A c18 grafted helical honeycomb magnetic polymer composite material, a preparation method and application thereof

Abstract

The application provides a C18 grafted helical honeycomb magnetic polymer composite material and a preparation method and application thereof, and belongs to the technical field of adsorption functional materials. The C18 is grafted to the surface of the polymer material through an organic amine ring-opening reaction with the magnetic polymer as a matrix, and the helical honeycomb composite material with good magnetism, high C18 loading rate and stable performance is efficiently synthesized. Compared with the prior art, the preparation method is simple, the morphology is controllable, the loaded C18 is to the surface of the composite material, the performance of the material is greatly improved, the material has high stability, and more remarkably, the transformation from the spherical magnetic polymer composite material to the non-spherical (helical honeycomb) magnetic polymer composite material is realized and the material has high adsorption performance, so that the application provides a feasible scheme for the research in the field of non-spherical magnetic polymers.

Description

Technical Field

[0001] This invention relates to the field of adsorption functional materials technology, and in particular to a C18-grafted spiral honeycomb magnetic polymer composite material, its preparation method, and its application. Background Technology

[0002] In recent years, benzene compounds, as a class of organic pollutants containing aromatic structures, have been widely recovered during fossil fuel extraction as solvents for industrial production. When their concentration exceeds a certain level, they pose a threat to the natural environment. Long-term exposure to benzene compounds can cause central and peripheral nervous system disorders. For example, benzene can harm the hematopoietic system, leading to anemia and infections. Long-term exposure can damage hearing, causing hearing loss and endocrine disorders. Toluene can cause permanent damage to the brain and kidneys. Prolonged inhalation can reduce the levels of luteinizing hormone and follicle-stimulating hormone; affect female fertility, increasing the risk of miscarriage; and alter the number of immune cells, damaging the immune system. Xylene is carcinogenic, and long-term exposure may induce malignant tumors. Therefore, removing benzene compounds from wastewater is of great significance to human health.

[0003] Magnetic polymer microspheres have been extensively studied due to their ultra-high adsorption capacity and instantaneous solid-liquid separation ability. Their ease of recovery and low synthesis cost have also attracted widespread attention in practical applications, showing great promise for the adsorption and treatment of organic pollutants in water. Currently, methods for preparing magnetic polymer microspheres include emulsion polymerization, chemical precipitation, suspension polymerization, and dispersion polymerization. However, the microspheres obtained by these methods mostly have a spherical structure. While these magnetic polymer microspheres can achieve separation and purification effects for certain pollutants, they often suffer from low adsorption capacity and slow adsorption rates. Therefore, developing magnetic polymer composite materials with both high adsorption capacity and ultra-fast adsorption capability is an urgent problem to be solved in water treatment applications. Summary of the Invention

[0004] In view of this, the present invention aims to provide a C18-grafted helical honeycomb magnetic polymer composite material, its preparation method, and its application. The C18-grafted helical honeycomb magnetic polymer composite material provided by the present invention has a non-spherical helical honeycomb structure, high adsorption efficiency, and stable adsorption performance, exhibiting excellent separation and purification effects on benzene compounds in the aquatic environment.

[0005] To achieve the above-mentioned objectives, the present invention provides the following technical solution: This invention provides a method for preparing a C18-grafted helical honeycomb magnetic polymer composite material, comprising the following steps: Nano-sized iron oxide, oleic acid, and an alcohol solvent were heated and mixed to obtain oleic acid-coated iron oxide; The oleic acid-coated iron oxide, glycidyl methacrylate, divinylbenzene, dispersant, initiator and organic solvent are mixed and subjected to dispersion polymerization to obtain a magnetic polymer composite material rich in epoxy groups. The epoxy-rich magnetic polymeric composite material was mixed with N,N-dimethyloctadecylamine and an organic solvent to carry out an epoxy-amine polymerization reaction, thereby obtaining a C18-grafted spiral honeycomb magnetic polymeric composite material.

[0006] Preferably, the preparation method of the nano-ferric oxide includes the following steps: Ferric chloride, ethylene glycol, sodium acetate, and polyethylene glycol were mixed and subjected to a solvothermal reaction to obtain nano-iron oxide. The solvothermal reaction is carried out at a temperature of 180~250℃ for a time of 12~16h.

[0007] Preferably, the mass ratio of the nano-ferric oxide to oleic acid is 1:(2~8). The heating and mixing temperature is 65~85℃, and the time is 1~3h.

[0008] Preferably, the mass ratio of oleic acid-coated iron oxide to glycidyl methacrylate and divinylbenzene is (1~4):(2~6):(2~6).

[0009] Preferably, the dispersant is ethylene glycol, and the volume ratio of the organic solvent to the dispersant is (5~9):(2~6). The initiator is azobisisobutyronitrile, and the mass concentration of the initiator in the organic solvent is 0.2%~0.6%.

[0010] Preferably, the dispersion polymerization reaction is carried out at a temperature of 60-90°C for 3-5 hours.

[0011] Preferably, the mass ratio of the epoxy-rich magnetic polymeric composite material to N,N-dimethyloctadecylamine is (2~5):(2~20). The epoxy-amine polymerization reaction is carried out at a temperature of 50~95℃ for 6~12h.

[0012] The present invention provides a C18-grafted helical honeycomb magnetic polymeric composite material prepared by the above preparation method, comprising a magnetic polymeric composite material with a helical honeycomb structure and a surface rich in epoxy groups, and a C18 organic amine grafted onto the surface of the magnetic polymeric composite material. The magnetic polymeric composite material comprises nano-ferric oxide and an epoxy-rich polymer coated on the surface of the nano-ferric oxide.

[0013] This invention provides the application of the above-mentioned C18-grafted spiral honeycomb magnetic polymer composite material in the adsorption of benzene compounds in water.

[0014] Preferably, the benzene series compounds include one or more of benzene, toluene, ethylbenzene, xylene, trimethylbenzene, phenol, and chlorobenzene.

[0015] This invention provides a method for preparing a C18-grafted helical honeycomb magnetic polymeric composite material, comprising the following steps: heating and mixing nano-ferric oxide, oleic acid, and an alcohol solvent to obtain oleic acid-coated ferric oxide; mixing the oleic acid-coated ferric oxide, glycidyl methacrylate, divinylbenzene, a dispersant, an initiator, and an organic solvent to carry out a dispersion polymerization reaction to obtain an epoxy-rich magnetic polymeric composite material; mixing the epoxy-rich magnetic polymeric composite material with N,N-dimethyloctadecylamine and an alcohol solvent to carry out an epoxy-amine polymerization reaction to obtain a C18-grafted helical honeycomb magnetic polymeric composite material. This invention uses a magnetic polymer as a matrix and grafts C18 onto the surface of the polymer material through an organic amine ring-opening reaction, efficiently synthesizing a helical honeycomb composite material with a helical honeycomb structure, good magnetic properties, high C18 loading, and stable performance. Compared with existing technologies, the preparation method provided by this invention is simple and the morphology is controllable. The C18 grafted onto the surface of the composite material greatly improves the material's performance, resulting in high stability. More importantly, it achieves the transformation of the magnetic polymer composite material from spherical to non-spherical (spiral honeycomb) and exhibits highly efficient adsorption performance, providing a feasible solution for research in the field of non-spherical magnetic polymers. The C18-grafted spiral honeycomb magnetic polymer composite material prepared by this invention has a rich porous structure and a large number of alkyl groups on its surface, exhibiting a high adsorption capacity for benzene series compounds in the aquatic environment. It can be used for the removal of benzene series compounds and further separation and purification. In addition, due to its good magnetism, it has an instantaneous solid-liquid separation capability after adsorption, making it easy to separate from the aquatic environment without causing secondary pollution. Attached Figure Description

[0016] Figure 1 Scanning electron microscope image of the C18-grafted spiral honeycomb magnetic polymer composite material prepared in Example 1; Figure 2 Scanning electron microscope image of the C18-grafted spiral honeycomb magnetic polymer composite material prepared in Example 3; Figure 3 Scanning electron microscope image of the C18-grafted spiral honeycomb magnetic polymer composite material prepared in Example 4; Figure 4 Morphology of the composite material prepared without the addition of ethylene glycol; Figure 5 The image shows the morphology of the composite material prepared using n-butanol as a dispersant. Figure 6 The maximum adsorption capacity of each compound for the C18-grafted spiral honeycomb magnetic polymer composite material; Figure 7 Adsorption rate diagram of C18-grafted spiral honeycomb magnetic polymer composite material. Detailed Implementation

[0017] This invention provides a method for preparing a C18-grafted helical honeycomb magnetic polymer composite material, comprising the following steps: Nano-sized iron oxide, oleic acid, and an alcohol solvent were heated and mixed to obtain oleic acid-coated iron oxide; The oleic acid-coated iron oxide, glycidyl methacrylate, divinylbenzene, dispersant, initiator and organic solvent are mixed and subjected to dispersion polymerization to obtain a magnetic polymer composite material rich in epoxy groups. The epoxy-rich magnetic polymeric composite material was mixed with N,N-dimethyloctadecylamine and an alcohol solvent to carry out an epoxy-amine polymerization reaction, thereby obtaining a C18-grafted spiral honeycomb magnetic polymeric composite material.

[0018] This invention involves heating and mixing nano-ferric oxide, oleic acid, and an alcohol solvent to obtain oleic acid-coated ferric oxide. In this invention, the nano-ferric oxide is preferably black nano-ferric oxide; the particle size of the nano-ferric oxide is preferably 100-400 nm, more preferably 300 nm.

[0019] This invention does not have specific requirements regarding the source of the nano-ferric oxide; commercially available nano-ferric oxide or self-prepared nano-ferric oxide can be used. When self-preparing nano-ferric oxide, the preparation method preferably includes the following steps: Ferric chloride, ethylene glycol, sodium acetate, and polyethylene glycol were mixed and subjected to a solvothermal reaction to obtain nano-iron oxide.

[0020] In this invention, the preferred mass ratio of ferric chloride to ethylene glycol is (4~8) g : (80~160) mL, more preferably 4 g : 80 mL. In this invention, the preferred mass ratio of ferric chloride, sodium acetate, and polyethylene glycol is (4~8) g : (8~16) g : (1~4) g, more preferably 4 g : 8 g : 1 g.

[0021] In this invention, the solvothermal reaction is preferably carried out in a reaction vessel, the temperature of the solvothermal reaction is preferably 180~250℃, more preferably 230℃, and the time is 12~16h, more preferably 14h.

[0022] Following the solvothermal reaction, the present invention preferably performs post-treatment on the resulting solvothermal reaction solution, the post-treatment preferably including the following steps: The solvothermal reaction solution was cooled to room temperature, and magnetic solid-liquid separation was performed. The resulting solid was then washed and dried.

[0023] In this invention, the detergent used for washing is preferably ethanol and water in sequence; the drying is preferably vacuum drying, the drying temperature is preferably 70°C, and the drying time is preferably 12 hours.

[0024] In this invention, the mass ratio of nano-ferric oxide to oleic acid is preferably 1:(2~8), more preferably 1:5. In this invention, the alcohol solvent is preferably anhydrous ethanol, and the mass ratio of nano-ferric oxide to anhydrous ethanol is preferably (3~6) g:(300~500) mL, more preferably 3 g:300 mL. Before heating, this invention preferably involves ultrasonic dispersion of the nano-ferric oxide, oleic acid, and alcohol solvent. In this invention, oleic acid can make ferric oxide hydrophobic, thereby increasing the rate of subsequent polymerization reactions.

[0025] In this invention, the heating and mixing is preferably carried out in a water bath, and the heating and mixing temperature is preferably 65~85℃, more preferably 75℃; the time is preferably 1~3h, more preferably 2h. In this invention, the heating and mixing is preferably carried out under mechanical stirring conditions.

[0026] After obtaining the oleic acid-coated iron oxide, the present invention mixes the oleic acid-coated iron oxide, glycidyl methacrylate, divinylbenzene, dispersant, initiator, and organic solvent to carry out a dispersion polymerization reaction to obtain a magnetic polymer composite material rich in epoxy groups. In the present invention, the preferred mass ratio of the oleic acid-coated iron oxide to glycidyl methacrylate and divinylbenzene is (1~4):(2~6):(2~6), more preferably (2~3):(3~5):(3~5), and even more preferably 3:3:3.

[0027] In this invention, the dispersant is preferably ethylene glycol, and the organic solvent is preferably acetonitrile. In this invention, the volume ratio of the organic solvent to the dispersant is preferably (5~9):(2~6), specifically preferably 9:2, 8:3, 7:4, 6:5, or 5:6, and more preferably 9:2 or 8:3.

[0028] In this invention, the initiator is preferably azobisisobutyronitrile (AIBN), and the mass fraction of the initiator in the organic solvent is preferably 0.2% to 0.6%, more preferably 0.3% to 0.5%.

[0029] In this invention, the preferred mixing method is as follows: first, oleic acid coated with ferric oxide is mixed with an organic solvent, and then a dispersant, glycidyl methacrylate, and divinylbenzene monomer are added and ultrasonically dispersed. In this invention, the ultrasonic dispersion is preferably performed in an ultrasonic cleaner; the ultrasonic dispersion time is preferably 5-15 minutes, more preferably 10 minutes.

[0030] In this invention, the dispersion polymerization reaction is preferably carried out under water bath conditions, the temperature of the dispersion polymerization reaction is preferably 60~90℃, more preferably 70~80℃, and the time is preferably 3~5h, more preferably 4h. This invention uses an ultrasonic cleaner for ultrasonic dispersion to mix the entire reaction system, and adds ethylene glycol as a dispersant to make the entire system more uniformly dispersed, achieving controllable preparation of the morphology of the magnetic composite material, transforming it from spherical to non-spherical, greatly improving the synthesis efficiency of the magnetic polymer.

[0031] Following the dispersion polymerization reaction, the present invention preferably performs post-processing on the obtained dispersion polymerization product, the post-processing preferably including the following steps: The polymerization dispersion reaction product was cooled to room temperature, and solid-liquid separation was performed. The resulting solid was then washed and dried.

[0032] In this invention, the solid-liquid separation is preferably magnetic separation, and the magnet used for magnetic separation is preferably a square magnet. In this invention, the washing preferably includes sequential ethanol washing and water washing. In this invention, the drying is preferably vacuum drying; the drying temperature is preferably 70°C; and the drying time is preferably 12 hours.

[0033] After obtaining the epoxy-rich magnetic polymeric composite material, the present invention mixes the epoxy-rich magnetic polymeric composite material with N,N-dimethyloctadecylamine and an organic solvent to carry out an epoxy-amine polymerization reaction, thereby obtaining a C18-grafted helical honeycomb magnetic polymeric composite material. In the present invention, the organic solvent is preferably one of acetonitrile, methanol, and N,N-dimethylamide, and more preferably methanol.

[0034] In this invention, the mass ratio of the epoxy-rich magnetic polymer composite material to N,N-dimethyloctadecylamine is preferably (2~5):(2~20), more preferably (2~5):(5~10), and even more preferably (3~4):(6~8).

[0035] In this invention, the epoxy-amine polymerization reaction is preferably carried out in a constant-temperature water bath. The temperature of the epoxy-amine polymerization reaction is 50~95℃, more preferably 60~90℃, and even more preferably 70~80℃. The time of the epoxy-amine polymerization reaction is preferably 6~12h, more preferably 8~10h. The constant-temperature water bath heating method used in this invention ensures uniform heating of the entire reaction system and precise control of the reaction, greatly improving the synthesis efficiency of C18-grafted spiral honeycomb magnetic polymer composite materials.

[0036] Following the epoxy-amine polymerization reaction, the present invention preferably performs post-treatment on the resulting epoxy-amine polymerization reaction solution, the post-treatment preferably including the following steps: The epoxy-amine polymerization reaction solution was cooled to room temperature, and solid-liquid separation was performed. The resulting solid was then washed and dried.

[0037] In this invention, the solid-liquid separation is preferably magnetic separation, and the magnet used for magnetic separation is preferably a square magnet. In this invention, the washing preferably includes sequential ethanol washing and water washing. In this invention, the drying is preferably vacuum drying; the drying temperature is preferably 70°C; and the drying time is preferably 12 hours.

[0038] This invention provides a C18-grafted helical honeycomb magnetic polymeric composite material prepared by the above-described method, comprising a magnetic polymeric composite material with a surface rich in epoxy groups having a helical honeycomb structure, and a C18 organic amine grafted onto the surface of the magnetic polymeric composite material. In this invention, the magnetic polymeric composite material comprises nano-ferric oxide and an epoxy-rich polymer coating the surface of the nano-ferric oxide.

[0039] In this invention, the surface of the C18-grafted helical honeycomb magnetic polymer composite material contains abundant pore structures and a large number of C18 alkyl groups. In this invention, the specific surface area of ​​the C18-grafted helical honeycomb magnetic polymer composite material is preferably 60.38~70.21 m². 2 / g, with a porosity preferably of 35%~45% and an average pore size preferably of 83.19~104.6nm.

[0040] As a specific embodiment of the present invention, the C18 grafted spiral honeycomb magnetic polymer composite material is gray in color.

[0041] This invention provides the application of the above-mentioned C18-grafted helical honeycomb magnetic polymer composite material in the adsorption of benzene series compounds in water. In this invention, the benzene series compounds preferably include one or more of benzene, toluene, ethylbenzene, xylene, trimethylbenzene, phenol, and chlorobenzene.

[0042] In this invention, the method of application preferably includes the following steps: The C18-grafted spiral honeycomb magnetic polymer composite material is mixed with the water to be treated for adsorption, and the adsorbed water is then magnetically separated.

[0043] In this invention, the concentration of benzene compounds in the water to be treated is preferably 100-800 mg / L.

[0044] In this invention, the preferred ratio of the volume of the water to be treated to the mass of the C18-grafted spiral honeycomb magnetic polymer composite material is (20~100) mL: (0.02~0.1) g, more preferably 50 mL: 0.05 g.

[0045] In this invention, the adsorption is preferably carried out under oscillation conditions, and the adsorption time is preferably ≥12h, more preferably 12~48h.

[0046] In this invention, the magnetic separation time is preferably 5 to 10 minutes, more preferably 6 to 8 minutes.

[0047] In this invention, after magnetic separation, the adsorbed water is preferably analyzed by ultra-fast liquid chromatography to obtain the content of residual benzene compounds in the water. This invention does not have special requirements for the specific conditions of the ultra-fast liquid chromatography; methods familiar to those skilled in the art can be used.

[0048] The following detailed description, in conjunction with embodiments, illustrates the C18-grafted spiral honeycomb magnetic polymer composite material, its preparation method, and its applications. However, these descriptions should not be construed as limiting the scope of protection of this invention.

[0049] Examples 1-8 The preparation method of C18 grafted helical honeycomb magnetic polymer composite material adopts the following steps: (1) 4g of ferric chloride, 80mL of ethylene glycol, 8g of sodium acetate and 1g of polyethylene glycol were added to the reaction vessel in sequence. The reaction was carried out at 230℃ for 12h. After the reaction was completed, the solution was cooled to room temperature, poured into a beaker and collected after solid-liquid separation by magnet. The precipitate was washed with ethanol and water in sequence and dried under vacuum at 70℃ for 12h to obtain black nano-iron oxide. (2) Add black nano-ferric oxide and 300 mL of anhydrous ethanol into a three-necked flask and disperse by ultrasonication; heat the reaction in a constant temperature water bath, slowly add oleic acid, adjust the temperature to 75℃, and mechanically stir for 2 hours at this temperature to obtain oleic acid-coated ferric oxide. (3) Dissolve the vacuum-dried oleic acid coated iron oxide in acetonitrile solution and transfer it to a three-necked flask. Add ethylene glycol, glycidyl methacrylate and divinylbenzene monomer in sequence and ultrasonically disperse for 10 min. Then dissolve the initiator azobisisobutyronitrile in acetonitrile solution and slowly add it dropwise to the three-necked flask. Stir mechanically and adjust the temperature to 80°C to carry out dispersion polymerization reaction. After dispersion polymerization is completed, cool naturally to room temperature. Pour the solution into a beaker and collect the precipitate after solid-liquid separation by magnet. Wash the precipitate with ethanol and water in sequence. Vacuum dry at 70°C for 12 h to obtain a magnetic polymer composite material rich in epoxy groups. (4) The obtained epoxy-rich magnetic polymer composite material was added to a three-necked flask, dissolved in methanol organic solution, sealed with a polytetrafluoroethylene screw stopper, and ultrasonically dispersed for 10 min. Then the three-necked flask was transferred to a water bath for heating, and N,N-dimethyloctadecylamine was slowly added dropwise. The reaction temperature was set at 85℃, and the epoxy-amine polymerization reaction was carried out at this temperature for 10 h. After the reaction was completed, it was naturally cooled to room temperature. The solution was poured into a beaker and the precipitate was collected after solid-liquid separation by a magnet. The precipitate was washed with methanol and water in sequence, and vacuum dried at 70℃ for 12 h to finally obtain a gray C18 grafted spiral honeycomb magnetic polymer composite material.

[0050] The amounts of raw materials used in Examples 1-8 are shown in Table 1.

[0051] Table 1. Amount of raw materials used in Examples 1-8

[0052] Comparative Example 1 Compared with Example 1, the difference is that ethylene glycol is not added as a dispersant, but all other operations are the same.

[0053] Comparative Example 2 Compared with Example 1, the difference is that ethylene glycol is replaced with n-butanol, and all other operations are the same.

[0054] Structural characterization Scanning electron microscope image of the C18-grafted helical honeycomb magnetic polymer composite material prepared in Example 1 is shown below. Figure 1 As shown. By Figure 1 As can be seen, the C18-grafted spiral honeycomb magnetic polymer composite material prepared by this invention has a regular morphology and exhibits a distinct honeycomb spiral structure.

[0055] Compared with the C18-grafted spiral honeycomb magnetic polymer composite material prepared in Example 1, the composite materials prepared in Examples 2-8 gradually exhibit a spherical shape based on the spiral honeycomb structure. The morphologies of the composite materials obtained in Examples 3 and 4 are as follows: Figure 2 , 3As shown, the surface of the composite material gradually becomes smooth, rich in alkyl groups, and has a high adsorption capacity for benzene compounds in environmental water samples, enabling efficient removal and rapid separation of benzene compounds.

[0056] Figure 4 , 5 The images show the morphology of the composite materials prepared without ethylene glycol (Comparative Example 1) and with n-butanol as a dispersant (Comparative Example 2), respectively. It can be seen that when ethylene glycol is not used, the material exhibits obvious agglomeration and poor dispersion. When n-butanol is used as a dispersant, there is a tendency for the material to form spherical shapes, but this is not obvious.

[0057] Performance testing (1) The high-efficiency adsorption, removal and purification performance of C18-grafted spiral honeycomb magnetic polymer composite material for benzene series compounds in environmental water samples was evaluated. The method is as follows: Weigh 1, 2, 3, 5, 8, and 10 mg of benzene, toluene, ethylbenzene, xylene, trimethylbenzene, phenol, and chlorobenzene standards into 100 mL volumetric flasks, dissolve them in a small amount of methanol, and dilute to the mark with water to prepare standard solutions of 100, 200, 300, 500, 800, and 1000 mg / L, respectively. Add 40 mL of the prepared solution to a round-bottom flask, then add 40 mg of the C18-grafted spiral honeycomb magnetic polymer composite material prepared in Example 1. After shaking and adsorption for 12 h, solid-liquid separation is performed by magnet, and the supernatant is quantitatively analyzed by ultra-fast liquid chromatography.

[0058] Table 2 shows the maximum adsorption capacity and adsorption equilibrium time for different benzene compounds in the C18-grafted spiral honeycomb magnetic polymer composite material.

[0059] Table 2. Maximum adsorption capacity and time to adsorption equilibrium for different benzene compounds in C18-grafted spiral honeycomb magnetic polymeric composite materials.

[0060] Figure 6 The maximum adsorption capacity of the composite material for each compound was calculated using the Langmuir adsorption isotherm. It can be seen that the C18-grafted spiral honeycomb magnetic polymer composite material exhibits excellent adsorption performance for various benzene compounds, with maximum saturated adsorption capacities exceeding 300 mg / g.

[0061] Figure 7 Adsorption rate diagram of C18-grafted helical honeycomb magnetic polymer composite material. Figure 5 It can be seen that the C18-grafted spiral honeycomb magnetic polymer composite material can rapidly adsorb each benzene compound within the first 10 minutes and reach equilibrium adsorption within 30 minutes.

[0062] (2) Tables 3 and 4 show the maximum adsorption capacity and equilibrium time of different benzene compounds for the magnetic polymer composite material prepared without the addition of ethylene glycol and the composite material prepared using n-butanol as a dispersant.

[0063] Table 3. Maximum adsorption capacity and time to adsorption equilibrium for different benzene compounds in the composite material without the addition of ethylene glycol.

[0064] Table 4. Maximum adsorption capacity and time to adsorption equilibrium for different benzene compounds in composite materials using n-butanol as dispersant.

[0065] It is evident that without a dispersant, the adsorption capacity of the material for benzene series compounds is <400 mg / g. When n-butanol is used as a dispersant, the adsorption capacity of the composite material shows only a significant improvement. However, the composite material prepared using ethylene glycol as a dispersant exhibits a substantial improvement in the maximum saturated adsorption capacity for each benzene series compound compared to the other two materials, with the maximum adsorption capacity for benzene reaching 732.34 mg / g. Therefore, the C18-grafted spiral honeycomb magnetic polymer composite material provided by this invention possesses ultra-high adsorption capacity and ultra-fast adsorption capability for benzene series compounds in aquatic environments.

[0066] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for preparing a C18-grafted helical honeycomb magnetic polymer composite material, comprising the following steps: Nano-sized iron oxide, oleic acid, and an alcohol solvent were heated and mixed to obtain oleic acid-coated iron oxide; The oleic acid-coated iron oxide, glycidyl methacrylate, divinylbenzene, dispersant, initiator and organic solvent are mixed and subjected to dispersion polymerization to obtain a magnetic polymer composite material rich in epoxy groups. The epoxy-rich magnetic polymeric composite material was mixed with N,N-dimethyloctadecylamine and an organic solvent to carry out an epoxy-amine polymerization reaction, thereby obtaining a C18-grafted spiral honeycomb magnetic polymeric composite material. The mass ratio of oleic acid-coated iron oxide to glycidyl methacrylate and divinylbenzene is (1~4):(2~6):(2~6). The volume ratio of the organic solvent to the dispersant is (5~9):(2~6); The mass ratio of the epoxy-rich magnetic polymeric composite material to N,N-dimethyloctadecylamine is (2~5):(2~20).

2. The preparation method according to claim 1, characterized in that, The preparation method of the nano-ferric oxide includes the following steps: Ferric chloride, ethylene glycol, sodium acetate, and polyethylene glycol were mixed and subjected to a solvothermal reaction to obtain nano-iron oxide. The solvothermal reaction is carried out at a temperature of 180~250℃ for a time of 12~16h.

3. The preparation method according to claim 1, characterized in that, The mass ratio of nano-ferric oxide to oleic acid is 1:(2~8). The heating and mixing temperature is 65~85℃, and the time is 1~3h.

4. The preparation method according to claim 1, characterized in that, The dispersant is ethylene glycol, the initiator is azobisisobutyronitrile, and the mass concentration of the initiator in the organic solvent is 0.2%~0.6%.

5. The preparation method according to claim 1, characterized in that, The dispersion polymerization reaction is carried out at a temperature of 60~90℃ for 3~5 hours.

6. The preparation method according to claim 1, characterized in that, The epoxy-amine polymerization reaction is carried out at a temperature of 50~95℃ for 6~12h.

7. A C18-grafted spiral honeycomb magnetic polymeric composite material prepared by the preparation method according to any one of claims 1 to 6, comprising a magnetic polymeric composite material having a spiral honeycomb structure and a surface rich in epoxy groups, and a C18 organic amine grafted onto the surface of the magnetic polymeric composite material; The magnetic polymeric composite material comprises nano-ferric oxide and an epoxy-rich polymer coated on the surface of the nano-ferric oxide.

8. The application of the C18-grafted spiral honeycomb magnetic polymeric composite material of claim 7 in the adsorption of benzene compounds in water.

9. The application according to claim 8, characterized in that, The benzene series compounds include one or more of benzene, toluene, ethylbenzene, xylene, trimethylbenzene, phenol, and chlorobenzene.

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