CN115262231A - Self-repairing self-cleaning electromagnetic shielding fabric coating and preparation method and application thereof - Google Patents
Self-repairing self-cleaning electromagnetic shielding fabric coating and preparation method and application thereof Download PDFInfo
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
- D06M15/576—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them containing fluorine
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
- D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/80—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with boron or compounds thereof, e.g. borides
- D06M11/82—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with boron or compounds thereof, e.g. borides with boron oxides; with boric, meta- or perboric acids or their salts, e.g. with borax
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- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a self-repairing self-cleaning electromagnetic shielding fabric coating, a preparation method and application thereof, wherein the coating comprises the following raw materials in parts by weight: 40-80 parts of comb-shaped hydrophobic polyurethane, 2-20 parts of pomegranate-shaped magnetic silicon dioxide nanospheres, 0.1-1 part of pyrene borate, 0.2-5 parts of graphene and 2-20 parts of mixed solution of ethanol and water. The invention provides a novel self-repairing self-cleaning electromagnetic shielding fabric coating, which is based on pomegranate-shaped magnetic silica nanospheres and self-repairing polyurethane, has an electromagnetic shielding function and a super-hydrophobic self-cleaning function, can self-repair damaged parts to recover the functions, and solves the problems of poor electromagnetic shielding performance, no self-cleaning property, no durability and the like of an outdoor composite material. The method is simple, the preparation process is green and environment-friendly, and the method is easy for large-area outdoor application.
Description
Technical Field
The invention belongs to an electromagnetic shielding coating material, and particularly relates to a self-repairing self-cleaning electromagnetic shielding coating, and a preparation method and application thereof.
Background
With the explosive development of fifth generation communication technology, human life is inseparable from electronic communication devices. However, the electromagnetic interference generated by these devices during operation not only affects the normal operation of nearby electronic devices, but also has adverse effects on human health. In order to protect precision equipment and human bodies from external radiation, it is very important to develop a self-repairing electromagnetic shielding material with high efficiency. The polymer-based composite material is widely applied to the field of electromagnetic shielding due to the advantages of low density, corrosion resistance, low cost, good processing performance and the like. At present, the electromagnetic shielding performance of the polymer matrix composite material can be effectively improved by adding conductive fillers such as carbon nanotubes, graphene, metal nanowires/particles, MXene and the like. The patent CN110698847A provides an aqueous polyurethane-MXene electromagnetic shielding bionic nano composite material film and a preparation method thereof, wherein the method utilizes a shell bionic strategy and uses Ti 3 C 2 T x /Ti 2 CT x MXene and waterborne polyurethane with urethane groups are used as raw materials, so that a high-efficiency electromagnetic shielding composite material film with good mechanical property is constructed, and the film has excellent mechanical property and good electromagnetic shielding property. Patent CN111925642A proposes that firstly, a carbon nano tube aqueous dispersion is prepared, then, a synthesized self-repairing cationic aqueous polyurethane emulsion is added into the carbon nano tube aqueous dispersion, and the carbon nano tube is coated on the surface of a polyurethane emulsion particle by utilizing electrostatic adsorption interaction among ions with different charges, so that a self-repairing composite material is finally obtained. Most polymer-based materials are inevitably easy to be mechanically damaged, thereby generating structural defects such as cracks and the like, greatly reducing the physical properties and shortening the service life.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the problems in the prior art, the invention provides a novel self-repairing self-cleaning electromagnetic shielding fabric coating, based on pomegranate-shaped magnetic silica nanospheres and self-repairing polyurethane, the coating not only has an electromagnetic shielding function, but also has a super-hydrophobic self-cleaning function, and meanwhile, the coating can also self-repair damaged parts and recover the functions, so that the problems of poor electromagnetic shielding performance, no self-cleaning property, no durability and the like of an outdoor composite material are solved.
The invention also provides a preparation method and application of the self-repairing self-cleaning electromagnetic shielding fabric coating.
The technical scheme is as follows: in order to achieve the purpose, the invention provides a self-repairing self-cleaning electromagnetic shielding fabric coating which comprises the following raw materials in parts by weight: 40-80 parts of comb-shaped hydrophobic polyurethane, 2-20 parts of pomegranate-shaped magnetic silicon dioxide nanospheres, 0.1-1 part of pyrene borate, 0.2-5 parts of graphene and 2-20 parts of mixed solution of ethanol and water; the pomegranate-shaped structure is more conducive to electromagnetic wave absorption.
The preparation method of the comb-shaped hydrophobic polyurethane comprises the following steps:
(1) Adding 10-60 parts of acetone and 0.05-1 part of dimethyl phenyl phosphorus into 1-10 parts of thioglycerol and 1-20 parts of N- (1-pyrene) maleimide by weight part, reacting, purifying and drying to obtain a pyrene-containing dihydric alcohol monomer;
(2) According to the weight parts, 20-80 parts of acetone and 0.05-2 parts of dimethyl phenyl phosphorus are added into 1-15 parts of thioglycerol and 1-45 parts of tridecyl methacrylate for reaction, and then the mixture is purified and dried to obtain a fluorine-containing dihydric alcohol monomer;
(3) According to the parts by weight, preheating 1-20 parts of isophorone diisocyanate, 2-60 parts of polycaprolactone and 20-80 parts of acetone in an oil bath, keeping stirring to form a uniform solution, then adding 0.05-2 parts of dibutyltin dilaurate, and keeping reacting; then, respectively adding 0.5-10 parts of fluorine-containing dihydric alcohol monomer and 0.5-15 parts of pyrene-containing dihydric alcohol monomer, and continuously keeping the reaction; and (3) reducing the oil bath temperature, adding 0.5-5 parts of chain extender bis (2-hydroxyethyl) disulfide, and continuously reacting to obtain the comb-shaped hydrophobic polyurethane (MPU).
Wherein, the reaction is continuously carried out for 1-8h at the temperature of 20-70 ℃ in the step (1), and the pyrene-containing diol monomer is obtained after purification and drying; continuously reacting for 1-8h at 20-80 ℃ in the step (2), purifying and drying to obtain a fluorine-containing dihydric alcohol monomer; placing the mixture in an oil bath at the temperature of 40-80 ℃ for preheating and keeping stirring to form a uniform solution in the step (3), then adding 0.05-2 parts of dibutyltin dilaurate, and keeping reacting for 2-6h; then, respectively adding 0.5-10 parts of fluorine-containing monomer and 0.5-15 parts of pyrene-containing monomer, and continuously reacting for 1-3h; adjusting the oil bath temperature to 30-70 ℃, adding 0.5-5 parts of chain extender bis (2-hydroxyethyl) disulfide, and continuously reacting for 2-6h to obtain the comb-shaped hydrophobic polyurethane.
Preferably, the polycaprolactone has a number average molecular weight of 800 to 2000, the comb-shaped hydrophobic polyurethane has the number average molecular weight of 10000-30000.
The preparation method of the pomegranate-shaped magnetic silicon dioxide nanospheres comprises the following steps:
adding 0.1-2 parts of Fe into 0.5-2 parts of ammonia water and 10-60 parts of ethanol/deionized water mixture by weight 3 O 4 Dispersing the particles, dripping 0.3-3 parts of dopamine into the dispersion liquid under the mechanical stirring, and collecting Fe after stirring 3 O 4 @ PDA nanoparticles, fe to be prepared 3 O 4 Dispersing the @ PDA nano particles in 20-150 parts of deionized water again, and adding 0.5-2 parts of ammonia water and 0.1-2 parts of surfactant; and then, dropwise adding a mixed solution of 10-50 parts of n-hexane and 5-40 parts of tetraethyl orthosilicate into the dispersion liquid, magnetically collecting a product after reaction, adding the product into 50-200 parts of ethanol, and performing reflux treatment to finally obtain the pomegranate-shaped magnetic silica nanospheres.
Wherein, a mixed solution of 10-50 parts of n-hexane and 5-40 parts of tetraethyl orthosilicate is dripped into the dispersion liquid, and after the reaction is carried out for 6-24h at the temperature of 25-65 ℃, a product is collected by a magnet, washed and dried.
Preferably, wherein said Fe 3 O 4 The particle size of the particles is 20-500nm.
The preparation method of the self-repairing self-cleaning electromagnetic shielding fabric coating comprises the following steps:
adding 0.1-1 part of pyrene borate, 0.5-5 parts of pomegranate-shaped magnetic silicon dioxide nanospheres and 0.2-2 parts of graphene (G) into a mixed solution containing ethanol and water according to parts by weight, washing after reaction, and drying to obtain the pomegranate-shaped magnetic silicon dioxide nanosphere modified stoneGrapheme (mFe) 3 O 4 @SiO 2 -G)；
Uniformly mixing 100-200 parts by weight of comb-shaped hydrophobic polyurethane and 5-50 parts by weight of pomegranate-shaped magnetic silicon dioxide nanosphere modified graphene, and drying to obtain the self-repairing self-cleaning electromagnetic shielding fabric coating.
Adding pyrene borate, pomegranate-shaped magnetic silicon dioxide nanospheres and graphene (G) into a mixed solution containing ethanol and water, reacting for 1-5h at 25-65 ℃, washing, and drying to obtain the pomegranate-shaped magnetic silicon dioxide nanosphere modified graphene.
The self-repairing self-cleaning electromagnetic shielding fabric coating is widely applied to flexible sensors, intelligent wearable materials, self-healing materials and military stealth materials.
The self-repairing self-cleaning electromagnetic shielding fabric coating is prepared by uniformly mixing comb-shaped hydrophobic polyurethane and pomegranate-shaped magnetic silicon dioxide nanosphere modified graphene, coating the mixture on the surface of a fabric and drying the fabric at a high temperature.
Preferably, the thickness of the coating is 1-20 mm, and the coating is carried out on the surface of the fabric by at least one of brushing, rolling, dipping, spraying and curtain coating.
The self-repairing self-cleaning electromagnetic shielding coating provided by the invention not only solves the durability of the surface performance of the existing functional coating, but also solves the problems of low electric conductivity, general electromagnetic shielding performance, poor compatibility and the like of the existing polymer-based composite material. After the surface of the coating is subjected to physical abrasion or organic matter pollution, due to excellent photo-thermal and electro-thermal characteristics, the dynamic disulfide bond of the PMNs-FG/MPU fabric coating and the pi-pi effect between the graphene and the PPU side chain, the self-repairing process can be stimulated by solar radiation or current, and the fabric coating has excellent self-repairing performance, so that the durability of the coating in outdoor use is ensured. Meanwhile, the film is endowed with excellent self-cleaning performance by the fluorination modification of the graphene. The novel pomegranate-shaped magnetic microsphere PMNs wrapping the plurality of high-magnetism Fe3O4 nano particles show excellent electromagnetic shielding performance, when the thickness of the coating is 1mm, the electromagnetic shielding energy efficiency (EMI SE) value of the coating is as high as 50dB, and the requirement of a commercial electromagnetic shielding material is met. The method is simple, the preparation process is green and environment-friendly, and the method is easy for large-area outdoor application.
The self-repairing self-cleaning electromagnetic shielding coating provided by the invention mainly combines the dielectric loss and the magnetic loss of PMNs-FG, thereby obtaining excellent electromagnetic shielding performance; a micro-nano structure and the modification of low surface energy substances are formed on the surface of the coating based on the PMNs-FG, the coating has excellent hydrophobicity to common liquid, and a self-cleaning function can be realized; inspired by geckos, the coating shows excellent self-repairing performance by utilizing a combination strategy of dynamic reversible disulfide bond and pi-pi stacking interaction of polyurethane and PMNs-FG, and the acting force of a conductive medium and resin is enhanced by forming pi-pi interaction between a special pyrene structure on a polyurethane branched chain and the surface of graphene. Therefore, the coating not only repairs the damaged surface structure, but also can realize higher repair efficiency, so that various properties of the repaired coating are closer to those of the original coating.
In the preparation process, a fluorine-containing dihydric alcohol monomer, a pyrene-containing dihydric alcohol monomer and pyrene borate are used. Wherein the preparation of the comb polyurethane comprises the following steps: on the basis of a typical prepolymer method, a diol monomer containing a special structure (a fluorocarbon chain structure and a pyrene ring structure) is obtained through a mercapto-alkene click reaction, and can react with an isocyanate group to successfully introduce the special structure into a polyurethane system in a branched chain form. Simultaneously, a novel self-repairing strategy is adopted: the self-repairing performance of the organic-inorganic composite coating is usually completed by the heat migration of the resin, and the acting force between the resin and the inorganic matter is small, so the repairing efficiency of the strategy is usually low. In the invention, the acting force between the resin and the conductive filler is improved through hydrogen bonds, hydrophobic acting force, pi-pi effect and other modes, the conductive filler is helped to participate in the self-repairing process, the self-repairing efficiency of the material is improved, and the performance of the repaired material is closer to the initial state.
Has the beneficial effects that: compared with the prior art, the invention has the following advantages:
(1) Based on the special pomegranate-shaped structure of the magnetic microspheres, the coating can be endowed with excellent electromagnetic shielding property;
(2) The composite fabric coating shows excellent super-hydrophobic self-cleaning property;
(3) Based on the comb-shaped structure of polyurethane, the fabric coating can automatically repair the damaged part after being worn by external force or broken by stretching, and recover the mechanical, electromagnetic shielding and self-cleaning properties of the fabric coating;
(4) The preparation process of the composite fabric coating is green and environment-friendly and has no pollution;
(5) Can be coated on other substrates and can be applied in the fields of intelligent wearable, flexible sensors, military stealth and the like.
Drawings
FIG. 1 is an FT-IR spectrum of a fluorine-containing diol monomer (M-PFM), a pyrene-containing diol monomer (M-NPM) and a comb-like hydrophobic polyurethane (MPU) synthesized in example 4. FT-IR spectrogram can successfully prove that the fluorine-containing dihydric alcohol monomer and the pyrene-containing dihydric alcohol monomer are grafted into polyurethane to form comb-shaped and hydrophobic effects.
FIG. 2 is a TEM image of pomegranate-shaped magnetic Particles (PMNs) in example 4. Multiple Fe can be seen by TEM 3 O 4 The nano-particles are coated by polydopamine PDA, and a SiO2 shell is formed by hydrolysis of tetraethyl orthosilicate TEOS, so that the pomegranate-shaped magnetic nano-particles are finally formed.
Fig. 3 is an SEM image of PMNs loaded graphene in example 4, and it can be seen from the SEM photograph that PMNs have been successfully loaded on the graphene sheet layer.
Fig. 4 is a graph of the self-healing process (optical microscopy image and water contact angle image) of the composite fabric coating of example 4. The figure shows that the coating has cracks and the super-hydrophobic property is lost after the damage, but the coating cracks disappear after the repair, and the super-hydrophobic performance of the damaged part is recovered.
FIG. 5 is a graph of the self-healing process for the blank coating of example 4, showing that the damaged coating cannot be healed.
FIG. 6 is a graph of the self-cleaning process of the composite fabric coating of example 4, showing that the simulated soil on the surface of the coating can be removed by water droplets without residue, indicating that the surface of the coating has excellent self-cleaning properties.
Fig. 7 shows the electromagnetic shielding performance of different fabric coatings in example 4 in the X-band. Due to the high conductivity and good magnetic properties of the PMNs loaded graphene (PMNs-FG), the flexible PMNs-FG/MPU composite fabric coatings exhibit excellent EMI shielding performance, which can reach about 50dB, compared to other coatings.
FIG. 8 is a graph of resistivity before and after self-healing (a) for the PMNs-FG/PPU coatings of example 4, stress-strain curves before and after self-healing (b) for the PMNs-FG/PPU coatings, and EMI SE values in the X-band (c) before and after self-healing for the PMNs-FG/PPU coatings. After the PMNs-FG/PPU coating is repaired, the electric conductivity, the mechanical property and the electromagnetic shielding property of the PMNs-FG/PPU coating are recovered, and the PMNs-FG/PPU coating has an excellent self-repairing function.
Detailed Description
The present invention is further illustrated by the following examples.
The raw materials used in the examples of the present invention are commercially available, or commercially available raw materials of the same type may be used.
The following examples are all calculated in parts by weight.
Example 1
(1) Adding 1 part of thioglycerol and 1 part of N- (1-pyrene) maleimide into a round-bottom flask, adding 10 parts of acetone as a solvent and 0.05 part of xylyl phosphine as a catalyst, continuously reacting for 1 hour at 70 ℃, and purifying and drying to obtain the pyrene-containing dihydric alcohol monomer.
Adding 1 part of thioglycerol and 1 part of tridecyl methacrylate into a round-bottom flask, adding 20 parts of acetone as a solvent and 0.05 part of dimethyl phenyl phosphorus as a catalyst, continuously reacting for 1 hour at 80 ℃, purifying and drying to obtain the fluorine-containing dihydric alcohol monomer.
Adding 1 part of isophorone diisocyanate, 2 parts of polycaprolactone (molecular weight 2000) and 20 parts of acetone into a three-neck flask, placing the three-neck flask in an oil bath at 80 ℃ for preheating, keeping stirring to form a uniform solution, then adding 0.05-2 parts of dibutyltin dilaurate, and keeping reacting for 2 hours. Then, 0.5 part of fluorine-containing diol monomer and 0.5 part of pyrene-containing diol monomer are added respectively, and the reaction is kept for 1 hour. Finally, the oil bath temperature was adjusted to 70 ℃, 0.5 part of chain extender bis (2-hydroxyethyl) disulfide was added, and the reaction was continued for 2 hours to obtain comb-like hydrophobic polyurethane (MPU) (molecular weight: 30000 by GPC).
(2) 0.5 part of ammonia water (concentration 25%), 10 parts of an ethanol/deionized water mixture (volume ratio 1:2) was added to a three-necked flask, and then 0.1 part of Fe was added by ultrasonic treatment 3 O 4 Particles (20 nm) were dispersed in the solution. 0.3 Part of Dopamine (PDA) is added into the dispersion liquid in a dropwise manner under the mechanical stirring, and after the continuous stirring for 2 hours, fe is collected 3 O 4 @ PDA nano particles, washed with deionized water and dried. Fe to be prepared 3 O 4 The @ PDA nanoparticles were redispersed in 20 parts of deionized water and 0.1 part of cetyltrimethylammonium chloride containing 0.5 part of ammonia (25% concentration) was added. Subsequently, a mixed solution of 10 parts of n-hexane and 5 parts of tetraethyl orthosilicate was added dropwise to the dispersion, reacted at 65 ℃ for 6 hours, and then the product was collected with a magnet, washed, and dried. Adding the product into 50 parts of ethanol, performing reflux treatment at 65 ℃ for 2h to remove the template, and finally obtaining pomegranate-shaped magnetic silica nanospheres (PMNs) (mFe) 3 O 4 @SiO 2 )。
(3) 0.1 part of 1-pyrene borate and 0.5 part of mFe 3 O 4 @SiO 2 And 0.2 parts of graphene (G) was added to 2 parts of a mixed solution (volume ratio = 1:1) containing ethanol and water. Reacting for 1h at 65 ℃, washing and drying to obtain pomegranate-shaped magnetic silicon dioxide nanosphere modified graphene (PMNs-FG) (mFe) 3 O 4 @SiO 2 -G)。
Uniformly mixing 100 parts of comb-shaped hydrophobic polyurethane and 5 parts of pomegranate-shaped magnetic silicon dioxide nanosphere modified graphene, coating the mixture on the surface of a fabric, and drying the fabric at 80 ℃ for 8 hours to obtain a self-repairing self-cleaning electromagnetic shielding fabric coating (PMNs-FG/MPU), wherein the thickness of the coating is 20mm.
Example 2
(1) Adding 10 parts of thioglycerol and 20 parts of N- (1-pyrene) maleimide into a round-bottom flask, adding 60 parts of acetone as a solvent and 1 part of xylyl phosphine as a catalyst, continuously reacting for 8 hours at 20 ℃, and purifying and drying to obtain the pyrene-containing dihydric alcohol monomer.
Adding 15 parts of thioglycerol and 45 parts of tridecyl methacrylate into a round-bottom flask, adding 80 parts of acetone as a solvent and 2 parts of dimethyl phenyl phosphorus as a catalyst, continuously reacting for 8 hours at 20 ℃, purifying and drying to obtain the fluorine-containing diol monomer.
Adding 20 parts of isophorone diisocyanate, 60 parts of polycaprolactone (molecular weight is 1000) and 80 parts of acetone into a three-neck flask, placing the three-neck flask in an oil bath at 40 ℃ for preheating, keeping stirring to form a uniform solution, then adding 2 parts of dibutyltin dilaurate, and keeping reacting for 6 hours. Then, 10 parts of fluorine-containing diol monomer and 15 parts of pyrene-containing diol monomer are added respectively, and the reaction is kept for 3 hours. Finally, the oil bath temperature was adjusted to 30 ℃, 5 parts of chain extender bis (2-hydroxyethyl) disulfide were added, and after continuing the reaction for 6 hours, comb-like hydrophobic polyurethane (MPU) was obtained (molecular weight: 15000 by GPC).
(2) 2 parts of aqueous ammonia (concentration 25%), 60 parts of an ethanol/deionized water mixture (volume ratio 1:2) were added to a three-necked flask, and then 2 parts of Fe were added by ultrasonic treatment 3 O 4 Particles (500 nm) were dispersed in the solution. Dropwise adding 3 Parts of Dopamine (PDA) into the dispersion under mechanical stirring, continuously stirring for 10h, and collecting Fe 3 O 4 @ PDA nano particles, washing with deionized water and drying. Fe to be prepared 3 O 4 The @ PDA nanoparticles were again dispersed in 150 parts of deionized water, and 2 parts of ammonium hydroxide (concentration 25%) and cetyltrimethylammonium bromide (cetyltrimethylammonium bromide) were added. Subsequently, a mixed solution of 50 parts of n-hexane and 40 parts of tetraethyl orthosilicate was added dropwise to the dispersion, and after 24 hours of reaction at a temperature of 25 ℃, the product was collected with a magnet, washed, and dried. Adding the product into 200 parts of ethanol, performing reflux treatment at 65 ℃ for 8 hours to remove the template, and finally obtaining pomegranate-shaped magnetic silica nanospheres (PMNs) (mFe) 3 O 4 @SiO 2 )。
(3) 1 part of 1-pyrene borate and 5 parts of mFe 3 O 4 @SiO 2 And 2 parts of graphene (G) were added to 20 parts of a mixed solution (volume ratio = 1:1) containing ethanol and water. Reacting for 5h at 25 ℃, washing and drying to obtain pomegranate-shaped magnetic silicon dioxide nanosphere modified graphene (PMNs-FG)(mFe 3 O 4 @SiO 2 -G)。
Uniformly mixing 200 parts of comb-shaped hydrophobic polyurethane and 50 parts of pomegranate-shaped magnetic silicon dioxide nanosphere modified graphene, coating the mixture on the surface of a fabric, and drying the fabric at 80 ℃ for 8 hours to obtain a self-repairing self-cleaning electromagnetic shielding fabric coating (PMNs-FG/MPU), wherein the thickness of the coating is 8mm.
Example 3
(1) Adding 3 parts of thioglycerol and 7 parts of N- (1-pyrene) maleimide into a round-bottom flask, adding 20 parts of acetone as a solvent and 0.1 part of xylyl phosphine as a catalyst, continuously reacting for 5 hours at 40 ℃, and purifying and drying to obtain the pyrene-containing dihydric alcohol monomer.
Adding 4 parts of thioglycerol and 10 parts of tridecyl methacrylate into a round-bottom flask, adding 30 parts of acetone as a solvent and 0.15 part of dimethyl phenyl phosphorus as a catalyst, continuously reacting for 5 hours at 40 ℃, purifying and drying to obtain the fluorine-containing dihydric alcohol monomer.
Adding 8 parts of isophorone diisocyanate, 20 parts of polycaprolactone (molecular weight 1500) and 40 parts of acetone into a three-neck flask, placing the three-neck flask in an oil bath at 50 ℃ for preheating, keeping stirring to form a uniform solution, then adding 0.5 part of dibutyltin dilaurate, and keeping reacting for 3 hours. Then, 2 parts of fluorine-containing diol monomer and 5 parts of pyrene-containing diol monomer are added respectively, and the reaction is kept for 2 hours. Finally, the oil bath temperature was adjusted to 40 ℃,2 parts of chain extender bis (2-hydroxyethyl) disulfide were added, and reaction was continued for 3 hours to obtain comb-like hydrophobic polyurethane (MPU) (molecular weight: 25000 measured by GPC).
(2) 0.8 part of ammonia water (concentration 25%), 30 parts of an ethanol/deionized water mixture (volume ratio 1:2) was added to a three-necked flask, and then 0.8 part of Fe was added by ultrasonic treatment 3 O 4 Particles (100 nm) were dispersed in the solution. Under mechanical stirring, 1.2 Parts of Dopamine (PDA) is added into the dispersion liquid in a dropwise manner, and after continuous stirring for 5 hours, fe is collected 3 O 4 @ PDA nano particles, washing with deionized water and drying. Fe to be prepared 3 O 4 The @ PDA nanoparticles were again dispersed in 60 parts of deionized water, and 0.8 part of octadecyl trimethyl ammonium chloride containing 0.8 part of ammonia (concentration 25%) was added. Followed byDropping a mixed solution of 20 parts of n-hexane and 15 parts of tetraethyl orthosilicate into the dispersion liquid, reacting at the temperature of 30 ℃ for 10 hours, collecting a product by a magnet, washing and drying. Adding the product into 90 parts of ethanol, performing reflux treatment at 65 ℃ for 4 hours to remove the template, and finally obtaining pomegranate-shaped magnetic silica nanospheres (PMNs) (mFe) 3 O 4 @SiO 2 )。
(3) 0.5 part of 1-pyrene borate and 2 parts of mFe 3 O 4 @SiO 2 And 0.8 part of graphene (G) was added to 8 parts of a mixed solution (volume ratio = 1:1) containing ethanol and water. Reacting at 35 ℃ for 4h, washing and drying to obtain pomegranate-shaped magnetic silicon dioxide nanosphere modified graphene (PMNs-FG) (mFe) 3 O 4 @SiO 2 -G)。
Uniformly mixing 120 parts of comb-shaped hydrophobic polyurethane and 20 parts of pomegranate-shaped magnetic silicon dioxide nanosphere modified graphene, coating the mixture on the surface of a fabric, and drying the fabric at 80 ℃ for 8 hours to obtain a self-repairing self-cleaning electromagnetic shielding fabric coating (PMNs-FG/MPU), wherein the thickness of the coating is 14mm.
Example 4
(1) Adding 5 parts of thioglycerol and 11 parts of N- (1-pyrene) maleimide into a round-bottom flask, adding 30 parts of acetone serving as a solvent and 0.4 part of dimethyl phenyl phosphorus serving as a catalyst, continuously reacting for 3 hours at 50 ℃, purifying and drying to obtain the pyrene-containing dihydric alcohol monomer.
Adding 8 parts of thioglycerol and 22 parts of tridecyl methacrylate into a round-bottom flask, adding 50 parts of acetone as a solvent and 1 part of xylyl phosphine as a catalyst, continuously reacting for 3 hours at 50 ℃, purifying and drying to obtain the fluorine-containing dihydric alcohol monomer.
11 parts of isophorone diisocyanate, 32 parts of polycaprolactone (molecular weight: 1200) and 50 parts of acetone are added into a three-neck flask, the three-neck flask is placed in an oil bath at 60 ℃ for preheating, stirring is kept to form a uniform solution, and then 1.2 parts of dibutyltin dilaurate is added, and the reaction is kept for 4 hours. Then, 5 parts of fluorine-containing diol monomer and 8 parts of pyrene-containing diol monomer are added respectively, and the reaction is kept for 3 hours. Finally, the oil bath temperature was adjusted to 50 ℃, 3 parts of chain extender bis (2-hydroxyethyl) disulfide were added, and after continuing the reaction for 4 hours, comb-like hydrophobic polyurethane (MPU) was obtained (molecular weight: 20000 by GPC test).
(2) 1.2 parts of aqueous ammonia (concentration 25%), 40 parts of an ethanol/deionized water mixture (volume ratio 1:2) were added to a three-necked flask, and then 1.2 parts of Fe was added by ultrasonic treatment 3 O 4 Particles (250 nm) were dispersed in the solution. Under mechanical stirring, 1.6 Parts of Dopamine (PDA) is added into the dispersion liquid in a dropwise manner, and after continuous stirring for 6 hours, fe is collected 3 O 4 @ PDA nano particles, washing with deionized water and drying. Fe to be prepared 3 O 4 The @ PDA nanoparticles were redispersed in 80 parts of deionized water and 1.2 parts of ammonium behenyl trimethyl chloride containing 1.2 parts of ammonia (25% concentration) was added. Subsequently, a mixed solution of 30 parts of n-hexane and 22 parts of tetraethyl orthosilicate was added dropwise to the dispersion, and after reaction at 35 ℃ for 14 hours, the product was collected with a magnet, washed, and dried. Adding the product into 110 parts of ethanol, performing reflux treatment at 65 ℃ for 5 hours to remove the template, and finally obtaining pomegranate-shaped magnetic silica nanospheres (PMNs) (mFe) 3 O 4 @SiO 2 )。
(3) 0.6 part of 1-pyrene borate and 2.5 parts of mFe are mixed 3 O 4 @SiO 2 And 1 part of graphene (G) was added to 10 parts of a mixed solution (volume ratio = 1:1) containing ethanol and water. Reacting at 40 ℃ for 4h, washing and drying to obtain pomegranate-shaped magnetic silicon dioxide nanosphere modified graphene (PMNs-FG) (mFe) 3 O 4 @SiO 2 -G)。
(4) After 150 parts of comb-shaped hydrophobic polyurethane and 26 parts of pomegranate-shaped magnetic silicon dioxide nanosphere modified graphene are uniformly mixed, the mixture is coated on the surface of a fabric and dried at 80 ℃ for 8 hours to obtain a self-repairing self-cleaning electromagnetic shielding fabric coating (PMNs-FG/MPU), and the thickness of the coating is 1mm.
Example 5
(1) Adding 8 parts of thioglycerol and 15 parts of N- (1-pyrene) maleimide into a round-bottom flask, adding 50 parts of acetone serving as a solvent and 0.8 part of xylyl phosphine serving as a catalyst, continuously reacting for 2 hours at 60 ℃, and purifying and drying to obtain the pyrene-containing dihydric alcohol monomer.
Adding 12 parts of thioglycerol and 40 parts of tridecyl methacrylate into a round-bottom flask, adding 70 parts of acetone as a solvent and 1.5 parts of xylyl phosphine as a catalyst, continuously reacting for 2 hours at 60 ℃, purifying and drying to obtain the fluorine-containing diol monomer.
14 parts of isophorone diisocyanate, 50 parts of polycaprolactone (molecular weight 800) and 70 parts of acetone are added into a three-neck flask, the three-neck flask is placed in an oil bath at 70 ℃ for preheating, stirring is kept to form a uniform solution, and then 1.6 parts of dibutyltin dilaurate is added, and the reaction is kept for 3 hours. Then, 8 parts of fluorine-containing diol monomer and 12 parts of pyrene-containing diol monomer are added respectively, and the reaction is kept for 2 hours. Finally, the oil bath temperature was adjusted to 50 ℃, 4 parts of chain extender bis (2-hydroxyethyl) disulfide were added, and reaction was continued for 5 hours to obtain comb-like hydrophobic polyurethane (MPU) (molecular weight: 10000 by GPC).
(2) 1.5 parts of ammonia (concentration 25%), 50 parts of an ethanol/deionized water mixture (volume ratio 1:2) were added to a three-necked flask, and then 1.5 parts of Fe was added by ultrasonic treatment 3 O 4 Particles (400 nm) were dispersed in the solution. Dropping 2 Parts of Dopamine (PDA) into the dispersion liquid under mechanical stirring, continuously stirring for 8h, and collecting Fe 3 O 4 @ PDA nano particles, washing with deionized water and drying. Fe to be prepared 3 O 4 The @ PDA nanoparticles were re-dispersed in 120 parts of deionized water, and 1.5 parts of ammonium hydroxide (concentration 25%) and 1.5 parts of cetyltrimethylammonium bromide were added. Subsequently, a mixed solution of 40 parts of n-hexane and 30 parts of tetraethyl orthosilicate was added dropwise to the dispersion, and after reaction at 45 ℃ for 16 hours, the product was collected with a magnet, washed and dried. Adding the product into 150 parts of ethanol, performing reflux treatment at 65 ℃ for 6 hours to remove the template, and finally obtaining pomegranate-shaped magnetic silica nanospheres (PMNs) (mFe) 3 O 4 @SiO 2 )。
(3) 0.8 part of 1-boric acid pyrene and 4 parts of mFe 3 O 4 @SiO 2 And 1.5 parts of graphene (G) were added to 15 parts of a mixed solution (volume ratio = 1:1) containing ethanol and water. Reacting at 45 ℃ for 2h, washing and drying to obtain pomegranate-shaped magnetic silicon dioxide nanosphere modified graphene (PMNs-FG) (mFe) 3 O 4 @SiO 2 -G)。
Uniformly mixing 180 parts of comb-shaped hydrophobic polyurethane and 45 parts of pomegranate-shaped magnetic silicon dioxide nanosphere modified graphene, coating the mixture on the surface of the fabric, and drying the fabric at 80 ℃ for 8 hours to obtain a self-repairing type self-cleaning electromagnetic shielding fabric coating (PMNs-FG/MPU), wherein the thickness of the coating is 5mm.
Test example 1
The test method comprises the following steps:
(1) Fourier Infrared Spectroscopy test (FT-IR)
The chemical structures of the monomer and MPU of example 4 were tested by Fourier Infrared Spectroscopy, and ATR Total reflection test was carried out at room temperature, with a wavelength range of 500-4000cm -1 。
The FT-IR spectrogram in FIG. 1 successfully proves that the fluorine-containing diol monomer and the pyrene-containing diol monomer have been grafted into polyurethane and form comb-like and hydrophobic effects.
(2) Transmission electron microscope Test (TEM)
The core-shell structure of the PMNs in example 4 was observed with a transmission electron microscope at a test voltage of 200kV.
It can be seen from the TEM of FIG. 2 that a plurality of Fe 3 O 4 The nanoparticles were coated with polydopamine PDA and hydrolyzed to form SiO by tetraethylorthosilicate TEOS 2 And (3) a shell, and finally forming the pomegranate-shaped magnetic nanoparticles, wherein a plurality of nano ferroferric oxide particles similar to pomegranate seeds are arranged in the sphere.
(3) Scanning Electron Microscope (SEM)
The microscopic morphology of the PMNs-FG of example 4 was tested using a scanning electron microscope at a test voltage of 5kV.
It can be seen from the SEM of fig. 3 that a plurality of pomegranate-shaped structured magnetic nanoparticles have been successfully loaded onto the graphene sheet layer.
(4) Self-repair performance test
Blank PU coating: the preparation method is the same as example 4, except that: no chain extender hydroxyethyl disulfide was added.
Respectively scratching a notch with the length of 2cm and the depth of 0.5cm on the surfaces of the blank PU coating and the PMNs-FG/MPU composite coating by using a blade, then placing the blank PU coating and the PMNs-FG/MPU composite coating in an oven at 50 ℃, and recording the shape change of scratches in the self-repairing process of the blank PU coating and the PMNs-FG/MPU composite coating in example 4 by using an optical microscope, wherein the times of an objective lens and an eyepiece are respectively multiplied by 50 and multiplied by 10.
The self-repairing process diagram (optical microscopy image and water contact angle diagram) of the composite fabric coating is shown in FIG. 4. In FIG. 4, it is shown that the damaged coating has cracks and the superhydrophobic performance is lost, but the cracks of the repaired coating disappear and the superhydrophobic performance of the damaged part is restored.
FIG. 5 shows that the blank PU coating has no repair even at 50 ℃ for 15 minutes, which indicates that the PU coating has no self-repair function, and the hydroxyethyl disulfide plays a main determining role in the self-repair function of the coating.
(5) Super-hydrophobic and self-cleaning performance
The hydrophobicity of the coating prepared in example 4 was evaluated using a contact angle measuring instrument DSA 100. Firstly, placing a coated fabric on a horizontal table, dripping liquid drops, observing and recording the shapes of the liquid drops, and calculating by software simulation to obtain the size of a contact angle. When the rolling angle is tested, the horizontal table top is replaced by an inclined plane with an adjustable angle, and the horizontal table top is set to a proper angle to observe whether water drops can freely slide down from the coating.
FIG. 4 shows that the scratch coating loses super-hydrophobic property in the damaged area, the contact angle is reduced to 115.06 degrees, the contact angle of the damaged part is recovered to 153.6 degrees after self-repairing, and the coating is shown to have self-repairing super-hydrophobic property.
In fig. 6 it is shown that the simulated stains on the surface of the coating can be removed by water droplets without residue, indicating that the surface of the coating has excellent self-cleaning properties.
(6) Electromagnetic shielding performance test
The S parameters of the samples of example 4 were measured by the waveguide method using a vector network analyzer in the X-band frequency range according to ASTM D5568-08. The S parameters correspond to transmission (S12 and S21) and reflection (S11 and S22) of the transverse electromagnetic wave. The self-healing composite films were cut into 22.86mm by 10.16mm samples for testing. From the S parameter, R, A and the T value are calculated. R and T can be expressed as R = | S11- 2 ＝|S22| 2 And T = | S12 2 ＝|S21| 2 . Using the formula a + R + T =1, a can be calculated from the results of R and T. Therefore, the reflectance and effective absorbance can be easily defined as SE R = 10log (1-R) and SE A ＝-10log[T/(1-R)]. For SE>15dB, multiple reflection (SE) M ) And can be ignored.
Due to the high conductivity and good magnetism of the PMNs loaded graphene (PMNs-FG), compared with other coatings (pomegranate-shaped structure magnetic nanoparticles PMNs, graphene and comb-shaped polyurethane blended coating Fe) as shown in FIG. 7 3 O 4 NPs/FG/MPU, graphene and comb-shaped polyurethane blended coating FG/MPU, pomegranate-shaped structure magnetic nanoparticles and comb-shaped polyurethane blended coating PMNs/MPU, pure comb-shaped polyurethane coating MPU), and the flexible PMNs-FG/MPU composite fabric coating shows excellent EMI shielding performance, and the EMI efficiency can reach about 50dB.
Wherein, the pomegranate-shaped magnetic nanoparticles PMNs are the product of the step (2) in the embodiment 4 of the present invention;
the nano-particle PMNs modified graphene and comb-shaped polyurethane blended coating PMNs-FG/MPU is the coating prepared in the embodiment 4 of the invention;
pomegranate-shaped structure magnetic nanoparticle PMNs, graphene and comb-shaped polyurethane direct blending coating Fe 3 O 4 NPs/FG/MPU is the coating prepared according to the method of example 4 of the present invention without using step (3);
the graphene and comb-shaped polyurethane blended coating FG/MPU is a coating prepared by the method of the step (4) directly with graphene after comb-shaped hydrophobic polyurethane (MPU) is prepared by the method of the embodiment 4 of the invention;
the pomegranate-shaped structure magnetic nano particles and the comb-shaped polyurethane blended coating PMNs/MPUs are coatings prepared by the method of the step (4) directly from comb-shaped hydrophobic polyurethane (MPU) and magnetic silica nanospheres (PMNs) without using the step (3) according to the method of the embodiment 4 of the invention;
the pure comb polyurethane coating MPU was a coating prepared from the product of step (1) of example 4 of this invention.
(7) A four-probe resistance tester is adopted to test the resistivity of the PMNs-FG/MPU coating prepared in the example 4 before and after the repeated self-repairing; testing a stress-strain curve before and after self-repairing of the PMNs-FG/MPU composite coating by using a universal drawing machine, wherein the drawing speed is 0.5cm/s; s parameters before and after self-repair of PMNs-FG/PPU coatings were measured by the waveguide method using a vector network analyzer in the X-band frequency range according to ASTM D5568-08. FIG. 8 is a graph showing the resistivity of the PMNs-FG/PPU coating of example 4 before and after self-repair, the stress-strain curve of the PMNs-FG/PPU coating before and after self-repair, and the EMI SE value of the PMNs-FG/PPU coating in the X band before and after self-repair. After the PMNs-FG/PPU coating is repaired, the electric conductivity, the mechanical property and the electromagnetic shielding property of the PMNs-FG/PPU coating are recovered, and the PMNs-FG/PPU coating has an excellent self-repairing function.
Claims (10)
1. A self-repairing self-cleaning electromagnetic shielding fabric coating is characterized by comprising the following raw materials in parts by weight: 40-80 parts of comb-shaped hydrophobic polyurethane, 2-20 parts of pomegranate-shaped magnetic silicon dioxide nanospheres, 0.1-1 part of pyrene borate, 0.2-5 parts of graphene and 2-20 parts of mixed solution of ethanol and water.
2. The self-repairing self-cleaning electromagnetic shielding fabric coating of claim 1, wherein the comb-like hydrophobic polyurethane is prepared by the following steps:
(1) According to parts by weight, adding 10-60 parts of acetone and 0.05-1 part of dimethyl phenyl phosphorus into 1-10 parts of thioglycerol and 1-20 parts of N- (1-pyrene) maleimide, reacting, purifying and drying to obtain a pyrene-containing dihydric alcohol monomer;
(2) According to the weight parts, 20-80 parts of acetone and 0.05-2 parts of dimethyl phenyl phosphorus are added into 1-15 parts of thioglycerol and 1-45 parts of tridecyl methacrylate for reaction, and then the mixture is purified and dried to obtain a fluorine-containing dihydric alcohol monomer;
(3) According to the parts by weight, preheating 1-20 parts of isophorone diisocyanate, 2-60 parts of polycaprolactone and 20-80 parts of acetone in an oil bath, keeping stirring to form a uniform solution, then adding 0.05-2 parts of dibutyltin dilaurate, and keeping reacting; then, respectively adding 0.5-10 parts of fluorine-containing dihydric alcohol monomer and 0.5-15 parts of pyrene-containing dihydric alcohol monomer, and continuously keeping the reaction; and (3) reducing the oil bath temperature, adding 0.5-5 parts of chain extender bis (2-hydroxyethyl) disulfide, and continuously reacting to obtain the comb-shaped hydrophobic polyurethane.
3. The self-repairing self-cleaning electromagnetic shielding fabric coating of claim 2, wherein in step (1), the reaction is continued for 1-8h at 20-70 ℃, and the pyrene-containing diol monomer is obtained after purification and drying; continuously reacting for 1-8h at 20-80 ℃ in the step (2), purifying and drying to obtain a fluorine-containing dihydric alcohol monomer; placing the mixture in an oil bath at the temperature of 40-80 ℃ for preheating and keeping stirring to form a uniform solution in the step (3), then adding 0.05-2 parts of dibutyltin dilaurate, and keeping reacting for 2-6h; then, respectively adding 0.5-10 parts of fluorine-containing monomer and 0.5-15 parts of pyrene-containing monomer, and continuously keeping the reaction for 1-3h; adjusting the oil bath temperature to 30-70 ℃, adding 0.5-5 parts of chain extender bis (2-hydroxyethyl) disulfide, and continuously reacting for 2-6h to obtain the comb-shaped hydrophobic polyurethane.
4. The self-repairing self-cleaning electromagnetic shielding fabric coating of claim 1, wherein the comb-like hydrophobic polyurethane has a number average molecular weight of 10000-30000.
5. The self-repairing self-cleaning electromagnetic shielding fabric coating of claim 1, wherein the preparation steps of the pomegranate-shaped magnetic silica nanospheres are as follows:
adding 0.1-2 parts of Fe into 0.5-2 parts of ammonia water and 10-60 parts of ethanol/deionized water mixture by weight 3 O 4 Dispersing the particles, dripping 0.3-3 parts of dopamine into the dispersion liquid under the mechanical stirring, and collecting Fe after stirring 3 O 4 @ PDA nanoparticles, fe to be prepared 3 O 4 Dispersing the @ PDA nano particles in 20-150 parts of deionized water again, and adding 0.5-2 parts of ammonia water and 0.1-2 parts of surfactant; and then, dropwise adding a mixed solution of 10-50 parts of n-hexane and 5-40 parts of tetraethyl orthosilicate into the dispersion liquid, magnetically collecting a product after reaction, adding the product into 50-200 parts of ethanol, and performing reflux treatment to finally obtain the pomegranate-shaped magnetic silica nanospheres.
6. The self-repairing self-cleaning electromagnetic shielding fabric coating of claim 5, wherein a mixed solution of 10-50 parts of n-hexane and 5-40 parts of tetraethyl orthosilicate is added dropwise into the dispersion, and after reaction at a temperature of 25-65 ℃ for 6-24h, the product is collected by a magnet, washed and dried.
7. A method for preparing a self-repairing self-cleaning electromagnetic shielding fabric coating of claim 1, comprising the steps of:
adding 0.1-1 part of pyreneborate, 0.5-5 parts of pomegranate-shaped magnetic silicon dioxide nanospheres and 0.2-2 parts of graphene (G) into a mixed solution containing ethanol and water according to parts by weight, reacting, washing and drying to obtain the pomegranate-shaped magnetic silicon dioxide nanosphere modified graphene (mFe) 3 O 4 @SiO 2 -G)；
Uniformly mixing 100-200 parts by weight of comb-shaped hydrophobic polyurethane and 5-50 parts by weight of pomegranate-shaped magnetic silicon dioxide nanosphere modified graphene, and drying to obtain the self-repairing self-cleaning electromagnetic shielding fabric coating.
8. The preparation method according to claim 1, wherein the pyrene borate, the pomegranate-shaped magnetic silica nanospheres and the graphene (G) are added into a mixed solution containing ethanol and water, and after the mixture is reacted for 1-5 hours at 25-65 ℃, the pomegranate-shaped magnetic silica nanospheres modified graphene is obtained after washing and drying.
9. A self-healing self-cleaning electromagnetic shielding fabric coating according to claim 1, preferably widely used in flexible sensors, smart wearable, self-healing materials, military stealth materials.
10. The application of claim 9, wherein the self-repairing self-cleaning electromagnetic shielding fabric coating is prepared by uniformly mixing comb-shaped hydrophobic polyurethane and pomegranate-shaped magnetic silica nanosphere modified graphene, coating the mixture on the surface of the fabric, and drying the fabric at high temperature.
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