CN112044413A - Chitosan modified polyacrylic acid hydrogel adsorption material and preparation method thereof - Google Patents
Chitosan modified polyacrylic acid hydrogel adsorption material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of hydrogel adsorption materials, and discloses a chitosan modified polyacrylic acid hydrogel adsorption material which comprises the following formula raw materials and components: acrylic acid, methacrylic acid, modified chitosan microspheres, an initiator and a cross-linking agent. According to the chitosan modified polyacrylic acid hydrogel adsorption material, glutaraldehyde is used as a cross-linking agent, amino in chitosan and amino in acrylamide are subjected to condensation reaction with glutaraldehyde respectively to realize that acrylamide is grafted with chitosan microspheres, acrylamide, acrylic acid and methacrylic acid are polymerized to form a polypropylene-based hydrogel material, chitosan forms a composite hydrogel material in a chemical bonding mode, the chemical and physical stability of the hydrogel material is enhanced, amino and hydroxyl contained in chitosan, and the polypropylene-based polymer contains amino and carboxyl, is subjected to complex reaction with heavy metal ions such as copper, cadmium and chromium and methylene blue, and has the effect of adsorbing pollutants.
Description
Technical Field
The invention relates to the technical field of hydrogel adsorption materials, in particular to a chitosan modified polyacrylic acid hydrogel adsorption material and a preparation method thereof.
Background
However, in recent years, the water resource environment of China is continuously deteriorated, the quality of the water body environment is continuously reduced, accidents caused by pollution cause serious social influence and large economic loss, the health of people is threatened, the social development is damaged, the water body pollutants mainly comprise industrial wastewater, domestic wastewater and farmland wastewater which are discharged without treatment, and garbage pollutants which are randomly discarded at the river, the pollutants mainly comprise heavy metal ions and compounds thereof such as copper, cadmium, chromium and the like, aromatic compounds, halogen compounds and organic dyes such as methylene blue, methyl orange and the like, and the water body ecological environment is seriously polluted.
At present, the main methods for sewage treatment include a chemical neutralization method, a chemical precipitation method, a biodegradation method, a physical adsorption method, a physical flocculation method and the like, chitosan is a biomass material and contains abundant hydroxyl and amino, an adsorption material can be prepared to perform a complex reaction with heavy metal ions such as copper, cadmium, chromium and the like and methylene blue cationic dye, so that the effects of adsorbing pollutants and purifying a water source are achieved, but the chitosan has biodegradability and is unstable and easy to decompose in a natural environment, polypropylene-based hydrogel is a three-dimensional network structure gel and has strong hydrophilicity, a cross-linked network exists inside, the chitosan-polypropylene-based hydrogel can be rapidly swelled and undissolved in water, the polypropylene-based hydrogel contains a large amount of hydroxyl, amino, carboxyl and other groups, most of the existing chitosan-polypropylene-based hydrogel is modified by physical blending or doping, the chitosan-polypropylene-based hydrogel is easy to decompose after absorbing water and swelling through weak physical acting force for physical crosslinking, and how to form more stable chemical crosslinking hydrogel by chitosan and polypropylene-based polymer through chemical acting force and a chemical bonding mode becomes a difficult point.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a chitosan modified polyacrylic acid hydrogel adsorption material and a preparation method thereof, which enable chitosan and polypropylene-based polymer to form a stable chemical crosslinking hydrogel adsorption material through chemical bonding dispersion.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a chitosan modified polyacrylic acid hydrogel adsorption material comprises the following formula raw materials and components in parts by weight: 25-30 parts of acrylic acid, 20-24 parts of methacrylic acid, 20-42 parts of modified chitosan microspheres, 10-20 parts of an initiator and 3-6 parts of a cross-linking agent, wherein the initiator is potassium persulfate, and the cross-linking agent is N, N-methylene bisacrylamide.
Preferably, the preparation method of the modified chitosan microsphere comprises the following steps:
(1) adding 4-8% by mass of acetic acid solution into a reaction bottle, adding chitosan, stirring for dissolving, placing the reaction bottle into an ultrasonic disperser, performing ultrasonic dispersion treatment for 1-2h, adding a liquid paraffin solvent into the reaction bottle, placing the reaction bottle into a constant-temperature water bath kettle, heating to 45-55 ℃, uniformly stirring for 10-20min by using an automatic stirrer, adding an emulsifier Tween 20, performing emulsification for 20-40min by uniform stirring, heating to 60-70 ℃, adding a cross-linking agent glutaraldehyde, stirring at uniform speed for reaction for 1-2h, then adding sodium hydroxide, adjusting the pH of the solution to 10-11, heating to 75-85 ℃, adding an accelerator epichlorohydrin, stirring at uniform speed for reaction for 4-6h, placing the solution into an ice water bath for cooling, adding distilled water until a large amount of precipitate is generated, filtering to remove the solvent, sequentially adding the solid mixture into an ether solution, uniformly stirring for 10-15h, filtering to remove the solvent, washing the solid product with ether and ethanol, and fully drying;
(2) putting the solid product into an ethanol solvent, adding acrylamide, a cross-linking agent glutaraldehyde and a condensing agent 2- (7-benzotriazole oxide) -N, N, N ', N' -tetramethylurea hexafluorophosphate, then adding a liquid paraffin solvent and an emulsifier Tween 20, putting a reaction bottle into a constant-temperature water bath, heating to 140 ℃, uniformly stirring for reaction for 20-30h, putting the solution into an ice water bath for cooling, adding distilled water until a large amount of precipitate is generated, filtering to remove the solvent, putting the solid mixture into an ether solution, uniformly stirring for 10-15h, filtering to remove the solvent, washing the solid product with ether and ethanol, and fully drying to prepare the acrylamide grafted modified chitosan microsphere.
Preferably, the mass ratio of the chitosan, the Tween 20, the glutaraldehyde and the epichlorohydrin in the step (1) is 1:0.08-0.12:0.4-0.6: 0.8-1.4.
Preferably, the mass ratio of the solid product in the step (2), acrylamide, glutaraldehyde and 2- (7-benzotriazole oxide) -N, N, N ', N' -tetramethylurea hexafluorophosphate is 1:8-15:3-6: 5-10.
Preferably, the automatic stirrer comprises a stirring rod, a power line fixedly connected inside the stirring rod, a waterproof sleeve fixedly connected inside the stirring rod, one end of the power line and a plug fixedly connected with the stirring rod, a rotator movably connected at the lower end of the stirring rod, a rotator fixedly connected with the power line, a limiting rod arranged inside the rotator, a thread arranged on the surface of the limiting rod, a limiting rod movably connected with a threaded ring, and a stirring fan fixedly connected with the threaded ring.
Preferably, the preparation method of the chitosan modified polyacrylic acid hydrogel adsorption material comprises the following steps:
(1) adding distilled water solvent and 20-42 parts of modified chitosan microspheres into a reaction bottle, performing ultrasonic dispersion treatment on the solution at 40-60 ℃ for 1-2h at the ultrasonic frequency of 25-35KHz, adding 25-30 parts of acrylic acid, 20-24 parts of methacrylic acid, 3-6 parts of cross-linking agent N, N-methylene bisacrylamide and 10-20 parts of initiator potassium persulfate, placing the reaction bottle in a constant-temperature water bath, heating to 50-80 ℃, reacting for 18-24h, performing vacuum drying on the solution to remove the solvent, placing a solid product in a dialysis bag, adding distilled water solvent to perform dialysis impurity removal, and preparing the chitosan modified polyacrylic acid hydrogel adsorbing material.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the chitosan modified polyacrylic acid hydrogel adsorption material uses glutaraldehyde as a cross-linking agent and epichlorohydrin as an accelerating agent to form chitosan microspheres with smaller particle size and larger specific surface area, then uses a condensing agent 2- (7-benzotriazole oxide) -N, N, N ', N' -tetramethylurea hexafluorophosphate to perform condensation reaction on amino in chitosan and amino in acrylamide and a cross-linking agent glutaraldehyde respectively to successfully realize acrylamide grafted chitosan microspheres, then uses free radical polymerization to polymerize acrylamide, acrylic acid and methacrylic acid to form a polypropylene-based hydrogel material, leads the chitosan to be grafted and copolymerized with a polypropylene-based polymer in a chemical bonding mode to form a composite hydrogel material, improves the dispersibility and compatibility of the chitosan in the polypropylene-based polymer, and greatly enhances the chemical and physical stability of the hydrogel material, the base body is stable and is not easy to decompose when the base body swells in water.
According to the chitosan modified polyacrylic acid hydrogel adsorption material, chitosan contains a large number of amino and hydroxyl groups, and the polypropylene-based polymer also contains rich amino and carboxyl groups, so that the chitosan modified polyacrylic acid hydrogel adsorption material can perform a complex reaction with heavy metal ions such as copper, cadmium and chromium, and cationic dyes such as methylene blue, and has the effects of adsorbing pollutants and purifying water sources.
Drawings
FIG. 1 is a schematic front view of a blender;
FIG. 2 is a schematic view of the mixing blade adjustment;
1. a stirring rod; 2. a power line; 3. a waterproof jacket; 4. a plug; 5. a rotator; 6. a limiting rod; 7. a threaded ring; 8. stirring fan blades.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: a chitosan modified polyacrylic acid hydrogel adsorption material comprises the following formula raw materials and components in parts by weight: 25-30 parts of acrylic acid, 20-24 parts of methacrylic acid, 20-42 parts of modified chitosan microspheres, 10-20 parts of an initiator and 3-6 parts of a cross-linking agent, wherein the initiator is potassium persulfate, and the cross-linking agent is N, N-methylene bisacrylamide.
The preparation method of the modified chitosan microsphere comprises the following steps:
(1) adding 4-8% acetic acid solution by mass into a reaction bottle, adding chitosan, stirring for dissolving, placing the reaction bottle in an ultrasonic disperser, performing ultrasonic dispersion treatment for 1-2h, adding liquid paraffin solvent into the reaction bottle, placing the reaction bottle in a constant-temperature water bath kettle, heating to 45-55 deg.C, stirring for 10-20min at constant speed by using an automatic stirrer, wherein the automatic stirrer comprises a stirring rod, a power line fixedly connected to the inside of the stirring rod, a waterproof sleeve fixedly connected to the inside of the stirring rod, a plug fixedly connected to one end of the power line, a rotator movably connected to the lower end of the stirring rod, a limit rod fixedly connected to the power line, a screw thread arranged on the surface of the limit rod, a screw thread ring movably connected to the limit rod, a stirring fan sheet fixedly connected to the screw thread ring, and an emulsifier Tween 20, stirring at constant speed for emulsifying for 20-40min, heating to 60-70 deg.C, adding cross-linking agent glutaraldehyde, stirring at constant speed for reaction for 1-2h, adding sodium hydroxide, adjusting pH to 10-11, heating to 75-85 deg.C, adding promoter epichlorohydrin, wherein the mass ratio of chitosan, Tween 20, glutaraldehyde and epichlorohydrin is 1:0.08-0.12:0.4-0.6:0.8-1.4, stirring at constant speed for reaction for 4-6h, cooling the solution in ice water bath, adding distilled water until a large amount of precipitate is generated, filtering to remove solvent, sequentially adding solid mixture into diethyl ether solution, stirring at constant speed for 10-15h, filtering to remove solvent, washing solid product with diethyl ether and ethanol, and drying thoroughly;
(2) putting the solid product into an ethanol solvent, adding acrylamide, a cross-linking agent glutaraldehyde and a condensing agent 2- (7-benzotriazole oxide) -N, N, N ', N' -tetramethylurea hexafluorophosphate, then adding a liquid paraffin solvent and an emulsifier Tween 20, wherein the mass ratio of the solid product, the acrylamide, the glutaraldehyde and the 2- (7-benzotriazole oxide) -N, N, N ', N' -tetramethylurea hexafluorophosphate is 1:8-15:3-6:5-10, putting a reaction bottle into a constant-temperature water bath, heating to 140 ℃, uniformly stirring and reacting for 20-30h, putting the solution into an ice water bath for cooling, adding distilled water until a large amount of precipitate is generated, filtering to remove the solvent, putting the solid mixture into an ether solution, stirring at a constant speed for 10-15h, filtering to remove the solvent, washing the solid product with diethyl ether and ethanol, and fully drying to prepare the acrylamide grafted modified chitosan microsphere.
The preparation method of the chitosan modified polyacrylic acid hydrogel adsorption material comprises the following steps:
(1) adding distilled water solvent and 20-42 parts of modified chitosan microspheres into a reaction bottle, performing ultrasonic dispersion treatment on the solution at 40-60 ℃ for 1-2h at the ultrasonic frequency of 25-35KHz, adding 25-30 parts of acrylic acid, 20-24 parts of methacrylic acid, 3-6 parts of cross-linking agent N, N-methylene bisacrylamide and 10-20 parts of initiator potassium persulfate, placing the reaction bottle in a constant-temperature water bath, heating to 50-80 ℃, reacting for 18-24h, performing vacuum drying on the solution to remove the solvent, placing a solid product in a dialysis bag, adding distilled water solvent to perform dialysis impurity removal, and preparing the chitosan modified polyacrylic acid hydrogel adsorbing material.
Example 1
(1) Preparing a modified chitosan microsphere component 1: adding 4% acetic acid solution by mass into a reaction bottle, adding chitosan, stirring and dissolving, placing the reaction bottle in an ultrasonic disperser, performing ultrasonic dispersion treatment for 1h, adding a liquid paraffin solvent into the reaction bottle, placing the reaction bottle in a constant-temperature water bath kettle, heating to 45 ℃, stirring for 10min at constant speed by using an automatic stirrer, wherein the automatic stirrer comprises a stirring rod, a power wire is fixedly connected inside the stirring rod, a waterproof sleeve is fixedly connected inside the stirring rod, one end of the power wire is fixedly connected with a plug, a rotator is movably connected at the lower end of the stirring rod and is fixedly connected with the power wire, a limiting rod is arranged inside the rotator, threads are arranged on the surface of the limiting rod, the limiting rod is movably connected with a threaded ring, a stirring fan sheet is fixedly connected with the threaded ring, adding emulsifier Tween 20, stirring at constant speed for emulsification for 20min, heating to 60 ℃, adding cross-linking agent glutaraldehyde, stirring at a constant speed for reaction for 1h, then adding sodium hydroxide, adjusting the pH of the solution to 10, heating to 75 ℃, adding accelerator epichlorohydrin, wherein the mass ratio of chitosan to tween-20 to glutaraldehyde to epichlorohydrin is 1:0.08:0.4:0.8, stirring at a constant speed for reaction for 4h, placing the solution in an ice-water bath for cooling, adding distilled water until a large amount of precipitate is generated, filtering to remove the solvent, sequentially adding a solid mixture into an ether solution, stirring at a constant speed for 10h, filtering to remove the solvent, washing the solid product with ether and ethanol, and fully drying;
putting the solid product into an ethanol solvent, adding acrylamide, a cross-linking agent glutaraldehyde and a condensing agent 2- (7-benzotriazole oxide) -N, N, N ', N' -tetramethylurea hexafluorophosphate, then adding a liquid paraffin solvent and an emulsifier Tween 20, wherein the mass ratio of the solid product, the acrylamide, the glutaraldehyde and the 2- (7-benzotriazole oxide) -N, N, N ', N' -tetramethylurea hexafluorophosphate is 1:8:3:5, putting a reaction bottle into a constant-temperature water bath, heating to 100 ℃, stirring at a constant speed for reaction for 20 hours, putting the solution into an ice water bath for cooling, adding distilled water until a large amount of precipitates are generated, filtering to remove the solvent, putting the solid mixture into an ether solution, stirring at a constant speed for 10 hours, filtering to remove the solvent, washing the solid product by using ether and ethanol, and fully drying to prepare the acrylamide grafted modified chitosan microsphere component 1.
(2) Preparing a chitosan modified polyacrylic acid hydrogel adsorption material 1: adding a distilled water solvent and 42 parts of modified chitosan microsphere component 1 into a reaction bottle, performing ultrasonic dispersion treatment on the solution at 40 ℃ for 1h, wherein the ultrasonic frequency is 25KHz, adding 25 parts of acrylic acid, 20 methacrylic acid, 3 parts of cross-linking agent N, N-methylene bisacrylamide and 10 parts of initiator potassium persulfate, placing the reaction bottle into a constant-temperature water bath kettle, heating to 50 ℃, reacting for 18h, performing vacuum drying on the solution to remove the solvent, placing a solid product into a dialysis bag, adding the distilled water solvent to perform a dialysis impurity removal process, and preparing the chitosan modified polyacrylic acid hydrogel adsorption material 1.
Example 2
(1) Preparing a modified chitosan microsphere component 2: adding 8 mass percent acetic acid solution into a reaction bottle, adding chitosan, stirring and dissolving, placing the reaction bottle in an ultrasonic dispersion instrument, carrying out ultrasonic dispersion treatment for 1h, adding a liquid paraffin solvent into the reaction bottle, placing the reaction bottle in a constant-temperature water bath kettle, heating to 55 ℃, stirring for 10min at constant speed by using an automatic stirrer, wherein the automatic stirrer comprises a stirring rod, a power wire is fixedly connected inside the stirring rod, a waterproof sleeve is fixedly connected inside the stirring rod, one end of the power wire is fixedly connected with a plug, a rotator is movably connected at the lower end of the stirring rod and is fixedly connected with the power wire, a limiting rod is arranged inside the rotator, threads are arranged on the surface of the limiting rod, the limiting rod is movably connected with a threaded ring, a stirring fan sheet is fixedly connected with the threaded ring, adding emulsifier Tween 20, stirring at constant speed for emulsification for 40min, heating to 60 ℃, adding cross-linking agent glutaraldehyde, stirring at a constant speed for reaction for 1h, then adding sodium hydroxide, adjusting the pH of the solution to 10, heating to 85 ℃, adding accelerator epichlorohydrin, wherein the mass ratio of chitosan to tween-20 to glutaraldehyde to epichlorohydrin is 1:0.12:0.4:0.8, stirring at a constant speed for reaction for 6h, placing the solution in an ice-water bath for cooling, adding distilled water until a large amount of precipitate is generated, filtering to remove the solvent, sequentially adding a solid mixture into an ether solution, stirring at a constant speed for 15h, filtering to remove the solvent, washing the solid product with ether and ethanol, and fully drying;
putting the solid product into an ethanol solvent, adding acrylamide, a cross-linking agent glutaraldehyde and a condensing agent 2- (7-benzotriazole oxide) -N, N, N ', N' -tetramethylurea hexafluorophosphate, then adding a liquid paraffin solvent and an emulsifier Tween 20, wherein the mass ratio of the solid product, the acrylamide, the glutaraldehyde and the 2- (7-benzotriazole oxide) -N, N, N ', N' -tetramethylurea hexafluorophosphate is 1:8:6:5, putting a reaction bottle into a constant-temperature water bath, heating to 140 ℃, stirring at a constant speed for reaction for 20 hours, putting the solution into an ice water bath for cooling, adding distilled water until a large amount of precipitates are generated, filtering to remove the solvent, putting the solid mixture into an ether solution, stirring at a constant speed for 10 hours, filtering to remove the solvent, washing the solid product by using ether and ethanol, and fully drying to prepare the acrylamide grafted modified chitosan microsphere component 2.
(2) Preparing a chitosan modified polyacrylic acid hydrogel adsorption material 2: adding a distilled water solvent and 37 parts of modified chitosan microsphere component 2 into a reaction bottle, performing ultrasonic dispersion treatment on the solution at 60 ℃ for 1h, wherein the ultrasonic frequency is 35KHz, adding 26 parts of acrylic acid, 21 methacrylic acid, 4 parts of cross-linking agent N, N-methylene bisacrylamide and 12 parts of initiator potassium persulfate, placing the reaction bottle into a constant-temperature water bath kettle, heating to 50 ℃, reacting for 24h, performing vacuum drying on the solution to remove the solvent, placing a solid product into a dialysis bag, adding the distilled water solvent to perform a dialysis impurity removal process, and preparing the chitosan modified polyacrylic acid hydrogel adsorption material 2.
Example 3
(1) Preparing a modified chitosan microsphere component 3: adding 6 mass percent acetic acid solution into a reaction bottle, adding chitosan, stirring and dissolving, placing the reaction bottle in an ultrasonic dispersion instrument, carrying out ultrasonic dispersion treatment for 1.5h, adding a liquid paraffin solvent into the reaction bottle, placing the reaction bottle in a constant-temperature water bath kettle, heating to 50 ℃, stirring for 15min at a constant speed by using an automatic stirrer, wherein the automatic stirrer comprises a stirring rod, a power wire is fixedly connected inside the stirring rod, a waterproof sleeve is fixedly connected inside the stirring rod, one end of the power wire is fixedly connected with a plug, a rotator is movably connected at the lower end of the stirring rod and is fixedly connected with the power wire, a limiting rod is arranged inside the rotator, threads are arranged on the surface of the limiting rod, the limiting rod is movably connected with a threaded ring, a stirring fan sheet is fixedly connected with the threaded ring, then emulsifier Tween 20 is added, stirring at a constant speed is carried out for emulsification for 30min, heating to 65 ℃, adding cross-linking agent glutaraldehyde, stirring at a constant speed for reaction for 1.5h, then adding sodium hydroxide, adjusting the pH of the solution to 11, heating to 80 ℃, adding accelerator epichlorohydrin, stirring at a constant speed for reaction for 5h, placing the solution in an ice water bath for cooling, adding distilled water until a large amount of precipitate is generated, filtering to remove the solvent, sequentially adding a solid mixture into an ether solution, stirring at a constant speed for 12h, filtering to remove the solvent, washing the solid product with ether and ethanol, and fully drying;
putting the solid product into an ethanol solvent, adding acrylamide, a cross-linking agent glutaraldehyde and a condensing agent 2- (7-benzotriazole oxide) -N, N, N ', N' -tetramethylurea hexafluorophosphate, then adding a liquid paraffin solvent and an emulsifier Tween 20, wherein the mass ratio of the solid product, the acrylamide, the glutaraldehyde and the 2- (7-benzotriazole oxide) -N, N, N ', N' -tetramethylurea hexafluorophosphate is 1:12:4.5:8, putting a reaction bottle into a constant-temperature water bath, heating to 120 ℃, stirring at a constant speed for reaction for 25h, putting the solution into an ice water bath for cooling, adding distilled water until a large amount of precipitates are generated, filtering to remove the solvent, putting the solid mixture into an ether solution, stirring at a constant speed for 12h, filtering to remove the solvent, washing the solid product by using ether and ethanol, and fully drying to prepare the acrylamide grafted modified chitosan microsphere component 3.
(2) Preparing a chitosan modified polyacrylic acid hydrogel adsorption material 3: adding a distilled water solvent and 21 parts of modified chitosan microsphere component 3 into a reaction bottle, performing ultrasonic dispersion treatment on the solution at 50 ℃ for 1.5h with the ultrasonic frequency of 30KHz, adding 27 parts of acrylic acid, 22-methacrylic acid, 5 parts of cross-linking agent N, N-methylene bisacrylamide and 15 parts of initiator potassium persulfate, placing the reaction bottle into a constant-temperature water bath kettle, heating to 65 ℃, reacting for 20h, performing vacuum drying on the solution to remove the solvent, placing a solid product into a dialysis bag, adding the distilled water solvent to perform a dialysis impurity removal process, and preparing the chitosan modified polyacrylic acid hydrogel adsorption material 3.
Example 4
(1) Preparing a modified chitosan microsphere component 4: adding 8 mass percent acetic acid solution into a reaction bottle, adding chitosan, stirring and dissolving, placing the reaction bottle in an ultrasonic dispersion instrument, carrying out ultrasonic dispersion treatment for 1h, adding a liquid paraffin solvent into the reaction bottle, placing the reaction bottle in a constant-temperature water bath kettle, heating to 55 ℃, stirring for 10min at constant speed by using an automatic stirrer, wherein the automatic stirrer comprises a stirring rod, a power wire is fixedly connected inside the stirring rod, a waterproof sleeve is fixedly connected inside the stirring rod, one end of the power wire is fixedly connected with a plug, a rotator is movably connected at the lower end of the stirring rod and is fixedly connected with the power wire, a limiting rod is arranged inside the rotator, threads are arranged on the surface of the limiting rod, the limiting rod is movably connected with a threaded ring, a stirring fan sheet is fixedly connected with the threaded ring, adding emulsifier Tween 20, stirring at constant speed for emulsification for 40min, heating to 60 ℃, adding cross-linking agent glutaraldehyde, stirring at a constant speed for reaction for 1h, then adding sodium hydroxide, adjusting the pH of the solution to 11, heating to 85 ℃, adding accelerator epichlorohydrin, wherein the mass ratio of chitosan to tween-20 to glutaraldehyde to epichlorohydrin is 1:0.12:0.4:0.8, stirring at a constant speed for reaction for 6h, placing the solution in an ice-water bath for cooling, adding distilled water until a large amount of precipitate is generated, filtering to remove the solvent, sequentially adding a solid mixture into an ether solution, stirring at a constant speed for 15h, filtering to remove the solvent, washing the solid product with ether and ethanol, and fully drying;
putting the solid product into an ethanol solvent, adding acrylamide, a cross-linking agent glutaraldehyde and a condensing agent 2- (7-benzotriazole oxide) -N, N, N ', N' -tetramethylurea hexafluorophosphate, then adding a liquid paraffin solvent and an emulsifier Tween 20, wherein the mass ratio of the solid product, the acrylamide, the glutaraldehyde and the 2- (7-benzotriazole oxide) -N, N, N ', N' -tetramethylurea hexafluorophosphate is 1:8:6:5, putting a reaction bottle into a constant-temperature water bath, heating to 100 ℃, stirring at a constant speed for reaction for 30h, putting the solution into an ice water bath for cooling, adding distilled water until a large amount of precipitates are generated, filtering to remove the solvent, putting the solid mixture into an ether solution, stirring at a constant speed for 15h, filtering to remove the solvent, washing the solid product by using ether and ethanol, and fully drying to prepare the acrylamide grafted modified chitosan microsphere component 4.
(2) Preparing a chitosan modified polyacrylic acid hydrogel adsorption material 4: adding a distilled water solvent and 25 parts of modified chitosan microsphere component 4 into a reaction bottle, performing ultrasonic dispersion treatment on the solution at 60 ℃ for 2 hours at the ultrasonic frequency of 25KHz, adding 28.5 parts of acrylic acid, 23 parts of methacrylic acid, 5.5 parts of cross-linking agent N, N-methylene bisacrylamide and 18 parts of initiator potassium persulfate, placing the reaction bottle in a constant-temperature water bath kettle, heating to 50 ℃, reacting for 24 hours, performing vacuum drying on the solution to remove the solvent, placing a solid product in a dialysis bag, adding the distilled water solvent to perform a dialysis impurity removal process, and preparing the chitosan modified polyacrylic acid hydrogel adsorption material 4.
Example 5
(1) Preparing a modified chitosan microsphere component 5: adding 8 mass percent acetic acid solution into a reaction bottle, adding chitosan, stirring and dissolving, placing the reaction bottle in an ultrasonic dispersion instrument, carrying out ultrasonic dispersion treatment for 2 hours, adding a liquid paraffin solvent into the reaction bottle, placing the reaction bottle in a constant-temperature water bath kettle, heating to 55 ℃, stirring for 20 minutes at constant speed by using an automatic stirrer, wherein the automatic stirrer comprises a stirring rod, a power wire is fixedly connected inside the stirring rod, a waterproof sleeve is fixedly connected inside the stirring rod, one end of the power wire is fixedly connected with a plug, a rotator is movably connected at the lower end of the stirring rod and is fixedly connected with the power wire, a limiting rod is arranged inside the rotator, threads are arranged on the surface of the limiting rod, the limiting rod is movably connected with a threaded ring, a stirring fan sheet is fixedly connected with the threaded ring, adding emulsifier Tween 20, stirring at constant speed for emulsification for 40 minutes, heating to 70 ℃, adding cross-linking agent glutaraldehyde, stirring at a constant speed for reaction for 2h, then adding sodium hydroxide, adjusting the pH of the solution to 11, heating to 85 ℃, adding accelerator epichlorohydrin, wherein the mass ratio of chitosan to tween-20 to glutaraldehyde to epichlorohydrin is 1:0.12:0.6:1.4, stirring at a constant speed for reaction for 6h, placing the solution in an ice-water bath for cooling, adding distilled water until a large amount of precipitate is generated, filtering to remove the solvent, sequentially adding a solid mixture into an ether solution, stirring at a constant speed for 15h, filtering to remove the solvent, washing the solid product with ether and ethanol, and fully drying;
putting the solid product into an ethanol solvent, adding acrylamide, a cross-linking agent glutaraldehyde and a condensing agent 2- (7-benzotriazole oxide) -N, N, N ', N' -tetramethylurea hexafluorophosphate, then adding a liquid paraffin solvent and an emulsifier Tween 20, wherein the mass ratio of the solid product, the acrylamide, the glutaraldehyde and the 2- (7-benzotriazole oxide) -N, N, N ', N' -tetramethylurea hexafluorophosphate is 1:15:6:10, putting a reaction bottle into a constant-temperature water bath, heating to 140 ℃, stirring at a constant speed for reaction for 30h, putting the solution into an ice water bath for cooling, adding distilled water until a large amount of precipitates are generated, filtering to remove the solvent, putting the solid mixture into an ether solution, stirring at a constant speed for 15h, filtering to remove the solvent, washing the solid product by using ether and ethanol, and fully drying to prepare the acrylamide grafted modified chitosan microsphere component 5.
(2) Preparing a chitosan modified polyacrylic acid hydrogel adsorption material 5: adding a distilled water solvent and 20 parts of modified chitosan microsphere component 5 into a reaction bottle, performing ultrasonic dispersion treatment on the solution at 60 ℃ for 2 hours at the ultrasonic frequency of 35KHz, adding 30 parts of acrylic acid, 24 methacrylic acid, 6 parts of cross-linking agent N, N-methylene bisacrylamide and 20 parts of initiator potassium persulfate, placing the reaction bottle into a constant-temperature water bath kettle, heating to 80 ℃, reacting for 24 hours, drying the solution in vacuum to remove the solvent, placing a solid product into a dialysis bag, adding the distilled water solvent to perform dialysis and impurity removal, and preparing the chitosan modified polyacrylic acid hydrogel adsorbing material 5.
Cu in an amount of 2% by mass respectively2+Adding the chitosan modified polyacrylic acid hydrogel adsorbing materials in the examples 1-5 into the aqueous solution, standing for 24h, and detecting Cu by using a 760CRT dual-beam ultraviolet-visible spectrophotometer2+Residual concentration of (C), adsorption rate ═ Cu2+Total concentration-Cu2+Residual concentration)/Cu2+The total concentration, the test standard is GB/T10533-.
In summary, according to the chitosan modified polyacrylic acid hydrogel adsorption material, glutaraldehyde is used as a cross-linking agent, epichlorohydrin is used as an accelerating agent to form chitosan microspheres with smaller particle size and larger specific surface area, a condensing agent 2- (7-benzotriazole oxide) -N, N, N ', N' -tetramethylurea hexafluorophosphate is used to perform condensation reaction on amino in chitosan and amino in acrylamide and a cross-linking agent glutaraldehyde respectively, acrylamide grafted chitosan microspheres are successfully realized, then free radical polymerization is performed to polymerize acrylamide, acrylic acid and methacrylic acid to form a polypropylene-based hydrogel material, chitosan is grafted and copolymerized with a polypropylene-based polymer in a chemical bonding manner to form a composite hydrogel material, so that the dispersibility and compatibility of chitosan in the polypropylene-based polymer are improved, greatly enhances the chemical and physical stability of the hydrogel material, swells in water, and has stable matrix and difficult decomposition.
The chitosan contains a large amount of amino and hydroxyl groups, the polypropylene-based polymer also contains rich amino and carboxyl groups, and the chitosan can perform a complex reaction with heavy metal ions such as copper, cadmium, chromium and the like, and cationic dyes such as methylene blue and the like, so that the effects of adsorbing pollutants and purifying water sources are achieved.
Claims (8)
1. The chitosan modified polyacrylic acid hydrogel adsorption material comprises the following formula raw materials and components in parts by weight, and is characterized in that: 25-30 parts of acrylic acid, 20-24 parts of methacrylic acid, 20-42 parts of modified chitosan microspheres, 10-20 parts of initiator and 3-6 parts of cross-linking agent.
2. The chitosan modified polyacrylic acid hydrogel adsorbent material of claim 1, wherein: the initiator is potassium persulfate.
3. The chitosan modified polyacrylic acid hydrogel adsorbent material of claim 1, wherein: the cross-linking agent is N, N-methylene bisacrylamide.
4. The chitosan modified polyacrylic acid hydrogel adsorbent material of claim 1, wherein: the preparation method of the modified chitosan microsphere comprises the following steps:
(1) adding chitosan into acetic acid solution with the mass fraction of 4-8%, stirring and dissolving, performing ultrasonic dispersion treatment on the solution for 1-2 hours, adding a liquid paraffin solvent, heating to 45-55 ℃, uniformly stirring for 10-20 minutes by using an automatic stirrer, adding an emulsifier Tween 20, performing an emulsification process for 20-40 minutes, heating to 60-70 ℃, adding a cross-linking agent glutaraldehyde, reacting for 1-2 hours, then adding sodium hydroxide, adjusting the pH of the solution to 10-11, heating to 75-85 ℃, adding an accelerant epichlorohydrin, reacting for 4-6 hours, cooling the solution, adding distilled water until a large amount of precipitate is generated, filtering, washing and drying;
(2) putting the solid product into an ethanol solvent, adding acrylamide, a cross-linking agent glutaraldehyde and a condensing agent 2- (7-benzotriazole oxide) -N, N, N ', N' -tetramethylurea hexafluorophosphate, then adding a liquid paraffin solvent and an emulsifier Tween 20, heating the solution to 100 ℃ for 140 ℃, reacting for 20-30h, cooling the solution, adding distilled water until a large amount of precipitates are generated, filtering, washing and drying to prepare the acrylamide grafted modified chitosan microsphere.
5. The chitosan modified polyacrylic acid hydrogel adsorbent material of claim 4, wherein: the mass ratio of the chitosan, the Tween 20, the glutaraldehyde and the epichlorohydrin in the step (1) is 1:0.08-0.12:0.4-0.6: 0.8-1.4.
6. The chitosan modified polyacrylic acid hydrogel adsorbent material of claim 4, wherein: the mass ratio of the solid product in the step (2), acrylamide, glutaraldehyde and 2- (7-benzotriazole oxide) -N, N, N ', N' -tetramethylurea hexafluorophosphate is 1:8-15:3-6: 5-10.
7. The chitosan modified polyacrylic acid hydrogel adsorbent material of claim 4, wherein: the automatic stirrer comprises a stirring rod, a power line fixedly connected inside the stirring rod, a waterproof sleeve fixedly connected inside the stirring rod, a power line one end and a plug fixedly connected with the stirring rod, a rotator movably connected at the lower end of the stirring rod, a rotator fixedly connected with the power line, a limiting rod arranged inside the rotator, a limiting rod surface provided with threads, a limiting rod movably connected with a threaded ring, and a stirring fan blade fixedly connected with the threaded ring.
8. The chitosan modified polyacrylic acid hydrogel adsorbent material of claim 1, wherein: the preparation method of the chitosan modified polyacrylic acid hydrogel adsorption material comprises the following steps:
(1) adding 20-42 parts of modified chitosan microspheres into a distilled water solvent, performing ultrasonic dispersion treatment on the solution at 40-60 ℃ for 1-2h with the ultrasonic frequency of 25-35KHz, adding 25-30 parts of acrylic acid, 20-24 parts of methacrylic acid, 3-6 parts of cross-linking agent N, N-methylene bisacrylamide and 10-20 parts of initiator potassium persulfate, heating the solution to 50-80 ℃, reacting for 18-24h, removing the solvent from the solution, and performing dialysis impurity removal on a solid product to prepare the chitosan modified polyacrylic acid hydrogel adsorbing material.
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