylic acid-based magnetic hydrogel adsorbing material 5: introducing nitrogen into the reaction bottleDischarging air, adding distilled water solvent and 22 parts of nano Fe3O4Grafting 5 parts of chitosan component and 12 parts of acrylamide, placing a reaction bottle in a constant-temperature water bath, heating to 110 ℃, uniformly stirring, adding 10 parts of cross-linking agent glutaraldehyde, uniformly stirring for reacting for 18 hours, reducing the temperature to 80 ℃, adding 23 parts of acrylic acid, 5 parts of NN-methylene bisacrylamide, 20 parts of initiator potassium persulfate and the remaining 8 parts of acrylamide, uniformly stirring for reacting for 10 hours, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to prepare the chitosan-acrylic acid-based magnetic hydrogel adsorbing material 5.
The chitosan-acrylic acid based magnetic hydrogel adsorption material is prepared by introducing high-temperature solvent method and thermal cracking calcination into urea serving as a nucleating agent and tetrabutylammonium bromide serving as an accelerating agent to obtain porous nano Fe3O4The surface area is large, the modified nano Fe is easily modified with oleic acid through a hydrothermal synthesis method, and the carboxylated nano Fe is prepared through oxidation of sodium periodate3O4Then using thionyl chloride and nano Fe3O4The carboxyl group is reacted to obtain the acyl chloride nano Fe with high activity3O4The acyl chloride group is condensed with hydroxyl in the chitosan, and the nano Fe is bonded by chemical covalent bond3O4Chitosan was grafted successfully.
Glutaraldehyde is taken as a cross-linking agent to carry out condensation reaction on amino in chitosan and amino in acrylamide to obtain nano Fe3O4Grafting alkenyl chitosan, and performing free radical polymerization reaction on the alkenyl group of the grafted alkenyl chitosan, acrylamide, acrylic acid and NN-methylene bisacrylamide to obtain the chitosan-acrylic acid-based magnetic hydrogel adsorbing material and nano Fe3O4The covalent grafting of chitosan greatly improves the nanometer Fe through a chemical bond crosslinking method3O4Compatibility with acrylic acid-based hydrogel and uniformly dispersed nano Fe3O4Endows the hydrogel material with excellent magnetic adsorption capacity, can recover the hydrogel material through an external magnetic field, avoids secondary pollution, and has chitosan-chitosanThe gadoleic acid-based magnetic hydrogel adsorbent contains a large amount of amino and carboxyl, and chitosan also contains a large amount of hydroxyl which can be dissolved in Cu2+、Cd2+The coordination complex reaction is carried out on the heavy metal ions, the heavy metal ions are absorbed, and the methylene blue cationic dye also has good absorption performance.

Claims (8)

1. A chitosan-acrylic acid based magnetic hydrogel adsorption material comprises the following formula raw materials and components, and is characterized in that: 18-22 parts of nano Fe3O4Grafted chitosan, 6-10 parts of cross-linking agent, 15-20 parts of initiator, 15-20 parts of acrylamide, 23-43 parts of acrylic acid and 3-5 parts of NN-methylene bisacrylamide.
2. A chitosan-acrylic acid based magnetic hydrogel adsorbent material as claimed in claim 1, wherein: the cross-linking agent is glutaraldehyde and the initiator is potassium persulfate.
3. A chitosan-acrylic acid based magnetic hydrogel adsorbent material as claimed in claim 1, wherein: the nano Fe3O4The preparation method of the grafted chitosan comprises the following steps:
(1) adding FeCl to ethylene glycol solvent3Heating tetrabutylammonium bromide and urea to 40-60 ℃, stirring at a constant speed for 20-40min, transferring the solution into a full-automatic reaction kettle, heating to 190-3O4；
(2) Adding porous nano Fe into octadecene as surfactant and solvent3O4And oleic acid, after being dispersed evenly by ultrasonic, the solution is transferred into a full-automatic reaction kettle, heated to 280-340 ℃, reacted for 2-6h, filtered and washed, the solid product is placed in a mixed solvent of ethyl acetate and acetone, after being dispersed evenly by ultrasonic, sodium periodate is added, the reaction is carried out for 3-6h at 40-60 ℃, the solvent is removed, and the washing is carried outDrying to obtain carboxylated nano Fe3O4；
(3) Adding carboxylated nano Fe into ethanol solvent3O4Adding thionyl chloride after ultrasonic dispersion is uniform, heating to 75-95 ℃, reacting for 10-18h, removing the solvent, washing and drying to prepare the acyl chloride nano Fe3O4；
(4) Adding chitosan into ethanol solvent, adding glacial acetic acid with mass fraction of more than or equal to 99.5%, stirring at constant speed for dissolving, and adding acyl chloride nano Fe3O4Heating to 60-90 ℃, stirring at a constant speed for reaction for 15-25h, removing the solvent, washing and drying to prepare the nano Fe3O4And (3) grafting chitosan.
4. A chitosan-acrylic acid based magnetic hydrogel adsorbent material as claimed in claim 3, wherein: the FeCl3The mass ratio of tetrabutylammonium bromide to urea is 1:2.8-3.5: 5-12.
5. A chitosan-acrylic acid based magnetic hydrogel adsorbent material as claimed in claim 3, wherein: the carboxylated nano Fe3O4And the mass ratio of the thionyl chloride is 1: 45-75.
6. A chitosan-acrylic acid based magnetic hydrogel adsorbent material as claimed in claim 3, wherein: the chitosan and acyl chloride nano Fe3O4The mass ratio of (A) to (B) is 6-10: 1.
7. A chitosan-acrylic acid based magnetic hydrogel adsorbent material as claimed in claim 3, wherein: the full-automatic reaction kettle comprises a reaction tank, a feed hole is arranged at the upper left of the reaction tank and is movably connected with a feed valve, a stirring heater is fixedly connected above the reaction tank and is movably connected with a stirring rod, a stirring fan blade is fixedly connected below the stirring rod, a heating rod is arranged inside the stirring rod, a discharge hole is arranged at the lower side of the reaction tank, a filtrate tank is fixedly connected below the reaction tank, a baffle is movably connected between the reaction tank and the filtrate tank, a filter membrane is fixedly connected above the filtrate tank, a filtrate outlet is arranged at the lower side of the filtrate tank, an air inlet pipe is fixedly connected at the left side of the reaction tank and is movably connected with an air inlet valve, an air inlet pump is movably connected below the air inlet pipe, the reaction tank is fixedly connected with an air outlet pipe on one side, the air outlet pipe is movably connected with an air outlet valve, and an air collecting pump is movably connected below the air outlet pipe.
8. A chitosan-acrylic acid based magnetic hydrogel adsorbent material as claimed in claim 1, wherein: the preparation method of the chitosan-acrylic acid based magnetic hydrogel adsorption material comprises the following steps:
(1) adding 18-22 parts of nano Fe into distilled water solvent3O4Grafting chitosan and 7-12 parts of acrylamide, heating to 90-110 ℃ in a nitrogen atmosphere, uniformly stirring, adding 6-10 parts of cross-linking agent glutaraldehyde, reacting for 10-18h, reducing the temperature to 70-80 ℃, adding 23-43 parts of acrylic acid, 3-5 parts of NN-methylene bisacrylamide, 15-20 parts of initiator potassium persulfate and the remaining 8 parts of acrylamide, reacting for 6-10h, filtering, washing and drying to prepare the chitosan-acrylic acid-based magnetic hydrogel adsorbing material.
CN202010394618.6A 2020-05-11 2020-05-11 Chitosan-acrylic acid-based magnetic hydrogel adsorption material and preparation method thereof Withdrawn CN111495336A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112029117A (en) * 2020-08-17 2020-12-04 嵊州市鉴亭新材料科技有限公司 Acrylic copolymer magnetic porous hydrogel adsorbent and preparation method thereof
CN112473746A (en) * 2020-12-08 2021-03-12 东华大学 Cu0Preparation method and application of (E) -ferroferric oxide @ chitosan nano material
CN112675824A (en) * 2020-12-15 2021-04-20 桐乡市融杭科技合伙企业(有限合伙) Fe3O4Chemically grafted polyacrylic acid-chitosan composite hydrogel and preparation method thereof
CN116371378A (en) * 2023-04-10 2023-07-04 国家粮食和物资储备局科学研究院 Magnetic adsorption material and preparation method and application thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112029117A (en) * 2020-08-17 2020-12-04 嵊州市鉴亭新材料科技有限公司 Acrylic copolymer magnetic porous hydrogel adsorbent and preparation method thereof
CN112473746A (en) * 2020-12-08 2021-03-12 东华大学 Cu0Preparation method and application of (E) -ferroferric oxide @ chitosan nano material
CN112675824A (en) * 2020-12-15 2021-04-20 桐乡市融杭科技合伙企业(有限合伙) Fe3O4Chemically grafted polyacrylic acid-chitosan composite hydrogel and preparation method thereof
CN116371378A (en) * 2023-04-10 2023-07-04 国家粮食和物资储备局科学研究院 Magnetic adsorption material and preparation method and application thereof

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