Flame-retardant super-hydrophobic magnetic photo-thermal sponge for oil-water separation and preparation method
By preparing superhydrophobic magnetic photothermal sponge, the problems of low absorption efficiency and flammability in oil-water separation are solved, and efficient and safe oil-water separation effect is achieved, which is suitable for oil spill treatment in complex environments.
Patent Information
- Application Number
- CN202510744138.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-05
- Publication Date
- 2025-08-15
AI Technical Summary
Existing polyurethane sponges lack selective absorption capacity in oil-water separation, are flammable and have low absorption efficiency, and are difficult to effectively deal with complex and high viscosity oil spills, which poses a fire risk.
The novel flame retardant AH/Fe-MOF-P was prepared by in-situ growth and chemical grafting methods, and a superhydrophobic magnetic photothermal sponge was constructed by phytic acid modified polyurethane sponge, combined with magnetic Fe3O4 powder and PDMS curing system, and a superhydrophobic magnetic photothermal sponge was constructed to achieve flame retardant, magnetic and superhydrophobicity.
The prepared superhydrophobic magnetic photothermal sponge has excellent flame retardancy, magnetism and superhydrophobicity. It can efficiently absorb high-concentration thick oil, have high separation efficiency, high reuse rate, and self-extinguishing within 2 seconds to prevent fire. It is suitable for oil-water separation in complex environments.
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Figure CN120484330A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of oil-water separation materials, and specifically discloses a flame-retardant super-hydrophobic magnetic photothermal sponge for oil-water separation and a preparation method thereof. Background Art
[0002] During offshore oil exploration and development and oil product transportation, oil spills may occur, causing serious environmental impacts. The handling of offshore oil spills involves multiple aspects, including environmental and safety, and has attracted increasing attention.
[0003] Traditional oil spill treatment strategies, such as in-situ incineration, chemical dispersion, and biodegradation, are not widely used due to limitations such as high energy consumption, low separation efficiency and recovery rates, and the risk of secondary pollution. Physical adsorption, a commonly used oil-water separation technology, has gained widespread recognition due to its advantages, including high separation efficiency, low cost, and environmental friendliness.
[0004] Among physical adsorption materials, polyurethane sponge (PU) is currently a hot topic in the field of oil-water separation due to its unique three-dimensional structure, high porosity, non-toxicity and excellent elasticity. However, polyurethane sponge is an amphiphilic material and lacks selective absorption capacity. Therefore, it is necessary to modify the surface of polyurethane sponge to make it superhydrophobic so that it can be used in the field of oil-water separation. In addition, the flammable polyurethane sponge poses a potential fire risk during actual use; since polyurethane sponge cannot achieve directional oil absorption, it will bring many operational inconveniences when facing special and complex oil spill treatment; for high-viscosity heavy oil, polyurethane sponge has many problems such as low absorption efficiency. Therefore, it is necessary to design and prepare a photothermal superhydrophobic polyurethane sponge that is flame retardant and magnetic and can efficiently absorb heavy oil. Summary of the Invention
[0005] In order to solve the technical problems pointed out in the background technology section, the present invention provides a green, environmentally friendly, simple and easy-to-operate method to prepare a super-hydrophobic magnetic photothermal sponge with excellent flame retardancy, which is resistant to acid and alkali, resistant to extrusion, has high adsorption capacity, good separation efficiency, and high reusability. The sponge can be mobile and absorb oil by magnetic drive. After burning, the sponge can self-extinguish within 2 seconds to prevent fire. Its photothermal effect can give the sponge the ability to efficiently absorb high-concentration heavy oil.
[0006] Specifically, the present invention discloses a method for preparing a super-hydrophobic magnetic photothermal polyurethane sponge with excellent flame retardancy that can be used for efficient oil-water separation. The method first involves preparing a novel flame retardant, AH / Fe-MOF-P, using an in-situ growth and chemical grafting method. Specifically, Al(OH)3 is surface-modified, and an amino-containing Fe-MOF is grown on the Al(OH)3 surface. This is then chemically grafted with the inorganic phosphorus compound Ca(H2PO4)2, and dried to obtain AH / Fe-MOF-P. The PDMS curing system, Fe3O4, and AH / Fe-MOF-P powder particles are then ultrasonically dispersed in an n-hexane solution. Finally, a polyurethane sponge modified with phytic acid (PA) is immersed in the solution, removed from the solution after ultrasonication, and dried to produce a super-hydrophobic magnetic photothermal sponge with excellent flame retardancy.
[0007] The preparation method of the new flame retardant AH / Fe-MOF-P is as follows: Al(OH)3 is stirred and dispersed in 70mL N,N-dimethylformamide (DMF), FeCl3 and 2-aminoterephthalic acid are added, and the stirring is continued. Then, the mixture is transferred to a polytetrafluoroethylene reactor, reacted at 120℃ for 12h, the reaction solution is centrifuged, washed with DMF and anhydrous ethanol in turn, and dried at 100℃ to obtain brown AH / Fe-MOF crystals; Ca(H2PO4)2 and deionized water are placed in a flask (a round-bottom flask with a capacity of 100mL), stirred at 80℃ for 30min, and then AH / Fe-MOF is added and the stirring reaction is continued for 1h, followed by washing with deionized water and anhydrous ethanol in turn, the precipitate is collected by centrifugation, and dried to obtain AH / Fe-MOF-P.
[0008] The mass ratio of FeCl3, 2-aminoterephthalic acid, and Al(OH)3 is 1:1.1:4;
[0009] The mass ratio of AH / Fe-MOF crystals to Ca(H2PO4)2 is 1:0.8-1.2.
[0010] The method for modifying the original polyurethane sponge with phytic acid PA is as follows: add the phytic acid ethanol solution into a beaker, stir it at room temperature for 20 minutes to dissolve, then add the original polyurethane sponge PU, stir it for 2 hours and then dry it to obtain PA@PU;
[0011] The mass concentration of the phytic acid / ethanol solution is 14 to 28 g / L. If the amount of phytic acid is increased, the phytic acid will acidify the polyurethane sponge and cause pore blockage in the polyurethane sponge.
[0012] The preparation method of super-hydrophobic magnetic photothermal polyurethane sponge with excellent flame retardancy is as follows: PDMS curing system is ultrasonicated in 40 mL of n-hexane for 30 min, appropriate amount of AH / Fe-MOF-P and Fe3O4 powder particles are added and ultrasonicated for 30 min to dissolve, and then 1 cm phytic acid modified PDMS is added.3 After ultrasonic treatment for 1 hour, the sponge was taken out, the excess impregnation liquid was squeezed out with tweezers, and the sponge was dried in a 90°C oven for 4 hours. After drying, it was washed in n-hexane and then dried at 80°C to obtain an excellent flame retardant superhydrophobic magnetic photothermal polyurethane sponge.
[0013] Among them, the mass ratio of PDMS curing system, AH / Fe-MOF-P and Fe3O4 is: 1:0.5-1:0.1-0.2.
[0014] The PDMS curing system uses the commonly used Dow Corning 184 product on the market, which contains a basic component (liquid A) and a curing agent (liquid B). The curing system can be obtained by ultrasonically mixing the curing agent (liquid B) and the basic component (liquid A) in a volume ratio of 1:10.
[0015] The super-hydrophobic magnetic photothermal sponge with excellent flame retardancy prepared by the present invention is used for oil-water separation.
[0016] Compared with the prior art, the present invention has the following advantages:
[0017] 1. The present invention uses phytic acid to modify polyurethane, and then adheres new flame retardant powder particles and magnetic Fe3O4 powder particles to a sponge skeleton through a curing system. Among them, phytic acid and flame retardant powder provide flame retardancy, and Fe3O4 nanoparticles provide magnetism. Both powder particles can construct a certain degree of roughness on the sponge skeleton, and the curing system provides low surface energy, making the sponge superhydrophobic. These raw materials are non-toxic, non-volatile, and free of secondary pollution, and the composite sponge can be produced in batches.
[0018] 2. The super-hydrophobic sponge prepared by the present invention has a hydrophobic angle of up to 155.3°, and the saturated oil absorption of n-hexane and chloroform are 24.2 g / g and 40.3 g / g, respectively. The ten-time separation efficiency of various organic solvents such as n-hexane and chloroform can reach more than 98%. After the sponge is ignited, it can self-extinguish within 2 seconds, preventing the spread of fire and causing no secondary fire.
[0019] 3. The super-hydrophobic sponge prepared by the present invention has good reusability and environmental stability. It can basically maintain its super-hydrophobic state after multiple squeezing and soaking in solutions with different salt concentrations and pH values for 12 hours. The sponge can be moved by magnetic drive, making oil spill cleanup more convenient.
[0020] 4. The super-hydrophobic sponge prepared by the present invention can effectively absorb high-viscosity heavy oil under certain lighting conditions. BRIEF DESCRIPTION OF THE DRAWINGS
[0021] Figure 1(a1) is a state diagram of a water drop on the surface of 1AH / Fe-MOF-P@Fe3O4@PA@PU and the original sponge in the present invention, (a2) is a water contact angle diagram of 1AH / Fe-MOF-P@Fe3O4@PA@PU in the present invention, (a3) is a state diagram of a water drop on the cross-section of 1AH / Fe-MOF-P@Fe3O4@PA@PU in the present invention, (a4) is a picture of the silver mirror phenomenon of 1AH / Fe-MOF-P@Fe3O4@PA@PU in water in the present invention, (a5) is a state diagram of the original sponge in water and 1AH / Fe-MOF-P@Fe3O4@PA@PU in the present invention floating on water, and (a6) is a state diagram of a water drop on 1AH / Fe-MOF-P@Fe3O4@PA@PU in the present invention changing with time.
[0022] Figure 2 This is the FESEM image of the composite sponge AH / Fe-MOF-P@Fe3O4@PA@PU in Example 1 of the present invention.
[0023] Figure 3 This is a flow chart of the adsorption of oil droplets by magnetic drive of the composite sponge AH / Fe-MOF-P@Fe3O4@PA@PU in Example 1 of the present invention.
[0024] Figure 4 This is the total EDS distribution spectrum of the composite sponge AH / Fe-MOF-P@Fe3O4@PA@PU in Example 1 of the present invention.
[0025] Figure 5 This is the selective absorption of n-hexane and chloroform in water by the composite sponge AH / Fe-MOF-P@Fe3O4@PA@PU in Example 1 of the present invention.
[0026] Figure 6 (a1) is the saturated absorption data of the composite sponge AH / Fe-MOF-P@Fe3O4@PA@PU of Example 1 of the present invention to various oils / organic reagents, (a2) is the composite sponge of Example 1 of the present invention
[0027] Ten-cycle absorption data of AH / Fe-MOF-P@Fe3O4@PA@PU for various oil / organic reagents.
[0028] Figure 7 This is the surface temperature change of the composite sponge AH / Fe-MOF-P@Fe3O4@PA@PU in Example 1 of the present invention after 10 light cycles at a light intensity of 10 kW.
[0029] Figure 8(a1-a4) are comparison diagrams of the combustion test experiments of original PU, PA@PU, AH@Fe-MOF@PA@PU and the composite sponge AH@Fe-MOF-P / Fe3O4@PA@PU in Example 1 of the present invention.
[0030] Figure 9 This is a graph showing the hydrophobic angle data of the composite sponge AH / Fe-MOF-P@Fe3O4@PA@PU in Example 1 of the present invention after being soaked in different salt (sodium chloride) concentrations for 12 hours.
[0031] Figure 10 This is a graph showing the hydrophobic angle data of the composite sponge AH / Fe-MOF-P@Fe3O4@PA@PU in Example 1 of the present invention after being soaked in different pH conditions for 12 hours. DETAILED DESCRIPTION
[0032] The present invention will be further described below with reference to the examples, but is not limited thereto.
[0033] 1. Oil / organic solution absorption capacity test
[0034] The oil absorption performance of the prepared composite sponge was tested by soaking it in various oils / organic solvents (such as petroleum ether, n-hexane, n-octane, chloroform, tetrahydrofuran, acetone, benzene, and toluene) for 5 minutes. First, the composite sponge was weighed and recorded as m1, and then immersed in 25 mL of oil or organic solvent for 5 minutes. After reaching mass absorption equilibrium, the sponge was picked out and drained (about 3 seconds) until no excess residual solvent dripped on the surface. The sponge was taken out and weighed as m2. The saturated absorption capacity of the sponge is represented by K, which can be calculated by the following formula: K = (m2-m1) / m1
[0035] 2. Oil-water separation efficiency and reusability test
[0036] The reusability of the composite sponge was tested by repeated absorption-extrusion cycles. The mass of the sponge before oil absorption was recorded as m1. The sponge was immersed in oil or organic solvent at ambient temperature for 5 minutes to saturate the sponge with absorption. The mass of the sponge at this time was recorded as m2. The saturated sponge was placed in a syringe and the syringe was manually pushed to compress the sponge until all the oil adsorbed by the sponge was squeezed out and no oil droplets were separated. The mass of the sponge after desorption was recorded as m3. It was placed in an oven at 60°C for drying for the next cycle. The oil-water separation efficiency was recorded as η, that is:
[0037] η=(m2-m3) / (m2-m1)
[0038] 3. Environmental stability test
[0039] The composite sponge was soaked in NaCl solutions with concentrations of 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, and 3.0% for 12 hours. The sponge was removed and rinsed with anhydrous ethanol (to remove residual particles on the sponge surface), dried, and water contact angle measurements were performed. The composite sponge was soaked in acidic and alkaline solutions with pH values of 1, 3, 5, 7, 9, 11, and 13 for 12 hours. The sponge was removed and rinsed with anhydrous ethanol (to remove residual particles on the sponge surface), dried, and water contact angle measurements were performed.
[0040] In the above implementation methods, three composite sponges were soaked and the average value of the three sets of data was taken to ensure the accuracy of the data.
[0041] Example 1
[0042] (1) Disperse 2g Al(OH)3 in 70mL DMF and stir in a beaker for 30min. Add 0.49g FeCl3 and 0.54g 2-aminoterephthalic acid and continue stirring for 30min. Then transfer the mixture to a 100mL polytetrafluoroethylene reactor and react at 120℃ for 12h. The resulting reaction solution is centrifuged at 3500rmp / min for 15min, and the precipitate is collected and washed three times with DMF and anhydrous ethanol respectively. The washed solid is placed in a vacuum drying oven at 120℃ for 12h to obtain AH / Fe-MOF crystals;
[0043] (2) 0.8 g of Ca(H2PO4)2 and 50 ml of deionized water were placed in a flask and stirred at 80°C and 600 rpm for 30 min. 0.8 g of AH@Fe-MOF was then added and stirred at 80°C for 1 h. After cooling to room temperature, the precipitate was collected by centrifugation and the solid was placed in a vacuum drying oven at 100°C for 12 h to obtain AH / Fe-MOF-P crystals.
[0044] (3) Cut the untreated PU into 1×1×1cm 3 Cubes were prepared and ultrasonically cleaned with ethanol and deionized water for 30 minutes to remove impurities on the surface of PU. After cleaning, the sponge was placed in a 60°C air drying oven for 12 hours. 1.5 g of phytic acid aqueous solution (the mass fraction of phytic acid is 70%) was dissolved in 50 mL of anhydrous ethanol and stirred until completely dissolved. The pretreated PU was added and stirred at 300 rpm for 2 hours. After stirring, the sponge was placed in an 80°C air drying oven for 12 hours to obtain PA@PU;
[0045] (4) Dissolve 0.4 g of Dow Corning 184 product A solution and 0.04 g of Dow Corning 184 product B solution in 40 mL of n-hexane and sonicate for 20 min. Add 0.35 g of AH / Fe-MOF-P and 0.05 g of Fe3O4 and continue sonicating for 20 min until the powder is completely dispersed. Then add PA@PU and continue sonicating for 1 h. Remove the sponge and place it in a 90°C forced air drying oven for 4 h to obtain AH / Fe-MOF-P@Fe3O4@PA@PU.
[0046] The saturated oil absorption of the composite sponge for n-hexane and chloroform is 24.2 g / g and 40.3 g / g, respectively. It self-extinguishes within 2 seconds after ignition, has medium magnetism, and a hydrophobic angle of 155.3°.
[0047] Example 2
[0048] (1) The preparation steps of AH / Fe-MOF were the same as step (1) in Example 1;
[0049] (2) The preparation steps of AH / Fe-MOF-P are the same as step (2) of Example 1;
[0050] (3) Cut the untreated PU into 1×1×1cm 3 Cubes were prepared and ultrasonically cleaned with ethanol and then deionized water for 30 minutes to remove impurities on the PU surface. After cleaning, the sponge was placed in a 60°C air drying oven for 12 hours. 1.0 g of phytic acid aqueous solution (70% by mass of phytic acid) was dissolved in 50 mL of anhydrous ethanol and stirred until completely dissolved. The pretreated PU was added and stirred at 300 rpm for 2 hours. After stirring, the sponge was placed in an 80°C air drying oven for 12 hours to obtain PA@PU.
[0051] (4) The preparation steps of AH / Fe-MOF-P@Fe3O4@PA@PU are the same as those in step (4) of Example 1;
[0052] The saturated oil absorption of the composite sponge for n-hexane and chloroform is 24.4 g / g and 40.5 g / g, respectively. It self-extinguishes within 5 seconds after ignition, has medium magnetic properties, and a hydrophobic angle of 155.1°.
[0053] Example 3
[0054] (1) The preparation steps of AH / Fe-MOF were the same as step (1) in Example 1;
[0055] (2) The preparation steps of AH / Fe-MOF-P are the same as step (2) of Example 1;
[0056] (3) Cut the untreated PU into 1×1×1cm 3Cubes were prepared and ultrasonically cleaned with ethanol and then deionized water for 30 minutes to remove impurities on the PU surface. After cleaning, the sponge was placed in a 60°C forced air drying oven for 12 hours. 2.0 g of phytic acid solution (70%) was dissolved in 50 mL of anhydrous ethanol and stirred until completely dissolved. The pretreated PU was added and stirred at 300 rpm for 2 hours. After stirring, the sponge was placed in an 80°C forced air drying oven for 12 hours to obtain PA@PU.
[0057] (4) The preparation steps of AH / Fe-MOF-P@Fe3O4@PA@PU are the same as those in step (4) of Example 1;
[0058] The saturated oil absorption of the composite sponge for n-hexane and chloroform is 23.2 g / g and 39.5 g / g, respectively. It self-extinguishes within 2 seconds after ignition, has medium magnetism, and a hydrophobic angle of 154.8°.
[0059] Example 4
[0060] (1) The preparation steps of AH / Fe-MOF were the same as step (1) in Example 1;
[0061] (2) The preparation steps of AH / Fe-MOF-P are the same as step (2) of Example 1;
[0062] (3) The preparation steps of PA@PU are the same as step (3) of Example 1;
[0063] (4) Dissolve 0.4 g of Dow Corning 184 product A solution and 0.04 g of Dow Corning 184 product B solution in 40 mL of n-hexane and sonicate for 20 min. Add 0.2 g of AH / Fe-MOF-P and 0.05 g of Fe3O4 and continue sonicating for 20 min until the powder is completely dispersed. Then add PA@PU and continue sonicating for 1 h. Take out the sponge and place it in a 90°C forced air drying oven for 4 h to obtain AH / Fe-MOF-P@Fe3O4@PA@PU.
[0064] The saturated oil absorption of the composite sponge for n-hexane and chloroform are 28.8 g / g and 44.8 g / g respectively. It burns completely within 20 seconds after ignition. It has medium magnetism and a hydrophobic angle of 153.8°.
[0065] Example 5
[0066] (1) The preparation steps of AH / Fe-MOF were the same as step (1) of Example 1;
[0067] (2) The preparation steps of AH / Fe-MOF-P are the same as step (2) of Example 1;
[0068] (3) The preparation steps of PA@PU are the same as step (3) of Example 1;
[0069] (4) Dissolve 0.4 g of Dow Corning 184 product A solution and 0.04 g of Dow Corning 184 product B solution in 40 mL of n-hexane and sonicate for 20 min. Add 0.25 g of AH / Fe-MOF-P and 0.05 g of Fe3O4 and continue sonicating for 20 min until the powder is completely dispersed. Then add PA@PU and continue sonicating for 1 h. Remove the sponge and place it in a 90°C forced air drying oven for 4 h to obtain AH / Fe-MOF-P@Fe3O4@PA@PU.
[0070] The saturated oil absorption of the composite sponge for n-hexane and chloroform are 27.4 g / g and 42.6 g / g, respectively. It burns completely within 25 seconds after ignition. It has medium magnetism and a hydrophobic angle of 154.7°.
[0071] Example 6
[0072] (1) The preparation steps of AH / Fe-MOF were the same as step (1) in Example 1;
[0073] (2) The preparation steps of AH / Fe-MOF-P are the same as step (2) of Example 1;
[0074] (3) The preparation steps of PA@PU are the same as step (3) of Example 1;
[0075] (4) Dissolve 0.4 g of Dow Corning 184 product A solution and 0.04 g of Dow Corning 184 product B solution in 40 mL of n-hexane and sonicate for 20 min. Add 0.3 g of AH / Fe-MOF-P and 0.05 g of Fe3O4 and continue sonicating for 20 min until the powder is completely dispersed. Then add PA@PU and continue sonicating for 1 h. Take out the sponge and place it in a 90°C forced air drying oven for 4 h to obtain AH / Fe-MOF-P@Fe3O4@PA@PU.
[0076] The saturated oil absorption of the composite sponge for n-hexane and chloroform are 25.8 g / g and 41.4 g / g respectively. It burns completely within 30 seconds after ignition. It has medium magnetism and a hydrophobic angle of 154.9°.
[0077] Example 7
[0078] (1) The preparation steps of AH / Fe-MOF were the same as step (1) in Example 1;
[0079] (2) The preparation steps of AH / Fe-MOF-P are the same as step (2) of Example 1;
[0080] (3) The preparation steps of PA@PU are the same as step (3) of Example 1;
[0081] (4) Dissolve 0.4 g of Dow Corning 184 product A solution and 0.04 g of Dow Corning 184 product B solution in 40 mL of n-hexane and sonicate for 20 min. Add 0.4 g of AH / Fe-MOF-P and 0.05 g of Fe3O4 and continue sonicating for 20 min until the powder is completely dispersed. Then add PA@PU and continue sonicating for 1 h. Take out the sponge and place it in a 90°C forced air drying oven for 4 h to obtain AH / Fe-MOF-P@Fe3O4@PA@PU.
[0082] The saturated oil absorption of the composite sponge for n-hexane and chloroform is 23.2 g / g and 38.6 g / g, respectively. It self-extinguishes within 2 seconds after ignition, has medium magnetism, and a hydrophobic angle of 155.2°.
[0083] Example 8
[0084] (1) The preparation steps of AH / Fe-MOF were the same as step (1) in Example 1;
[0085] (2) The preparation steps of AH / Fe-MOF-P are the same as step (2) of Example 1;
[0086] (3) The preparation steps of PA@PU are the same as step (3) of Example 1;
[0087] (4) Dissolve 0.4 g of Dow Corning 184 product A solution and 0.04 g of Dow Corning 184 product B solution in 40 mL of n-hexane and sonicate for 20 min. Add 0.35 g of AH / Fe-MOF-P and 0.04 g of Fe3O4 and continue sonicating for 20 min until the powder is completely dispersed. Then add PA@PU and continue sonicating for 1 h. Take out the sponge and place it in a 90°C forced air drying oven for 4 h to obtain AH / Fe-MOF-P@Fe3O4@PA@PU.
[0088] The saturated oil absorption of the composite sponge for n-hexane and chloroform is 24.4 g / g and 40.6 g / g, respectively. It self-extinguishes 2 seconds after ignition, has weak magnetism, and has a hydrophobic angle of 155.1°.
[0089] Example 9
[0090] (1) The preparation steps of AH / Fe-MOF were the same as step (1) in Example 1;
[0091] (2) The preparation steps of AH / Fe-MOF-P are the same as step (2) of Example 1;
[0092] (3) The preparation steps of PA@PU are the same as step (3) of Example 1;
[0093] (4) Dissolve 0.4 g of Dow Corning 184 product A solution and 0.04 g of Dow Corning 184 product B solution in 40 mL of n-hexane and sonicate for 20 min. Add 0.35 g of AH / Fe-MOF-P and 0.06 g of Fe3O4 and continue sonicating for 20 min until the powder is completely dispersed. Then add PA@PU and continue sonicating for 1 h. Remove the sponge and place it in a 90°C forced air drying oven for 4 h to obtain AH / Fe-MOF-P@Fe3O4@PA@PU.
[0094] The saturated oil absorption of the composite sponge for n-hexane and chloroform is 23.8 g / g and 39.6 g / g, respectively. It self-extinguishes within 2 seconds after ignition, has medium magnetism, and a hydrophobic angle of 154.8°.
[0095] Example 10
[0096] (1) The preparation steps of AH / Fe-MOF were the same as step (1) in Example 1;
[0097] (2) The preparation steps of AH / Fe-MOF-P are the same as step (2) of Example 1;
[0098] (3) The preparation steps of PA@PU are the same as step (3) of Example 1;
[0099] (4) Dissolve 0.4 g of Dow Corning 184 product A solution and 0.04 g of Dow Corning 184 product B solution in 40 mL of n-hexane and sonicate for 20 min. Add 0.35 g of AH / Fe-MOF-P and 0.08 g of Fe3O4 and continue sonicating for 20 min until the powder is completely dispersed. Then add PA@PU and continue sonicating for 1 h. Remove the sponge and place it in a 90°C forced air drying oven for 4 h to obtain AH / Fe-MOF-P@Fe3O4@PA@PU.
[0100] The saturated oil absorption of the composite sponge for n-hexane and chloroform is 22.8 g / g and 38.6 g / g, respectively. It can self-extinguish in 2 seconds after ignition, has strong magnetism, and a hydrophobic angle of 155.1°.
[0101] Example 11
[0102] (1) The preparation steps of AH / Fe-MOF were the same as step (1) in Example 1;
[0103] (2) 0.64 g of Ca(H2PO4)2 and 50 ml of deionized water were placed in a flask and stirred at 80°C and 600 rpm for 30 min. 0.8 g of AH@Fe-MOF was then added and stirred at 80°C for 1 h. After cooling to room temperature, the precipitate was collected by centrifugation and the solid was placed in a vacuum drying oven at 100°C for 12 h to obtain AH / Fe-MOF-P crystals.
[0104] (3) The preparation steps of PA@PU are the same as step (3) of Example 1;
[0105] (4) The preparation steps of AH / Fe-MOF-P@Fe3O4@PA@PU are the same as those in step (4) of Example 1;
[0106] The saturated oil absorption of the composite sponge for n-hexane and chloroform is 24.4 g / g and 40.6 g / g, respectively. It can self-extinguish within 5 seconds after ignition, has strong magnetism, and a hydrophobic angle of 155.0°.
[0107] Example 12
[0108] (1) The preparation steps of AH / Fe-MOF were the same as step (1) of Example 1;
[0109] (2) 0.96 g of Ca(H2PO4)2 and 50 ml of deionized water were placed in a flask and stirred at 80°C and 600 rpm for 30 min. 0.8 g of AH@Fe-MOF was then added and stirred at 80°C for 1 h. After cooling to room temperature, the precipitate was collected by centrifugation and the solid was placed in a vacuum drying oven at 100°C for 12 h to obtain AH / Fe-MOF-P crystals.
[0110] (3) The preparation steps of PA@PU are the same as step (3) of Example 1;
[0111] (4) The preparation steps of AH / Fe-MOF-P@Fe3O4@PA@PU are the same as those in step (4) of Example 1;
[0112] The saturated oil absorption of the composite sponge for n-hexane and chloroform is 23.5 g / g and 39.2 g / g, respectively. It can self-extinguish 2 seconds after ignition, has strong magnetism, and a hydrophobic angle of 155.1°.
[0113] Comparative Example 1
[0114] (1) The preparation steps of PA@PU are the same as step (3) of Example 1;
[0115] (2) Dissolve 0.4 g of Dow Corning 184 Product A and 0.04 g of Dow Corning 184 Product B in 40 mL of n-hexane and sonicate for 20 min. Add 0.05 g of Fe3O4 and continue sonicating for 20 min until the powder is completely dispersed. Then add PA@PU and continue sonicating for 1 h. Remove the sponge and place it in a 90°C forced air drying oven for 4 h to obtain Fe3O4@PA@PU.
[0116] The saturated oil absorption of the composite sponge for n-hexane and chloroform is 35.4 g / g and 67.8 g / g respectively. It burns completely in 8 seconds after ignition. It has medium magnetism and a hydrophobic angle of 152.8°.
[0117] Comparative Example 2
[0118] (1) The preparation steps of AH / Fe-MOF were the same as step (1) of Example 1;
[0119] (2) The preparation steps of AH / Fe-MOF-P are the same as step (2) of Example 1;
[0120] (3) Dissolve 0.5 g of Dow Corning 184 product A solution and 0.05 g of Dow Corning 184 product B solution in 40 mL of n-hexane and sonicate for 20 min. Add 0.35 g of AH / Fe-MOF-P and 0.05 g of Fe3O4 and continue sonicating for 20 min until the powder is completely dispersed. Then add the original PU and continue sonicating for 1 h. Take out the sponge and place it in a 90°C forced air drying oven for 4 h to obtain AH / Fe-MOF-P@Fe3O4@PU.
[0121] The saturated oil absorption of the composite sponge for n-hexane and chloroform are 26.4 g / g and 42.6 g / g, respectively. It burns completely within 27 seconds after ignition. It has medium magnetism and a hydrophobic angle of 152.8°.
[0122] Comparative Example 3
[0123] (1) The preparation steps of AH / Fe-MOF were the same as step (1) of Example 1;
[0124] (2) The preparation steps of PA@PU are the same as step (3) of Example 1;
[0125] (3) Dissolve 0.4 g of Dow Corning 184 product A solution and 0.04 g of Dow Corning 184 product B solution in 40 mL of n-hexane and sonicate for 20 min. Add 0.35 g of AH / Fe-MOF and 0.05 g of Fe3O4 and continue sonicating for 20 min until the powder is completely dispersed. Then add PA@PU and continue sonicating for 1 h. Remove the sponge and place it in a 90°C forced air drying oven for 4 h to obtain AH / Fe-MOF@Fe3O4@PA@PU.
[0126] The saturated oil absorption of the composite sponge for n-hexane and chloroform is 24.8 g / g and 40.9 g / g, respectively. It self-extinguishes within 6 seconds after ignition, has medium magnetic properties, and a hydrophobic angle of 154.8°.
[0127] Comparative Example 4
[0128] (1) The preparation steps of AH / Fe-MOF were the same as step (1) of Example 1;
[0129] (2) The preparation steps of AH / Fe-MOF-P are the same as step (2) of Example 1;
[0130] (3) The preparation steps of PA@PU are the same as step (3) of Example 1;
[0131] (4) Dissolve 0.4 g of Dow Corning 184 product A solution and 0.04 g of Dow Corning 184 product B solution in 40 mL of n-hexane and sonicate for 20 min. Add 0.35 g of AH / Fe-MOF-P and continue sonicating for 20 min until the powder is completely dispersed. Then add PA@PU and continue sonicating for 1 h. Remove the sponge and place it in a 90°C forced air drying oven for 4 h to obtain AH / Fe-MOF-P@PA@PU.
[0132] The saturated oil absorption of the composite sponge for n-hexane and chloroform is 26.4 g / g and 42.6 g / g, respectively. It self-extinguishes 2 seconds after ignition, has no magnetism, and has a hydrophobic angle of 154.2°.
Claims
1. A flame-retardant super-hydrophobic magnetic photothermal sponge, characterized by: The flame retardant super-hydrophobic magnetic photothermal sponge is obtained by ultrasonically dispersing flame retardant AH / Fe-MOF-P, PDMS curing system and Fe3O4 particle powder in a n-hexane solution, then immersing a phytic acid modified polyurethane sponge in the solution, ultrasonically treating the solution and drying the solution.
2. The flame-retardant super-hydrophobic magnetic photothermal sponge according to claim 1, characterized in that: The preparation method of the flame retardant AH / Fe-MOF-P is as follows: Al(OH)3 is stirred and dispersed in DMF, FeCl3 and 2-aminoterephthalic acid are added, and stirring is continued. Then, the mixture is transferred to a reactor for reaction, and the reaction solution is centrifuged, washed, and dried to obtain brown AH / Fe-MOF crystals; then Ca(H2PO4)2 and deionized water are placed in a flask and stirred, and then the AH / Fe-MOF crystals are added, and stirring and reaction are continued. After cooling to room temperature, the precipitate is collected by centrifugation and dried to obtain AH / Fe-MOF-P.
3. The flame-retardant super-hydrophobic magnetic photothermal sponge according to claim 2, characterized in that: The mass ratio of FeCl3, 2-aminoterephthalic acid, and Al(OH)3 is 1:1.1:4, and the reaction conditions in the reactor are: 120°C for 12 hours.
4. The flame-retardant super-hydrophobic magnetic photothermal sponge according to claim 2, characterized in that: The mass ratio of AH / Fe-MOF crystals to Ca(H2PO4)2 is 1:0.8-1.
2.
5. The flame-retardant super-hydrophobic magnetic photothermal sponge according to claim 1, characterized in that: The mass ratio of PDMS curing system, AH / Fe-MOF-P and Fe3O4 is: 1:0.5-1:0.1-0.
2.
6. The flame-retardant super-hydrophobic magnetic photothermal sponge according to claim 1, characterized in that: The method for modifying the polyurethane sponge with phytic acid is as follows: the polyurethane sponge is immersed in a phytic acid / ethanol solution and stirred for 2 hours.
7. The flame-retardant super-hydrophobic magnetic photothermal sponge according to claim 6, characterized in that: The mass concentration of the phytic acid / ethanol solution is 14-28 g / L.
8. A method for preparing the flame-retardant super-hydrophobic magnetic photothermal sponge according to claim 1, characterized in that: The preparation method comprises the following steps: (1) The flame retardant AH / Fe-MOF-P was prepared by in situ growth and chemical grafting; (2) The PDMS curing system was first ultrasonically dispersed in n-hexane solution, and then Fe3O4 and AH / Fe-MOF-P powder particles were added and ultrasonically treated. Finally, the phytic acid modified polyurethane sponge was immersed in it, taken out and dried after ultrasonic treatment to obtain a flame retardant superhydrophobic magnetic photothermal sponge.
9. The method for preparing the flame-retardant super-hydrophobic magnetic photothermal sponge according to claim 8, characterized in that: The amount of n-hexane used was 40 mL. The curing system was added and ultrasonicated for 30 min. After adding AH / Fe-MOF-P and Fe3O4, ultrasonication was performed for 30 min. After adding sponge, ultrasonication was performed for 1 h. The drying temperature was 90 ° C and the time was 4 h.
10. An application of the flame-retardant super-hydrophobic magnetic photothermal sponge according to claim 1, characterized in that: The flame-retardant super-hydrophobic magnetic photothermal sponge is used for oil-water separation.