CN113174083A - Preparation method and application of green super-hydrophobic magnetic sponge - Google Patents

Preparation method and application of green super-hydrophobic magnetic sponge Download PDF

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CN113174083A
CN113174083A CN202110474808.3A CN202110474808A CN113174083A CN 113174083 A CN113174083 A CN 113174083A CN 202110474808 A CN202110474808 A CN 202110474808A CN 113174083 A CN113174083 A CN 113174083A
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sponge
urushiol
super
drying
hydrophobic
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齐宝金
曹亚飞
陈飞
崔晨乙
朱润博
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Xian Jiaotong University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2361/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08J2361/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C08J2361/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2265—Oxides; Hydroxides of metals of iron
    • C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/01—Magnetic additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
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Abstract

A method for preparing green super-hydrophobic magnetic sponge comprises soaking melamine sponge in urushiol solution, drying, and soaking in Fe3O4And drying the suspension, soaking the suspension in urushiol solution, and drying to obtain the super-hydrophobic magnetic oil-water separation sponge. The invention extracts urushiol from raw lacquer, utilizes the characteristic that urushiol has adhesiveness due to having catechol group and the characteristic that urushiol has nonpolar long aliphatic chain, and the aliphatic chain provides low surface energy, and uses the urushiol as a binder to enable magnetic nano Fe3O4The particles adhere to the surface of the spongeForming a micro-nano structure, modifying with urushiol, completely drying to make it fully self-polymerize, reducing the surface energy of the sponge, and forming a super-hydrophobic sponge interface. Because of better hydrophobicity and lipophilicity, the super-hydrophobic magnetic material can be successfully applied to oil-water separation, and has good application prospect for carrying out water treatment in an environment-friendly way.

Description

Preparation method and application of green super-hydrophobic magnetic sponge
Technical Field
The invention belongs to the technical field of oil-water separation, and relates to a preparation method and application of a green super-hydrophobic magnetic sponge.
Background
With the rapid development of the economic industry society, a large amount of oily wastewater is generated in the industries of metallurgy, petroleum, textile, chemical industry and the like while the industries are correspondingly and rapidly developed, the wastewater containing a large amount of oil and organic matters flows into rivers and lakes to cause water body damage which is difficult to reverse, and huge burden is brought to the healthy life of human beings and the environment of the earth. Therefore, efficient oil-water separation is an important work of current research. The traditional gravity-driven separation, in-situ combustion, filtration, biodegradation and the use of fluorine-containing compounds in the preparation process of some separation materials have the defects of low separation efficiency, low reusability, secondary environmental damage and the like. Therefore, the preparation of the high-efficiency and environment-friendly oil-water separation material becomes a difficult problem which needs to be solved urgently.
Since 1997, the super-hydrophobic interface is found in the lotus effect, which is the phenomenon that the contact angle of the material surface and water is more than 150 degrees and the rolling angle is less than 5 degrees, and is widely applied to various separation tasks such as liquid-liquid separation, gas-liquid separation and the like.
Aiming at the problems that the surface needs to be modified by fluoride with low surface energy, dopamine polymerization is needed to achieve the purpose of adhesion, and the preparation of the environment-friendly and simply-operated super-hydrophobic magnetic sponge cannot be realized at present, the preparation method of the green super-hydrophobic magnetic sponge is needed to be provided.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a preparation method and application of a green super-hydrophobic magnetic sponge, so that the problem that the surface energy is modified by fluoride to reduce the surface energy is solved, dopamine polymerization is not needed to achieve the adhesion purpose, and the preparation of the environment-friendly super-hydrophobic magnetic sponge with simple operation is realized.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing green super-hydrophobic magnetic sponge comprises soaking melamine sponge in urushiol solution, drying, and soaking in Fe3O4And drying the suspension, soaking the suspension in urushiol solution, and drying to obtain the super-hydrophobic magnetic oil-water separation sponge.
The further improvement of the invention is that before the melamine sponge is dipped in the urushiol solution, the melamine sponge is sequentially ultrasonically cleaned in acetone, absolute ethyl alcohol and deionized water, and then dried.
In a further development of the invention, the urushiol solution is prepared by the following process: adding urushiol into ethanol, and dispersing to obtain a urushiol solution with the mass concentration of 3-5%.
In a further development of the invention, urushiol is prepared by the following process: mixing raw lacquer and absolute ethyl alcohol according to the mass ratio of 1: 1.5-2, stirring, filtering to obtain filtrate, and concentrating the filtrate to obtain urushiol.
The invention is further improved in that the melamine sponge is soaked in the urushiol solution for 30 s-1 h.
In a further development of the invention, Fe3O4The suspension is prepared by the following steps: mixing Fe3O4Mixing with deionized water according to the mass ratio of 10-20: 1, and then performing ultrasonic dispersion for 20min under 200W to obtain nano Fe3O4And (4) suspending the solution.
A further improvement of the invention consists in further impregnating the steel with Fe3O45-10 s in the suspension.
The invention is further improved in that the paint is dipped in the urushiol solution for 5 to 10 seconds.
The green super-hydrophobic magnetic sponge prepared by the method is applied to oil-water separation. Compared with the prior art, the invention has the following beneficial effects:
compared with the current situation that the existing super-hydrophobic material is applied to oil-water separation, the sponge is soaked in urushiol solution for the first time to achieve the adhesion effect; further by impregnating with Fe3O4Magnetic nano Fe is attached to the surface of turbid liquid3O4The particles form a rough micro-nano structure on the sponge through the adhesion of the nano particles to increase the roughness; and then the coating is soaked in urushiol solution and completely dried, so that a super-hydrophobic surface is formed through the low surface energy of urushiol, and the water contact angle is up to 158 degrees. The melamine sponge changes the wettability of water from hydrophilicity to super-hydrophobicity through the modification, and keeps lipophilicity to oil, so that the hydrophobic and oleophilic functions are realized.
Aiming at the phenomenon that water in the industry and in the nature contains a small amount of oil at present, the oil-water separation sponge can effectively absorb the oil, and the aim of removing the actual situation that the water contains a small amount of oil is fulfilled. Meanwhile, the magnetic nano particles have magnetism, and can be remotely recycled through an external magnetic field, so that the operation under the actual condition is facilitated.
Drawings
FIG. 1 is a 150-fold scanning electron micrograph of a sponge surface that has not been chemically treated.
FIG. 2 is a 3 k-fold scanning electron micrograph of the surface of the sponge that has not been chemically treated.
FIG. 3 is a graph of sponge surface passing 3 wt.% urushiol @ Fe3O4Scanning electron microscopy at 500 x treatment.
FIG. 4 is a sponge surface coated with 3 wt.% urushiol @ Fe3O41k times scanning electron micrograph of treatment.
FIG. 5 is a sponge surface coated with 3 wt.% urushiol @ Fe3O4Scanning electron microscopy 10k times of treatment.
Fig. 6 is an optical contact angle of a water droplet on a surface of a sponge that has not been chemically treated.
FIG. 7 is a water drop through 3 wt.% urushiol @ Fe3O4The optical contact angle of the sponge surface was treated.
FIG. 8 is a magnetic migration diagram of a chemically treated sponge.
Fig. 9 is an absorption energy diagram of different kinds of oil/organic solvents for the super-hydrophobic magnetic sponge prepared in example 3.
FIG. 10 shows the water contact angle 157.51 DEG of the sponge after modification in example 1
FIG. 11 shows the water contact angle 162.26 ° of the sponge after modification in example 2.
FIG. 12 shows the water contact angle 150.37 ° of the sponge after modification in example 4.
FIG. 13 shows the water contact angle of the sponge of example 5 after modification is 152.3 deg..
FIG. 14 shows the sponge water contact angle of 142.7 ℃ after modification in comparative example 1.
Detailed Description
The present invention will be described in detail below by way of examples with reference to the accompanying drawings.
Urushiol is one of the main components of raw lacquer, accounts for 50% -80%, is a bipolar molecule, contains catechol groups and aliphatic long chains, and can play a role in adhesion on one hand and surface energy reduction on the other hand; the melamine sponge has the advantages of open pore structure, high porosity, low density and the like, and is high in mechanical strength and low in cost. Therefore, the three-dimensional sponge surface modification can realize efficient oil-water separation.
The preparation method of the green super-hydrophobic magnetic sponge comprises the following steps: removing organic matter on the surface of melamine sponge, soaking in urushiol solution, drying, and soaking in Fe3O4And drying the solution, soaking the dried solution in urushiol solution, and drying to obtain the super-hydrophobic magnetic oil-water separation sponge. The method specifically comprises the following steps:
1) ultrasonically cleaning 2cm × 2cm × 2cm melamine sponge in acetone, absolute ethyl alcohol and deionized water in sequence, and drying in an electrothermal blowing drying oven at 60 ℃ for 12 hours; the instrument used for ultrasonic cleaning is an ultrasonic cleaner.
2) Mixing raw lacquer (purchased from Sichuan Mianyang Henghui Hengchan Co., Ltd., China Sichuan Ann raw lacquer research institute) and absolute ethyl alcohol according to a mass ratio of 1: 1.5-2, stirring at 800r/min for 24h, performing suction filtration for 4 times, and performing rotary evaporation on the filtrate at 60 ℃ by using a rotary evaporator to further purify the filtrate to obtain a brown viscous liquid, namely urushiol;
adding 0.495-0.842g of urushiol into ethanol by taking absolute ethanol as a solvent to prepare 3-5 wt.% urushiol solution, and dispersing by using a shaking table for 30s to obtain the urushiol solution which is uniformly mixed for later use.
3) Putting the melamine sponge treated in the step 1) into a urushiol solution, soaking for 30 s-1 h, taking out, and drying in an electric drum air drying box at 70-85 ℃ for 4-6 h to obtain the melamine sponge with adhesiveness.
4) FeCl is added3·6H2O and C6H5Na3O7(sodium citrate) is blended in 40-80 mL of ethylene glycol for 3h according to the molar ratio of 40: 1, and then sodium acetate is added, wherein FeCl3·6H2O and CH3Stirring for 6 hours with the molar ratio of COONa being 1: 4.5-6, pouring into a reaction kettle, reacting for 12 hours in a muffle furnace at 200 ℃, performing suction filtration, alternately washing with deionized water and ethanol, and drying in a vacuum oven at 60 ℃ for 12 hours to obtain nanoscale Fe3O4。
Mixing Fe3O4Mixing with deionized water according to the mass ratio of 10-20: 1, and then performing ultrasonic dispersion for 20min under 200W to obtain nano Fe3O4And (5) suspending liquid for later use.
Preparation of Fe by the method of the invention3O4Or commercial nanoscale Fe3O4May be used.
5) Adding the melamine sponge obtained in the step 3) into Fe3O4Dipping the suspension for 5-10 s, and then drying the suspension in an electric air blowing drying box at 65-75 ℃ until the suspension is completely dried.
6) And (3) putting the completely dried sponge obtained in the step 5) into a urushiol solution for soaking for 5-10 s. Taking out, and drying in an electric air blowing drying box at 70-75 ℃ for 24h to obtain the super-hydrophobic magnetic oil-water separation sponge.
The prepared super-hydrophobic magnetic oil-water separation sponge is placed into an oil-water mixture, oil can be absorbed by the sponge based on the surface super-hydrophobic characteristic, the sponge can be sucked out through an external magnetic field, the oil can be separated out through simple physical methods such as extrusion and the like, and the oil-water separation sponge can be recycled, so that the environment-friendly oil-water separation is realized.
Example 1
1) Ultrasonically cleaning 2cm × 2cm × 2cm melamine sponge in acetone, absolute ethyl alcohol and deionized water in sequence, and drying in an electrothermal blowing drying oven at 60 ℃ for 12 hours; the instrument used for ultrasonic cleaning is an ultrasonic cleaner.
2) Stirring and mixing 100g of raw lacquer and 200mL of absolute ethyl alcohol at the speed of 800r/min for 24h, carrying out suction filtration for 4 times, and carrying out rotary evaporation on the filtrate at the temperature of 60 ℃ by using a rotary evaporator to further purify the filtrate to obtain a tan viscous liquid, namely urushiol; preparing urushiol solution by using absolute ethyl alcohol as a solvent, respectively adding 0.495g of urushiol into 16g of ethanol to prepare 3 wt.% of urushiol solution, and dispersing by using a shaking table for 30s to obtain uniformly mixed urushiol solution for later use.
3) And (3) putting the melamine sponge treated in the step (1) into a urushiol solution, soaking for 30s, taking out, and then drying in an electric drum air drying box at 80 ℃ for 6h to obtain the adhesive melamine sponge.
4) 1.35g FeCl3·6H2O and 45mg C6H5Na3O7After blending in 80mL of ethylene glycol for 3h, 2.5CH was added3COONa is stirred for 6 hours, poured into a reaction kettle, reacted in a muffle furnace for 12 hours at 200 ℃, filtered, washed by deionized water and ethanol alternately, and dried in a vacuum oven for 12 hours at 60 ℃. Mixing Fe3O4Mixing with deionized water at a mass ratio of 20: 1, ultrasonic dispersing at 200W for 20min to obtain nanometer Fe3O4And (5) suspending liquid for later use.
5) Adding the sponge obtained in the step 3 into Fe3O4And soaking the suspension for 5s, and then drying the suspension in an electric air blowing drying box at 65-75 ℃ until the suspension is completely dried.
6) And (4) putting the sponge obtained in the step (5) into a urushiol solution for soaking for 5 seconds. Taking out, and drying in an electric air blowing drying box at 70-75 ℃ for 24h until the surface is completely solidified to obtain the magnetic super-hydrophobic sponge.
The contact angle of the super-hydrophobic sponge is 157.51 degrees.
Referring to fig. 1 and 2, it is evident that the untreated sponge surface is smooth and free of any roughness.
Referring to fig. 3, 4 and 5, a clear contrast to the unmodified sponge can be seen, 3 wt.% @ Fe3O4The modified sponge has obvious nanoscale Fe3O4The particles form a micro-nano structure.
Referring to fig. 6 and 7, the contact angle in fig. 7 is 0 °, when the sponge is both hydrophilic and oleophilic, passing through 3 wt.% urushiol @ Fe3O4The water contact angle of the treated sponge surface is 158.55 degrees, and at the moment, the sponge surface is super-hydrophobic and also keeps the oleophilic property.
Referring to fig. 8, it is apparent that the right sponge is modified to be magnetic and can move after the magnetic field is increased by the additional magnet.
Referring to fig. 10, the sponge water contact angle of example 1 after modification is 157.51 °.
Example 2
1) Ultrasonically cleaning 2cm × 2cm × 2cm melamine sponge in acetone, absolute ethyl alcohol and deionized water in sequence, and drying in an electrothermal blowing drying oven at 60 ℃ for 12 hours; the instrument used for ultrasonic cleaning is an ultrasonic cleaner.
2) Stirring and mixing 100g of raw lacquer and 200mL of absolute ethyl alcohol at the speed of 800r/min for 24h, carrying out suction filtration for 4 times, and carrying out rotary evaporation on the filtrate at the temperature of 60 ℃ by using a rotary evaporator to further purify the filtrate to obtain a tan viscous liquid, namely urushiol; preparing urushiol solution by using absolute ethyl alcohol as a solvent, respectively adding 0.495g of urushiol into 16g of ethanol to prepare 3 wt.% of urushiol solution, and dispersing by using a shaking table for 30s to obtain uniformly mixed urushiol solution for later use.
3) And (3) putting the melamine sponge treated in the step (1) into a urushiol solution, soaking for 60s, taking out, and then drying in an electric drum air drying box at 80 ℃ for 6h to obtain the adhesive melamine sponge.
4) 5.4g FeCl3·6H2O and 135mg C6H5Na3O7After blending in 80mL of ethylene glycol for 3h, 7.5g of CH was added3Stirring COONa for 6h, pouring into a reaction kettle, reacting in a muffle furnace at 200 ℃ for 12h, performing suction filtration, alternately washing with deionized water and ethanol, and drying in a vacuum oven at 60 ℃ for 12h to obtain Fe3O4. Mixing Fe3O4Mixing with deionized water at a mass ratio of 20: 1, ultrasonic dispersing at 200W for 20min to obtain nanometer Fe3O4And (5) suspending liquid for later use.
5) Adding the sponge obtained in the step 3 into Fe3O4And soaking the suspension for 5s, and then drying the suspension in an electric air blowing drying box at 65-75 ℃ until the suspension is completely dried.
6) And (4) putting the sponge obtained in the step (5) into a urushiol solution for soaking for 5 seconds. Taking out, and drying in an electric air blowing drying box at 70-75 ℃ for 24h until the surface is completely solidified to obtain the magnetic super-hydrophobic sponge.
Referring to fig. 11, example 2 modified the sponge water contact angle of 162.26 °.
Example 3
1) Ultrasonically cleaning 2cm × 2cm × 2cm melamine sponge in acetone, absolute ethyl alcohol and deionized water in sequence, and drying in an electrothermal blowing drying oven at 60 ℃ for 12 hours; the instrument used for ultrasonic cleaning is an ultrasonic cleaner.
2) Stirring and mixing 100g of raw lacquer and 200mL of absolute ethyl alcohol at the speed of 800r/min for 24h, carrying out suction filtration for 4 times, and carrying out rotary evaporation on the filtrate at the temperature of 60 ℃ by using a rotary evaporator to further purify the filtrate to obtain a tan viscous liquid, namely urushiol; preparing urushiol solution by using absolute ethyl alcohol as a solvent, respectively adding 0.495g of urushiol into 16g of ethanol to prepare 3 wt.% of urushiol solution, and dispersing by using a shaking table for 30s to obtain uniformly mixed urushiol solution for later use.
3) And (3) putting the melamine sponge treated in the step (1) into a urushiol solution, soaking for 120s, taking out, and drying in an electric drum air drying box at 80 ℃ for 6h to obtain the adhesive melamine sponge.
4) 5.4g FeCl3·6H2O and 135mg C6H5Na3O7After blending in 80mL of ethylene glycol for 3h, 7.5g of CH was added3Stirring COONa for 6h, pouring into a reaction kettle, reacting in a muffle furnace at 200 ℃ for 12h, performing suction filtration, alternately washing with deionized water and ethanol, and drying in a vacuum oven at 60 ℃ for 12h to obtain Fe3O4. Mixing Fe3O4Mixing with deionized water at a mass ratio of 20: 1, ultrasonic dispersing at 200W for 20min to obtain nanometer Fe3O4And (5) suspending liquid for later use.
5) Adding the sponge obtained in the step 3 into Fe3O4And soaking the suspension for 5s, and then drying the suspension in an electric air blowing drying box at 65-75 ℃ until the suspension is completely dried.
6) And (4) putting the sponge obtained in the step (5) into a urushiol solution for soaking for 5 seconds. Taking out, and drying in an electric air blowing drying box at 70-75 ℃ for 24h until the surface is completely solidified to obtain the magnetic super-hydrophobic sponge.
The contact angle of the super-hydrophobic sponge is 158.55 degrees.
Example 4
1) Ultrasonically cleaning 2cm × 2cm × 2cm melamine sponge in acetone, absolute ethyl alcohol and deionized water in sequence, and drying in an electrothermal blowing drying oven at 60 ℃ for 12 hours; the instrument used for ultrasonic cleaning is an ultrasonic cleaner.
2) Stirring and mixing 100g of raw lacquer and 200mL of absolute ethyl alcohol at the speed of 800r/min for 24h, carrying out suction filtration for 4 times, and carrying out rotary evaporation on the filtrate at the temperature of 60 ℃ by using a rotary evaporator to further purify the filtrate to obtain a tan viscous liquid, namely urushiol; preparing urushiol solution by using absolute ethyl alcohol as a solvent, respectively adding 0.842g of urushiol into 16g of ethanol to prepare 5 wt.% urushiol solution, and dispersing by using a shaking table for 30s to obtain uniformly mixed urushiol solution for later use.
3) And (3) putting the melamine sponge treated in the step (1) into a urushiol solution, soaking for 30min, taking out, and then drying in an electric drum air drying box at 85 ℃ for 6h to obtain the adhesive melamine sponge.
4) 5.4g FeCl3·6H2O and 135mg C6H5Na3O7After blending in 80mL of ethylene glycol for 3h, 7.5g of CH was added3COONa is stirred for 6 hours, poured into a reaction kettle, reacted in a muffle furnace for 12 hours at 200 ℃, filtered, washed by deionized water and ethanol alternately, and dried in a vacuum oven for 12 hours at 60 ℃. Mixing Fe3O4Mixing with deionized water at a mass ratio of 10: 1, ultrasonic dispersing at 200W for 20min to obtain nanometer Fe3O4And (5) suspending liquid for later use.
5) Adding the sponge obtained in the step 3 into Fe3O4And soaking the suspension for 5s, and then drying the suspension in an electric air blowing drying box at 65-75 ℃ until the suspension is completely dried.
6) And (4) putting the sponge obtained in the step (5) into urushiol solution with the corresponding mass fraction for soaking for 5 s. Taking out, and drying in an electric air blowing drying box at 70-75 ℃ for 24h until the surface is completely solidified to obtain the magnetic super-hydrophobic sponge.
Referring to fig. 12, example 4 modified sponge water contact angle 150.37 °.
Example 5
1) Ultrasonically cleaning 2cm × 2cm × 2cm melamine sponge in acetone, absolute ethyl alcohol and deionized water in sequence, and drying in an electrothermal blowing drying oven at 60 ℃ for 12 hours; the instrument used for ultrasonic cleaning is an ultrasonic cleaner.
2) Stirring and mixing 100g of raw lacquer and 200mL of absolute ethyl alcohol at the speed of 800r/min for 24h, carrying out suction filtration for 4 times, and carrying out rotary evaporation on the filtrate at the temperature of 60 ℃ by using a rotary evaporator to further purify the filtrate to obtain a tan viscous liquid, namely urushiol; preparing urushiol solution by using absolute ethyl alcohol as a solvent, respectively adding 0.842g of urushiol into 16g of ethanol to prepare 5 wt.% urushiol solution, and dispersing by using a shaking table for 30s to obtain uniformly mixed urushiol solution for later use.
3) And (3) putting the melamine sponge treated in the step (1) into a urushiol solution, soaking for 1h, taking out, and then drying in an electric drum air drying box at 85 ℃ for 6h to obtain the adhesive melamine sponge.
4) 5.4g FeCl3·6H2O and 135mg C6H5Na3O7After blending in 80mL of ethylene glycol for 3h, 7.5g of CH was added3COONa is stirred for 6 hours, poured into a reaction kettle, reacted in a muffle furnace for 12 hours at 200 ℃, filtered, washed by deionized water and ethanol alternately, and dried in a vacuum oven for 12 hours at 60 ℃. Mixing Fe3O4Mixing with deionized water at a mass ratio of 10: 1, ultrasonic dispersing at 200W for 20min to obtain nanometer Fe3O4And (5) suspending liquid for later use.
5) Adding the sponge obtained in the step 3 into Fe3O4And soaking the suspension for 5-10 s, and then drying in an electric air blowing drying box at 65-75 ℃ until the suspension is completely dried.
6) And (4) putting the sponge obtained in the step (5) into urushiol solution with the corresponding mass fraction for soaking for 5 s. Taking out, and drying in an electric air blowing drying box at 70-75 ℃ for 24h until the surface is completely solidified to obtain the magnetic super-hydrophobic sponge.
Referring to fig. 13, the contact angle of the resulting superhydrophobic sponge was 152.3 °.
Example 6
1) Ultrasonically cleaning 2cm × 2cm × 2cm melamine sponge in acetone, absolute ethyl alcohol and deionized water in sequence, and drying in an electrothermal blowing drying oven at 60 ℃ for 12 hours; the instrument used for ultrasonic cleaning is an ultrasonic cleaner.
2) Stirring and mixing 100g of raw lacquer and 150mL of absolute ethyl alcohol at the speed of 800r/min for 24h, carrying out suction filtration for 4 times, and carrying out rotary evaporation on the filtrate at the temperature of 60 ℃ by using a rotary evaporator to further purify the filtrate to obtain a tan viscous liquid, namely urushiol; preparing urushiol solution by using absolute ethyl alcohol as a solvent, respectively adding 0.646g of urushiol into 16g of ethanol to prepare 4 wt.% urushiol solution, and dispersing by using a shaking table for 30s to obtain uniformly mixed urushiol solution for later use.
3) And (3) putting the melamine sponge treated in the step (1) into a urushiol solution, soaking for 20min, taking out, and then drying in an electric drum air drying box at 70 ℃ for 6h to obtain the adhesive melamine sponge.
4) Mixing Fe3O4Mixing with deionized water at a mass ratio of 10: 1, ultrasonic dispersing at 200W for 20min to obtain nanometer Fe3O4And (5) suspending liquid for later use.
5) Adding the sponge obtained in the step 3 into Fe3O4The suspension was immersed for 7s and then dried in an electric air drying oven at 75 ℃ to complete dryness.
6) And (4) putting the sponge obtained in the step (5) into a urushiol solution for soaking for 10 s. Taking out, and drying in an electric air blowing drying box at 70 ℃ for 24h until the surface is completely solidified to obtain the magnetic super-hydrophobic sponge.
Example 7
1) Ultrasonically cleaning 2cm × 2cm × 2cm melamine sponge in acetone, absolute ethyl alcohol and deionized water in sequence, and drying in an electrothermal blowing drying oven at 60 ℃ for 12 hours; the instrument used for ultrasonic cleaning is an ultrasonic cleaner.
2) Stirring and mixing 100g of raw lacquer and 180mL of absolute ethyl alcohol at the speed of 800r/min for 24h, carrying out suction filtration for 4 times, and carrying out rotary evaporation on the filtrate at the temperature of 60 ℃ by using a rotary evaporator to further purify the filtrate to obtain a tan viscous liquid, namely urushiol; preparing urushiol solution by using absolute ethyl alcohol as a solvent, respectively adding 0.495g of urushiol into 16g of ethanol to prepare 3 wt.% of urushiol solution, and dispersing by using a shaking table for 30s to obtain uniformly mixed urushiol solution for later use.
3) And (3) putting the melamine sponge treated in the step (1) into a urushiol solution, soaking for 1h, taking out, and then drying for 4h at 88 ℃ in an electric drum air drying box to obtain the adhesive melamine sponge.
4) 1.35g FeCl3·6H2O and 45mg C6H5Na3O7After blending in 80mL of ethylene glycol for 3h, 2.5CH was added3COONa is stirred for 6 hours, poured into a reaction kettle, reacted in a muffle furnace for 12 hours at 200 ℃, filtered, washed by deionized water and ethanol alternately, and dried in a vacuum oven for 12 hours at 60 ℃. Mixing Fe3O4Mixing with deionized water at a mass ratio of 15: 1, ultrasonic dispersing at 200W for 20min to obtain nanometer Fe3O4And (5) suspending liquid for later use.
5) Adding the sponge obtained in the step 3 into Fe3O4The suspension was immersed for 10s and then dried in an electric air drying oven at 65 ℃ to complete dryness.
6) And (4) putting the sponge obtained in the step (5) into a urushiol solution for soaking for 10 s. Taking out, and drying in an electric air blowing drying oven at 75 ℃ for 24h until the surface is completely solidified to obtain the magnetic super-hydrophobic sponge.
Experimental example 8
Having urushiol @ Fe as prepared in example 33O4And (3) carrying out oil-water separation test on the super-hydrophobic magnetic sponge of the coating:
10mL of toluene, kerosene, cyclohexane, n-hexane, diesel oil, vegetable oil, chloroform and water are respectively taken to form an oil-water mixture. The prepared super-hydrophobic sponge is used for carrying out oil-water separation on the oil-water mixture, and the oil absorption capacity of the sponge is calculated by the following formula:
oil absorption capacity
Figure BDA0003046626060000111
Wherein m isiM is the self mass of the original spongewThe mass of the sponge saturated adsorption oil or organic solvent. Oil-water separation is an average value (at least three times) after multiple measurements. FIG. 9 shows a superhydrophobic magnetic spongeThe adsorption capacity to different kinds of oil, and the oil absorption capacity of the super-hydrophobic magnetic sponge is up to 19g/g as can be seen from figure 13.
Comparative example 1
1) Ultrasonically cleaning 2cm × 2cm × 2cm melamine sponge in acetone, absolute ethyl alcohol and deionized water in sequence, and drying in an electrothermal blowing drying oven at 60 ℃ for 12 hours; the instrument used for ultrasonic cleaning is an ultrasonic cleaner.
2) Stirring and mixing 100g of raw lacquer and 200mL of absolute ethyl alcohol at the speed of 800r/min for 24h, carrying out suction filtration for 4 times, and carrying out rotary evaporation on the filtrate at the temperature of 60 ℃ by using a rotary evaporator to further purify the filtrate to obtain a tan viscous liquid, namely urushiol; preparing urushiol solution by using absolute ethyl alcohol as a solvent, respectively adding 0.495g of urushiol into 16g of ethanol to prepare 3 wt.% of urushiol solution, and dispersing by using a shaking table for 30s to obtain uniformly mixed urushiol solution for later use.
3) And (2) putting the melamine sponge treated in the step (1) into a urushiol solution, soaking for 30s, taking out, and then drying in an electric drum air drying box at 70-75 ℃ for 24h until the surface is completely cured to obtain the hydrophobic sponge.
Referring to fig. 14, the resulting hydrophobic sponge contact angle was 142.7 °. It can be seen that the contact angle of the super-hydrophobic magnetic sponge prepared in the inventive example is larger than that of the comparative example.
And (2) placing an oil-water mixture mixed with a small amount of oil in a beaker, putting the prepared super-hydrophobic magnetic sponge into the mixture, fully adsorbing the mixture, and then recovering the sponge through a magnet, so that the oil is found to be absorbed by the sponge, and the purpose of removing the small amount of oil in the water is realized. According to the invention, the urushiol which is a fluorine-free binder is used for binding the magnetic nanoparticles, and the characteristic that urushiol contains unsaturated long alkyl chains and has low surface energy is utilized, so that two ways of improving the sponge roughness and reducing the surface energy are realized, the construction of a super-hydrophobic interface is realized, and the purposes of water repellency and oleophylicity of the hydrophobic interface are achieved. Due to the good hydrophobic and oleophylic characteristics, the method can be successfully applied to oil-water separation. The super-hydrophobic magnetic material has good application prospect for water treatment in an environment-friendly way. And aiming at the current situation that oil and water separation needs to be carried out through remote control in offshore oil leakage and the like, the problem can be well solved through the external magnetic field by the magnetic sponge.

Claims (9)

1. A preparation method of a green super-hydrophobic magnetic sponge is characterized in that melamine sponge is soaked in urushiol solution, dried and then soaked in Fe3O4And drying the suspension, soaking the suspension in urushiol solution, and drying to obtain the super-hydrophobic magnetic oil-water separation sponge.
2. The method for preparing the green super-hydrophobic magnetic sponge as claimed in claim 1, wherein before dipping the melamine sponge in the urushiol solution, the melamine sponge is sequentially ultrasonically cleaned in acetone, absolute ethyl alcohol and deionized water, and then dried.
3. The method for preparing the green superhydrophobic magnetic sponge according to claim 1, wherein the urushiol solution is prepared by the following process: adding urushiol into ethanol, and dispersing to obtain a urushiol solution with the mass concentration of 3-5%.
4. The method for preparing the green super-hydrophobic magnetic sponge as claimed in claim 3, wherein urushiol is prepared by the following steps: mixing raw lacquer and absolute ethyl alcohol according to the mass ratio of 1: 1.5-2, stirring, filtering to obtain filtrate, and concentrating the filtrate to obtain urushiol.
5. The method for preparing the green superhydrophobic magnetic sponge according to claim 1, wherein the melamine sponge is immersed in the urushiol solution for 30s to 1 h.
6. The method for preparing green super-hydrophobic magnetic sponge according to claim 1, wherein Fe3O4The suspension is prepared by the following steps: mixing Fe3O4Mixing with deionized water according to the mass ratio of 10-20: 1, and then performing ultrasonic dispersion for 20min under 200W to obtain nano Fe3O4And (4) suspending the solution.
7. The method for preparing green super-hydrophobic magnetic sponge according to claim 1, wherein the green super-hydrophobic magnetic sponge is further dipped in Fe3O45-10 s in the suspension.
8. The preparation method of the green super-hydrophobic magnetic sponge as claimed in claim 1, wherein the green super-hydrophobic magnetic sponge is further immersed in urushiol solution for 5-10 s.
9. Use of a green superhydrophobic magnetic sponge prepared according to the method of any one of claims 1-8 in oil-water separation.
CN202110474808.3A 2021-04-29 2021-04-29 Preparation method and application of green super-hydrophobic magnetic sponge Pending CN113174083A (en)

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CN114853114A (en) * 2022-05-25 2022-08-05 福建师范大学 Magnetic urushiol iron nanoparticle with photo-thermal effect and preparation method thereof
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