A composite fabric with electromagnetic shielding effectiveness, preparation method and application

Abstract

The present invention relates to the field of laminated composite fabrics, and discloses a composite fabric with electromagnetic shielding efficiency, a preparation method and an application. The preparation method includes: preparing an electromagnetic shielding coating, fixing it on the surface of a modified nylon 66 fabric through a thiol-ene click reaction to obtain an electromagnetic shielding fabric, using it as the inner layer of the composite fabric, and laminating the inner layer, an intermediate layer of polyester film and a surface layer of aluminum rolled material through a polyurethane hot melt adhesive. The obtained composite fabric has an electromagnetic shielding efficiency of low reflection and high absorption, and can be applied to tents.

Description

Technical Field

[0001] The present invention relates to the field of laminated composite fabrics, and particularly to a composite fabric with electromagnetic shielding efficiency, a preparation method and an application thereof. Background Art

[0002] In recent years, the rapid development of intelligent interaction products and wireless communication technologies has led to the widespread emergence of artificial electromagnetic radiation sources, and their energy levels have been continuously rising in the increasingly rapid growth. Under the conditions of limited space and limited frequency, the space electromagnetic energy increases by 10% annually. The resulting intricate electromagnetic radiation network covers a large number of relevant workers and the general public. The electromagnetic interference radiation with increasing energy and density will not only affect the normal operation of high-precision electronic devices, but also affect human health, increasing the risk of headaches, immune deficiencies and other diseases for relevant personnel. Therefore, it is urgent to take effective measures to prevent or reduce a series of problems caused by electromagnetic interference.

[0003] Electromagnetic interference mainly stems from electromagnetic induction, and the main body that generates electromagnetic induction is the electromagnetic interference radiation source. At present, the protection against electromagnetic radiation mainly relies on controlling the radiation source, distance protection and shielding protection. Although people can stay away from the radiation source to achieve self-protection, in actual work and life, radiation sources are almost everywhere, and people cannot avoid being exposed to extensive electromagnetic radiation pollution. Moreover, even if a certain distance is maintained, the influence of radiation cannot be completely eliminated. Therefore, doing a good job in shielding protection is the most effective means to prevent electromagnetic interference and achieve human protection. Generally, shielding is to cut off or block the electromagnetic field coupling path by using conductive or magnetic shielding materials, so as to limit electromagnetic radiation within a specified space range. Among many shielding materials, the flexible electromagnetic shielding material based on textiles, as a new type of flexible electromagnetic compatibility material, not only has excellent electromagnetic shielding characteristics, but also can maintain the flexibility, air permeability, comfort, fatigue resistance and easy cutting of textiles itself.

[0004] However, the current fabric-based electromagnetic shielding materials are mainly composed of inorganic shielding materials and organic fiber materials. Although they can endow textiles with certain electromagnetic shielding functions, the weak interfacial bonding force between the inorganic shielding layer and the organic fibers makes them prone to problems such as peeling, broken conduction routes and ineffective uniform absorption of electromagnetic waves in practical applications, resulting in their difficulty in long-term application. In addition, the existing electromagnetic shielding fabrics mainly endow textiles with electromagnetic shielding functions by improving conductivity, and the shielding mechanism is mainly reflection, and they cannot eliminate electromagnetic radiation at the root. Therefore, how to overcome the problems in the application of the above electromagnetic shielding fabrics and develop high-performance electromagnetic shielding fabrics with low reflection, high absorption and excellent bonding fastness between the functional layer and the fabric base has important practical and research significance.

[0005] Prior art, such as Chinese patent application CN109334183A, discloses an electromagnetic shielding composite material, including an electromagnetic absorption layer, an electromagnetic reflection layer and a release material layer, characterized in that: the absorption layer includes 12-15 parts of conductive filler and 40-45 parts of matrix filler by weight; the electromagnetic reflection layer includes 25-30 parts of fiber bottom layer and 50-55 parts of rubber matrix filler; the release material is a release paper layer or a release film layer. This composite material mainly imparts electromagnetic shielding function by improving conductivity, and the shielding mechanism is mainly reflection, which is easy to cause secondary electromagnetic pollution. Summary of the invention

[0006] The purpose of the present invention is to overcome the deficiencies of the prior art and provide a composite fabric with electromagnetic shielding performance and a preparation method thereof. The composite fabric has electromagnetic shielding performance with low reflection and high absorption.

[0007] In order to achieve the above object, the technical solution adopted by the present invention is as follows:

[0008] A method for preparing a composite fabric with electromagnetic shielding performance comprises the following steps:

[0009] Step (1), preparing an electromagnetic shielding coating;

[0010] S11, mixing 2-(chloromethyl)-2,3-dihydro-thieno[3,4-b]-1,4-dioxin, potassium thioacetate and N,N-dimethylformamide, reacting, extracting, drying and filtering after the reaction is completed to obtain an intermediate product;

[0011] The intermediate product, 30 wt% sodium methoxide methanol solution and tetrahydrofuran are mixed and reacted, and after the reaction is completed, the pH is neutralized, washed, dried, and filtered to obtain a modified thiophene monomer;

[0012] S12, mixing graphene oxide with 1 mol / L sulfuric acid aqueous solution, ultrasonically dispersing, adding modified thiophene monomer, ultrasonically dispersing, stirring, adding ammonium persulfate, reacting, filtering, washing, and drying after the reaction to obtain a graphene oxide / modified polythiophene composite material;

[0013] The graphene oxide / modified polythiophene composite material is mixed with water, ultrasonically dispersed, nickel nitrate and iron nitrate are added, stirred, pH is adjusted, reacted, and after the reaction is completed, filtered, washed, and dried to obtain an electromagnetic shielding additive;

[0014] S13, mixing the electromagnetic shielding additive with the waterborne polyurethane acrylate, adding 2,2-dimethoxy-2-phenylacetophenone, and stirring, and obtaining an electromagnetic shielding coating after the stirring is completed;

[0015] Step (2): Mix the nylon 66 fabric, 3-mercaptopropyltriethoxysilane (MPTES) with a mixed solvent of ethanol and water, adjust the pH, react, and after the reaction is completed, wash and dry to obtain the modified nylon 66 fabric;

[0016] Coat the electromagnetic shielding coating on both sides of the modified nylon 66 fabric, react, and after the reaction is completed, dry to obtain the electromagnetic shielding fabric;

[0017] Step (3): Use the electromagnetic shielding fabric as the inner layer, the aluminum rolling material as the outer layer, and the polyester film as the intermediate layer. Coat polyurethane hot melt adhesive on both sides thereof, place the electromagnetic shielding fabric and the aluminum rolling material on both sides of the intermediate layer respectively, and hot press to obtain the composite fabric with electromagnetic shielding performance.

[0018] Preferably, in the step (1) when preparing the electromagnetic shielding coating, in S11: the mass ratio of 2-(chloromethyl)-2,3-dihydro-thieno[3,4-b]-1,4-dioxin, potassium thioacetate, and N,N-dimethylformamide is 5:(5 - 6):(25 - 35); when preparing the intermediate product, the reaction conditions are: react at a temperature of 45 - 55 °C for 14 - 16 h; the mass ratio of the intermediate product, 30 wt% sodium methoxide methanol solution, and tetrahydrofuran is 2:(4 - 8):(140 - 160); when preparing the modified thiophene monomer, the reaction conditions are: react in a nitrogen atmosphere at room temperature for 4 - 6 h.

[0019] Preferably, in the step (1) when preparing the electromagnetic shielding coating, in S12: the mass ratio of graphene oxide, 1 mol / L sulfuric acid aqueous solution, modified thiophene monomer, and ammonium persulfate is 0.1:(120 - 160):(0.25 - 0.45):(0.8 - 1); when preparing the graphene oxide / modified polythiophene composite material, the reaction conditions are: react at a temperature of 0 - 5 °C for 20 - 24 h; the mass ratio of the graphene oxide / modified polythiophene composite material, water, nickel nitrate, and iron nitrate is 0.2:(180 - 200):(0.3 - 0.5):(0.8 - 1.2); when preparing the electromagnetic shielding additive, the reaction conditions are: react at pH = 10 - 11 and a temperature of 180 - 200 °C for 10 - 12 h.

[0020] Preferably, in the step (1) when preparing the electromagnetic shielding coating, in S13: the mass ratio of the electromagnetic shielding additive, waterborne polyurethane acrylate, and 2,2-dimethoxy-2-phenylacetophenone is (0.5 - 2):100:(0.5 - 0.7); the stirring conditions are: stir under light-shielding conditions at a rotation speed of 600 - 700 rpm for 30 - 50 min.

[0021] Preferably, when preparing the electromagnetic shielding coating, the waterborne polyurethane acrylate is prepared by the following steps: Mix isophorone diisocyanate (IPDI) with polyethylene glycol, stir, add dibutyltin dilaurate, react, after the reaction ends, add 2,2-dimethylolpropionic acid (DMPA), continue to react, after the reaction ends, add 2-hydroxyethyl methacrylate (HEMA), react again, after the reaction ends, add triethylamine, carry out a neutralization reaction, emulsify, and stir to obtain the waterborne polyurethane acrylate.

[0022] Further, the mass ratio of isophorone diisocyanate (IPDI), polyethylene glycol, dibutyltin dilaurate, 2,2-dimethylolpropionic acid (DMPA), 2-hydroxyethyl methacrylate (HEMA), and triethylamine is 7:(5.5 - 6.5):(0.05 - 0.1):(1.1 - 1.3):(1.8 - 2):(0.8 - 1); the reaction conditions are: react at a temperature of 60 - 70 °C for 1 - 2 h; the conditions for continuing the reaction are: continue to react at a temperature of 80 - 90 °C for 3 - 5 h; the conditions for reacting again are: react again at a temperature of 70 - 80 °C for 4 - 6 h; the conditions for the neutralization reaction are: carry out the neutralization reaction at room temperature for 0.5 - 1 h; the solid content after emulsification is controlled at 40 - 50 wt%.

[0023] Preferably, in the step (2), when preparing the modified nylon 66 fabric: the mass ratio of nylon 66 fabric, 3-mercaptopropyltriethoxysilane (MPTES), and the mixed solvent is 1:(8 - 12):(160 - 200); the volume ratio of ethanol to water in the mixed solvent is 9:1; the reaction conditions are: react at pH = 4 - 5 and a temperature of 60 - 80 °C for 2 - 3 h.

[0024] Preferably, in the step (2), when preparing the electromagnetic shielding fabric: the single-sided coating amount of the electromagnetic shielding coating is 25 - 45 g / m 2 ; the reaction conditions are: react under ultraviolet light irradiation of 350 - 370 nm for 30 - 50 min.

[0025] Preferably, in the step (3), when preparing the composite fabric with electromagnetic shielding performance: the sizing amounts of the inner-layer electromagnetic shielding fabric and the middle-layer polyester film, and the sizing amounts of the surface-layer aluminum rolled material and the middle-layer polyester film are both 15 - 25 g / m 2 ; the hot pressing conditions are: hot press at a temperature of 125 - 135 °C and a pressure of 2 - 2.5 N·cm -2 for 60 - 80 s.

[0026] Preferably, a composite fabric with electromagnetic shielding performance prepared by the preparation method of the composite fabric with electromagnetic shielding performance as described above.

[0027] Preferably, an application of a composite fabric with electromagnetic shielding effectiveness as described above on a tent.

[0028] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0029] The unique two-dimensional structure of graphene endows it with a large specific surface area, which can promote the scattering and multiple reflections of electromagnetic waves, resulting in more microwave absorption and improving the electromagnetic shielding effectiveness; nickel ferrite has the characteristics of wide raw material sources, good dispersibility, low cost, and excellent magnetic properties, such as domain wall resonance, natural resonance, and hysteresis loss. The present invention combines the in-situ polymerization method with the hydrothermal method, uses the conductive polymer modified polythiophene and magnetic nickel ferrite to jointly modify graphene, and the electromagnetic shielding additive prepared can generate interfacial polarization under the action of an external electric field, which helps to improve the dielectric loss of the material. Moreover, the impedance matching between the dielectric loss and the magnetic loss, the interfacial polarization generated by the multi-layer interface, and the electron polarization and dipole polarization in the magnetic nanoparticles can all improve the wave absorption performance of the composite fabric, thereby improving its electromagnetic shielding effectiveness.

[0030] At the same time, the present invention realizes the reduction of the reflection shielding effectiveness value while increasing the total shielding effectiveness value by doping the magnetic properties of the conductive network. When the nano-magnetic metal interacts with electromagnetic waves, the interfacial polarization and multiple scattering will consume the electromagnetic waves. Therefore, the introduction of nickel ferrite mainly enhances the shielding effectiveness of the composite fabric against electromagnetic waves by improving the absorption effect, and there is a significant synergistic effect between the electrical and magnetic components, showing a shielding mechanism mainly based on absorption and reducing the secondary pollution of electromagnetic waves.

[0031] In addition, the present invention uses graphene and modified polythiophene as the electrical components and nickel ferrite as the magnetic component, mixes them with vinyl-capped waterborne polyurethane acrylate to obtain an electromagnetic shielding coating, and constructs a conductive and magnetic dual-effect structure on the surface of the modified nylon 66 fabric by means of thiol-ene click reaction. This not only can improve the bonding fastness between the coating functional layer and the fabric substrate by covalent bonding, effectively avoiding problems such as the shedding of the functional layer and the fracture of the conductive path, but also better retains the mechanical flexibility, thermal stability, and breathability of the fabric substrate. The prepared composite fabric still has typical tensile-fracture characteristics of textiles, and the construction of the external functional layer of the fabric improves the breaking strength and breaking elongation of the electromagnetic shielding fabric as a whole.

[0032] The present invention sequentially composites an electromagnetic shielding fabric, a polyurethane hot melt adhesive, a polyester film, a polyurethane hot melt adhesive, and an aluminum rolled material in order, and hot presses to obtain a composite fabric. Among them, the aluminum rolled material has excellent electrical conductivity and shielding performance, and is an important barrier for electromagnetic shielding, which can ensure the stability of the entire fabric in a complex electromagnetic environment. However, the aluminum rolled material is easily damaged. Therefore, a layer of polyester film is composite on one side of the aluminum rolled material to enhance its wear resistance and tear resistance. Then, an electromagnetic shielding fabric is composite on the side of the polyester film without the aluminum rolled material to enhance the stability of the composite fabric and improve its electromagnetic shielding efficiency at the same time. Brief Description of the Drawings

[0033] Figure 1 is a process flow chart for preparing a composite fabric with electromagnetic shielding efficiency in the present invention;

[0034] Figure 2 is a structural schematic diagram for preparing a composite fabric with electromagnetic shielding efficiency in the present invention;

[0035] Figure 3 is a bar chart of the total electromagnetic shielding efficiency of the composite fabrics with electromagnetic shielding efficiency prepared in Examples 1-5 and Comparative Examples 1-3 of the present invention;

[0036] Figure 4 is a bar chart of the absorption electromagnetic shielding efficiency of the composite fabrics with electromagnetic shielding efficiency prepared in Examples 1-5 and Comparative Examples 1-3 of the present invention;

[0037] In the figure:

[0038] 1. Aluminum rolled material, 2. Polyurethane hot melt adhesive, 3. Polyester film, 4. Electromagnetic shielding fabric. Detailed Embodiments

[0039] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts shall fall within the protection scope of the present invention.

[0040] Example 1: This example discloses a preparation method of a composite fabric with electromagnetic shielding efficiency, including the following steps:

[0041] Step (1), prepare an electromagnetic shielding coating;

[0042] S11. Mix 2-(chloromethyl)-2,3-dihydro-thieno[3,4-b]-1,4-dioxin, potassium thioacetate and N,N-dimethylformamide, react at 55 °C for 14 h. After the reaction, obtain the crude reaction product. Add dichloromethane with a volume of 50% of the crude reaction product for extraction. Take the lower layer liquid, add anhydrous magnesium sulfate with a mass of 10% of the lower layer liquid and dry for 10 min. Filter, take the liquid component, and rotary evaporate at 35 °C for 4 h to obtain the intermediate product;

[0043] Among them, the mass ratio of 2-(chloromethyl)-2,3-dihydro-thieno[3,4-b]-1,4-dioxin, potassium thioacetate, and N,N-dimethylformamide is 5:6:35;

[0044] Mix the intermediate product, 30 wt% sodium methoxide methanol solution and tetrahydrofuran, react in a nitrogen atmosphere at room temperature for 6 h. After the reaction, add 0.1 mol / L hydrochloric acid aqueous solution to neutralize to pH 6 to obtain the crude reaction product. Add dichloromethane and water with a volume 3 times that of the crude reaction product and wash 4 times. Take the organic phase, add anhydrous magnesium sulfate with a mass of 10% of the organic phase and dry for 10 min. Filter, take the liquid component, and rotary evaporate at 35 °C for 4 h to obtain the modified thiophene monomer;

[0045] Among them, the mass ratio of the intermediate product, 30 wt% sodium methoxide methanol solution, and tetrahydrofuran is 2:8:160;

[0046] S12. Mix graphene oxide and 1 mol / L sulfuric acid aqueous solution, ultrasonically disperse for 6 h, add the modified thiophene monomer, ultrasonically disperse for 4 h, stir at 0 °C for 30 min, add ammonium persulfate, and react at 0 °C for 20 h. After the reaction, obtain the crude reaction product. Filter, take the precipitate, add ethanol and water with a mass 3 times that of the precipitate and wash 4 times, and dry at 80 °C for 20 h to obtain the graphene oxide / modified polythiophene composite material;

[0047] Among them, the mass ratio of graphene oxide, 1 mol / L sulfuric acid aqueous solution, modified thiophene monomer, and ammonium persulfate is 0.1:160:0.45:1;

[0048] Mix the graphene oxide / modified polythiophene composite material with water, ultrasonically disperse for 4 h, add nickel nitrate and iron nitrate, stir for 50 min, add 25 wt% ammonia water to adjust to pH 11, and react at 200 °C for 10 h. After the reaction, cool to room temperature to obtain the crude reaction product. Filter, take the precipitate, add water with a mass 3 times that of the precipitate and wash 4 times, and dry at 80 °C for 20 h to obtain the electromagnetic shielding additive;

[0049] Among them, the mass ratio of graphene oxide / modified polythiophene composite, water, nickel nitrate, and iron nitrate is 0.2:200:0.5:1.2;

[0050] S13. Mix the electromagnetic shielding additive with waterborne polyurethane acrylate, add 2,2-dimethoxy-2-phenylacetophenone, and stir for 30 min under dark conditions at a rotation speed of 700 rpm. After the stirring ends, an electromagnetic shielding coating is obtained;

[0051] Among them, the mass ratio of the electromagnetic shielding additive, waterborne polyurethane acrylate, and 2,2-dimethoxy-2-phenylacetophenone is 2:100:0.7;

[0052] The waterborne polyurethane acrylate is prepared through the following steps:

[0053] Mix isophorone diisocyanate (IPDI) with polyethylene glycol, stir for 15 min under a nitrogen atmosphere, add dibutyltin dilaurate, react at 70 °C for 1 h. After the reaction ends, add 2,2-dimethylolpropionic acid (DMPA), continue to react at 90 °C for 3 h. After the reaction ends, add 2-hydroxyethyl methacrylate (HEMA), react again at 80 °C for 4 h. After the reaction ends, cool to room temperature, add triethylamine, carry out a neutralization reaction at room temperature for 1 h, add water for emulsification, control the solid content at 50 wt%, and stir at a rotation speed of 700 rpm for 20 min to obtain waterborne polyurethane acrylate; the mass ratio of isophorone diisocyanate (IPDI), polyethylene glycol, dibutyltin dilaurate, 2,2-dimethylolpropionic acid (DMPA), 2-hydroxyethyl methacrylate (HEMA), and triethylamine is 7:6.5:0.1:1.3:2:1;

[0054] In step (2), mix nylon 66 fabric, 3-mercaptopropyltriethoxysilane (MPTES) with a mixed solvent of ethanol and water, add 0.5 mol / L acetic acid aqueous solution to adjust the pH value to 5, react at 80 °C for 2 h. After the reaction ends, take it out, wash it 4 times with ethanol, and dry it in a blast drying oven at 120 °C for 30 min to obtain modified nylon 66 fabric;

[0055] Among them, the mass ratio of nylon 66 fabric, 3-mercaptopropyltriethoxysilane (MPTES), and the mixed solvent is 1:12:200; the volume ratio of ethanol and water in the mixed solvent is 9:1;

[0056] Coat the electromagnetic shielding coating on both sides of the modified nylon 66 fabric, react under 370 nm ultraviolet light irradiation for 30 min. After the reaction ends, dry it in a blast drying oven at 100 °C for 30 min to obtain an electromagnetic shielding fabric;

[0057] Among them, the single-sided coating amount of the electromagnetic shielding paint is 45 g / m 2 ;

[0058] Step (3): Take the electromagnetic shielding fabric as the inner layer, the aluminum rolled material as the outer layer, and the polyester film as the intermediate layer. Coat polyurethane hot melt adhesive on both sides thereof, place the electromagnetic shielding fabric and the aluminum rolled material on both sides of the intermediate layer respectively, and hot press at a temperature of 135 °C and a pressure of 2.5 N·cm -2 for 60 s to obtain a composite fabric with electromagnetic shielding effectiveness;

[0059] Among them, the sizing amount of the inner layer electromagnetic shielding fabric and the intermediate layer polyester film, and the sizing amount of the outer layer aluminum rolled material and the intermediate layer polyester film are both 25 g / m 2 .

[0060] Example 2: This example discloses a preparation method of a composite fabric with electromagnetic shielding effectiveness, including the following steps:

[0061] Step (1): Prepare electromagnetic shielding paint;

[0062] S11: Mix 2-(chloromethyl)-2,3-dihydro-thieno[3,4-b]-1,4-dioxin, potassium thioacetate and N,N-dimethylformamide, react at a temperature of 45 °C for 16 h. After the reaction ends, obtain a crude reaction product, add dichloromethane accounting for 30% of the volume of the crude reaction product for extraction, take the lower layer liquid, add anhydrous magnesium sulfate accounting for 5% of the mass of the lower layer liquid to dry for 15 min, filter, take the liquid component, and rotary evaporate at a temperature of 25 °C for 6 h to obtain an intermediate product;

[0063] Among them, the mass ratio of 2-(chloromethyl)-2,3-dihydro-thieno[3,4-b]-1,4-dioxin, potassium thioacetate, and N,N-dimethylformamide is 5:5:25;

[0064] Mix the intermediate product, 30 wt% sodium methoxide methanol solution and tetrahydrofuran, react in a nitrogen atmosphere at room temperature for 4 h. After the reaction ends, add 0.1 mol / L hydrochloric acid aqueous solution to neutralize to pH 7 to obtain a crude reaction product. Add dichloromethane 5 times the volume of the crude reaction product and water to wash 2 times successively, take the organic phase, add anhydrous magnesium sulfate accounting for 5% of the mass of the organic phase to dry for 15 min, filter, take the liquid component, and rotary evaporate at a temperature of 25 °C for 6 h to obtain a modified thiophene monomer;

[0065] Among them, the mass ratio of the intermediate product, 30 wt% sodium methoxide methanol solution, and tetrahydrofuran is 2:4:140;

[0066] S12. Mix graphene oxide with an aqueous sulfuric acid solution of 1 mol / L, ultrasonically disperse for 4 h, add the modified thiophene monomer, ultrasonically disperse for 2 h, stir at 5 °C for 50 min, add ammonium persulfate, react at 5 °C for 24 h. After the reaction is completed, obtain the crude reaction product, filter, take the precipitate, wash it twice with ethanol and water which are 5 times the mass of the precipitate respectively, and dry at 60 °C for 24 h to obtain the graphene oxide / modified polythiophene composite material;

[0067] Among them, the mass ratio of graphene oxide, the aqueous sulfuric acid solution of 1 mol / L, the modified thiophene monomer, and ammonium persulfate is 0.1:120:0.25:0.8;

[0068] Mix the graphene oxide / modified polythiophene composite material with water, ultrasonically disperse for 2 h, add nickel nitrate and iron nitrate, stir for 30 min, add 25 wt% ammonia water to adjust the pH value to 10, react at 180 °C for 12 h. After the reaction is completed, cool to room temperature to obtain the crude reaction product, filter, take the precipitate, wash it twice with water which is 5 times the mass of the precipitate, and dry at 60 °C for 24 h to obtain the electromagnetic shielding additive;

[0069] Among them, the mass ratio of the graphene oxide / modified polythiophene composite material, water, nickel nitrate, and iron nitrate is 0.2:180:0.3:0.8;

[0070] S13. Mix the electromagnetic shielding additive with waterborne polyurethane acrylate, add 2,2 - dimethoxy - 2 - phenylacetophenone, stir at 600 rpm for 50 min under light - shielding conditions. After stirring is completed, obtain the electromagnetic shielding coating;

[0071] Among them, the mass ratio of the electromagnetic shielding additive, waterborne polyurethane acrylate, and 2,2 - dimethoxy - 2 - phenylacetophenone is 0.5:100:0.5; The preparation method of waterborne polyurethane acrylate is the same as that in Example 1;

[0072] Step (2). Mix nylon 66 fabric, 3 - mercaptopropyltriethoxysilane (MPTES) with a mixed solvent of ethanol and water, add an aqueous acetic acid solution of 0.5 mol / L to adjust the pH value to 4, react at 60 °C for 3 h. After the reaction is completed, take it out, wash it twice with ethanol, and dry it in a blast drying oven at 100 °C for 50 min to obtain the modified nylon 66 fabric;

[0073] Among them, the mass ratio of nylon 66 fabric, 3 - mercaptopropyltriethoxysilane (MPTES), and the mixed solvent is 1:8:160; The volume ratio of ethanol and water in the mixed solvent is 9:1;

[0074] Apply the electromagnetic shielding coating on both sides of the modified nylon 66 fabric, react for 50 min under the irradiation of 350 nm ultraviolet light, and after the reaction, dry it in a blast drying oven at 80 °C for 50 min to obtain the electromagnetic shielding fabric;

[0075] Among them, the single-sided coating amount of the electromagnetic shielding coating is 25 g / m 2 ;

[0076] Step (3): Take the electromagnetic shielding fabric as the inner layer, the aluminum rolled material as the outer layer, and the polyester film as the intermediate layer. Coat polyurethane hot melt adhesive on both sides, place the electromagnetic shielding fabric and the aluminum rolled material on both sides of the intermediate layer respectively, and hot press at 125 °C and 2 N·cm -2 pressure for 80 s to obtain a composite fabric with electromagnetic shielding effectiveness;

[0077] Among them, the sizing amount of the inner layer electromagnetic shielding fabric and the intermediate layer polyester film, as well as the sizing amount of the outer layer aluminum rolled material and the intermediate layer polyester film, are both 15 g / m 2 .

[0078] Example 3: This example discloses a preparation method of a composite fabric with electromagnetic shielding effectiveness, including the following steps:

[0079] Step (1): Prepare the electromagnetic shielding coating;

[0080] S11: Mix 2-(chloromethyl)-2,3-dihydro-thieno[3,4-b]-1,4-dioxin, potassium thioacetate and N,N-dimethylformamide, react at 52 °C for 14.5 h. After the reaction, obtain the crude reaction product, add dichloromethane with a volume of 45% of the crude reaction product for extraction, take the lower layer liquid, add anhydrous magnesium sulfate with a mass of 8% of the lower layer liquid to dry for 11 min, filter, take the liquid component, and rotary evaporate at 32 °C for 4.5 h to obtain the intermediate product;

[0081] Among them, the mass ratio of 2-(chloromethyl)-2,3-dihydro-thieno[3,4-b]-1,4-dioxin, potassium thioacetate, and N,N-dimethylformamide is 5:6:32;

[0082] Mix the intermediate product, 30 wt% sodium methoxide methanol solution and tetrahydrofuran, react in a nitrogen atmosphere at room temperature for 5.5 h. After the reaction, add 0.1 mol / L hydrochloric acid aqueous solution to neutralize to pH 6 to obtain the crude reaction product. Add dichloromethane with a volume 3 times that of the crude reaction product and water to wash 4 times successively. Take the organic phase, add anhydrous magnesium sulfate with a mass of 8% of the organic phase to dry for 11 min, filter, take the liquid component, and rotary evaporate at 32 °C for 4.5 h to obtain the modified thiophene monomer;

[0083] Among them, the mass ratio of the intermediate product, 30 wt% sodium methoxide methanol solution, and tetrahydrofuran is 2:7:155;

[0084] S12. Mix graphene oxide with 1 mol / L sulfuric acid aqueous solution, ultrasonically disperse for 5.5 h, add the modified thiophene monomer, ultrasonically disperse for 3.5 h, stir at 1 °C for 35 min, add ammonium persulfate, react at 1 °C for 21 h. After the reaction is completed, obtain the crude reaction product, filter, take the precipitate, successively add ethanol and water 3 times the mass of the precipitate and wash 4 times, and dry at 75 °C for 21 h to obtain the graphene oxide / modified polythiophene composite material;

[0085] Among them, the mass ratio of graphene oxide, 1 mol / L sulfuric acid aqueous solution, modified thiophene monomer, and ammonium persulfate is 0.1:150:0.4:0.95;

[0086] Mix the graphene oxide / modified polythiophene composite material with water, ultrasonically disperse for 3.5 h, add nickel nitrate and iron nitrate, stir for 45 min, add 25 wt% ammonia water to adjust the pH value to 11, react at 195 °C for 10.5 h. After the reaction is completed, cool to room temperature, obtain the crude reaction product, filter, take the precipitate, add water 3 times the mass of the precipitate and wash 4 times, and dry at 75 °C for 21 h to obtain the electromagnetic shielding additive;

[0087] Among them, the mass ratio of graphene oxide / modified polythiophene composite material, water, nickel nitrate, and iron nitrate is 0.2:195:0.45:1.1;

[0088] S13. Mix the electromagnetic shielding additive with waterborne polyurethane acrylate, add 2,2-dimethoxy-2-phenylacetophenone, stir at 675 rpm under light-shielded conditions for 35 min. After stirring is completed, obtain the electromagnetic shielding coating;

[0089] Among them, the mass ratio of the electromagnetic shielding additive, waterborne polyurethane acrylate, and 2,2-dimethoxy-2-phenylacetophenone is 1.6:100:0.65; The preparation method of waterborne polyurethane acrylate is the same as that in Example 1;

[0090] Step (2). Mix nylon 66 fabric, 3-mercaptopropyltriethoxysilane (MPTES) with a mixed solvent of ethanol and water, add 0.5 mol / L acetic acid aqueous solution to adjust the pH value to 5, react at 75 °C for 2 h. After the reaction is completed, take out, add ethanol and wash 4 times, and dry in a blast oven at 115 °C for 35 min to obtain the modified nylon 66 fabric;

[0091] Among them, the mass ratio of nylon 66 fabric, 3-mercaptopropyltriethoxysilane (MPTES), and the mixed solvent is 1:11:190; the volume ratio of ethanol to water in the mixed solvent is 9:1;

[0092] Coat the electromagnetic shielding coating on both sides of the modified nylon 66 fabric, react under 365 nm ultraviolet light irradiation for 35 min, after the reaction, dry in a blast drying oven at 95 °C for 35 min to obtain the electromagnetic shielding fabric;

[0093] Among them, the single-sided coating amount of the electromagnetic shielding coating is 40 g / m 2 ;

[0094] Step (3): Use the electromagnetic shielding fabric as the inner layer, aluminum rolled material as the outer layer, and polyester film as the intermediate layer. Coat polyurethane hot melt adhesive on both sides, place the electromagnetic shielding fabric and the aluminum rolled material on both sides of the intermediate layer respectively, and hot press at 132 °C and 2.3 N·cm -2 pressure for 65 s to obtain a composite fabric with electromagnetic shielding performance;

[0095] Among them, the sizing amount of the inner layer electromagnetic shielding fabric and the intermediate layer polyester film, as well as the sizing amount of the outer layer aluminum rolled material and the intermediate layer polyester film, are both 22 g / m 2 。

[0096] Example 4: This example discloses a preparation method of a composite fabric with electromagnetic shielding performance, including the following steps:

[0097] Step (1): Prepare the electromagnetic shielding coating;

[0098] S11. Mix 2-(chloromethyl)-2,3-dihydro-thieno[3,4-b]-1,4-dioxin, potassium thioacetate with N,N-dimethylformamide, react at 50 °C for 15 h. After the reaction, obtain the crude reaction product, add dichloromethane accounting for 40% of the volume of the crude reaction product for extraction, take the lower layer liquid, add anhydrous magnesium sulfate accounting for 7% of the mass of the lower layer liquid to dry for 12 min, filter, take the liquid component, and rotary evaporate at 30 °C for 5 h to obtain the intermediate product;

[0099] Among them, the mass ratio of 2-(chloromethyl)-2,3-dihydro-thieno[3,4-b]-1,4-dioxin, potassium thioacetate, and N,N-dimethylformamide is 5:5.5:30;

[0100] Mix the intermediate product, 30 wt% sodium methoxide methanol solution, and tetrahydrofuran, react for 5 h in a nitrogen atmosphere at room temperature. After the reaction, add 0.1 mol / L hydrochloric acid aqueous solution to neutralize to pH 6 to obtain the crude reaction product. Add dichloromethane and water, each 4 times the volume of the crude reaction product, and wash 3 times. Take the organic phase, add anhydrous magnesium sulfate at 7% of the mass of the organic phase and dry for 12 min, filter, take the liquid component, and rotary evaporate at 30 °C for 5 h to obtain the modified thiophene monomer;

[0101] Among them, the mass ratio of the intermediate product, 30 wt% sodium methoxide methanol solution, and tetrahydrofuran is 2:6:150;

[0102] S12: Mix graphene oxide and 1 mol / L sulfuric acid aqueous solution, ultrasonically disperse for 5 h, add the modified thiophene monomer, ultrasonically disperse for 3 h, stir at 2 °C for 40 min, add ammonium persulfate, and react at 2 °C for 22 h. After the reaction, obtain the crude reaction product, filter, take the precipitate, add ethanol and water, each 4 times the mass of the precipitate, and wash 3 times. Dry at 70 °C for 22 h to obtain the graphene oxide / modified polythiophene composite material;

[0103] Among them, the mass ratio of graphene oxide, 1 mol / L sulfuric acid aqueous solution, modified thiophene monomer, and ammonium persulfate is 0.1:140:0.35:0.9;

[0104] Mix the graphene oxide / modified polythiophene composite material and water, ultrasonically disperse for 3 h, add nickel nitrate and iron nitrate, stir for 40 min, add 25 wt% ammonia water to adjust to pH 11, and react at 190 °C for 11 h. After the reaction, cool to room temperature to obtain the crude reaction product, filter, take the precipitate, add water 4 times the mass of the precipitate and wash 3 times. Dry at 70 °C for 22 h to obtain the electromagnetic shielding additive;

[0105] Among them, the mass ratio of the graphene oxide / modified polythiophene composite material, water, nickel nitrate, and iron nitrate is 0.2:190:0.4:1;

[0106] S13: Mix the electromagnetic shielding additive and waterborne polyurethane acrylate, add 2,2-dimethoxy-2-phenylacetophenone, and stir at 650 rpm in the dark for 40 min. After stirring, obtain the electromagnetic shielding coating;

[0107] Among them, the mass ratio of the electromagnetic shielding additive, waterborne polyurethane acrylate, and 2,2-dimethoxy-2-phenylacetophenone is 1.2:100:0.6; The preparation method of the waterborne polyurethane acrylate is the same as that in Example 1;

[0108] Step (2): Mix the nylon 66 fabric, 3-mercaptopropyltriethoxysilane (MPTES) with a mixed solvent of ethanol and water, add an aqueous acetic acid solution of 0.5 mol / L to adjust the pH value to 5, react at 70 °C for 2.5 h. After the reaction, take out, wash with ethanol three times, and dry in a forced air oven at 110 °C for 40 min to obtain the modified nylon 66 fabric;

[0109] Among them, the mass ratio of the nylon 66 fabric, 3-mercaptopropyltriethoxysilane (MPTES), and the mixed solvent is 1:10:180; the volume ratio of ethanol and water in the mixed solvent is 9:1;

[0110] Coat the electromagnetic shielding coating on both sides of the modified nylon 66 fabric, react under 360 nm ultraviolet light irradiation for 40 min. After the reaction, dry in a forced air oven at 90 °C for 40 min to obtain the electromagnetic shielding fabric;

[0111] Among them, the single-sided coating amount of the electromagnetic shielding coating is 35 g / m 2 ;

[0112] Step (3): Take the electromagnetic shielding fabric as the inner layer, the aluminum rolling material as the outer layer, and the polyester film as the intermediate layer. Coat polyurethane hot melt adhesive on both sides, place the electromagnetic shielding fabric and the aluminum rolling material on both sides of the intermediate layer respectively, and hot press at 130 °C and 2.2 N·cm -2 pressure for 70 s to obtain the composite fabric with electromagnetic shielding performance;

[0113] Among them, the sizing amount of the inner layer electromagnetic shielding fabric and the intermediate layer polyester film, as well as the sizing amount of the outer layer aluminum rolling material and the intermediate layer polyester film, are both 20 g / m 2 .

[0114] Example 5: This example discloses a preparation method of a composite fabric with electromagnetic shielding performance, including the following steps:

[0115] Step (1): Prepare the electromagnetic shielding coating;

[0116] S11: Mix 2-(chloromethyl)-2,3-dihydro-thieno[3,4-b]-1,4-dioxin, potassium thioacetate with N,N-dimethylformamide, react at 48 °C for 15.5 h. After the reaction, obtain the crude reaction product, add dichloromethane accounting for 35% of the volume of the crude reaction product for extraction, take the lower layer liquid, add anhydrous magnesium sulfate accounting for 6% of the mass of the lower layer liquid to dry for 13 min, filter, take the liquid component, and rotary evaporate at 28 °C for 5.5 h to obtain the intermediate product;

[0117] Among them, the mass ratio of 2-(chloromethyl)-2,3-dihydro-thieno[3,4-b]-1,4-dioxin, potassium thioacetate, and N,N-dimethylformamide is 5:5:28;

[0118] Mix the intermediate product, 30 wt% sodium methoxide methanol solution, and tetrahydrofuran, and react for 4.5 h in a nitrogen atmosphere at room temperature. After the reaction, add 0.1 mol / L hydrochloric acid aqueous solution to neutralize to pH 7 to obtain the crude reaction product. Add dichloromethane and water, each 5 times the volume of the crude reaction product, and wash twice. Take the organic phase, add anhydrous magnesium sulfate at 6% of the mass of the organic phase and dry for 13 min. Filter, take the liquid component, and rotary evaporate at 28 °C for 5.5 h to obtain the modified thiophene monomer;

[0119] Among them, the mass ratio of the intermediate product, 30 wt% sodium methoxide methanol solution, and tetrahydrofuran is 2:5:145;

[0120] S12. Mix graphene oxide with 1 mol / L sulfuric acid aqueous solution, ultrasonically disperse for 4.5 h, add the modified thiophene monomer, ultrasonically disperse for 2.5 h, stir at 3 °C for 45 min, add ammonium persulfate, and react at 3 °C for 23 h. After the reaction, obtain the crude reaction product, filter, take the precipitate, add ethanol and water, each 5 times the mass of the precipitate, and wash twice. Dry at 65 °C for 23 h to obtain the graphene oxide / modified polythiophene composite material;

[0121] Among them, the mass ratio of graphene oxide, 1 mol / L sulfuric acid aqueous solution, modified thiophene monomer, and ammonium persulfate is 0.1:130:0.3:0.85;

[0122] Mix the graphene oxide / modified polythiophene composite material with water, ultrasonically disperse for 2.5 h, add nickel nitrate and iron nitrate, stir for 35 min, add 25 wt% ammonia water to adjust to pH 10, and react at 185 °C for 11.5 h. After the reaction, cool to room temperature to obtain the crude reaction product, filter, take the precipitate, add water 5 times the mass of the precipitate and wash twice. Dry at 65 °C for 23 h to obtain the electromagnetic shielding additive;

[0123] Among them, the mass ratio of the graphene oxide / modified polythiophene composite material, water, nickel nitrate, and iron nitrate is 0.2:185:0.35:0.9;

[0124] S13. Mix the electromagnetic shielding additive with waterborne polyurethane acrylate, add 2,2-dimethoxy-2-phenylacetophenone, and stir at 625 rpm in the dark for 45 min. After stirring, obtain the electromagnetic shielding coating;

[0125] Among them, the mass ratio of the electromagnetic shielding additive, waterborne polyurethane acrylate, and 2,2 - dimethoxy - 2 - phenylacetophenone is 0.8:100:0.55; the preparation method of the waterborne polyurethane acrylate is the same as that in Example 1;

[0126] Step (2): Mix the nylon 66 fabric, 3 - mercaptopropyltriethoxysilane (MPTES) with a mixed solvent of ethanol and water, add 0.5 mol / L acetic acid aqueous solution to adjust the pH value to 4, react at 65 °C for 3 h. After the reaction, take it out, wash it twice with ethanol, and dry it in a blast drying oven at 105 °C for 45 min to obtain the modified nylon 66 fabric;

[0127] Among them, the mass ratio of the nylon 66 fabric, 3 - mercaptopropyltriethoxysilane (MPTES), and the mixed solvent is 1:9:170; the volume ratio of ethanol and water in the mixed solvent is 9:1;

[0128] Coat the electromagnetic shielding coating on both sides of the modified nylon 66 fabric, react under 355 nm ultraviolet light irradiation for 45 min, and after the reaction, dry it in a blast drying oven at 85 °C for 45 min to obtain the electromagnetic shielding fabric;

[0129] Among them, the single - side coating amount of the electromagnetic shielding coating is 30 g / m 2 ;

[0130] Step (3): Use the electromagnetic shielding fabric as the inner layer, aluminum rolled material as the outer layer, and polyester film as the intermediate layer. Coat polyurethane hot - melt adhesive on both sides, place the electromagnetic shielding fabric and the aluminum rolled material on both sides of the intermediate layer respectively, and hot - press at 128 °C and 2.1 N·cm -2 pressure for 75 s to obtain the composite fabric with electromagnetic shielding effectiveness;

[0131] Among them, the sizing amount of the inner - layer electromagnetic shielding fabric and the intermediate - layer polyester film, as well as the sizing amount of the outer - layer aluminum rolled material and the intermediate - layer polyester film, are both 18 g / m 2 。

[0132] Comparative Example 1: This comparative example discloses a preparation method of a composite fabric, including the following steps:

[0133] Step (1): Prepare a modified coating;

[0134] Mix graphene oxide with water, ultrasonically disperse for 2 h, add nickel nitrate and iron nitrate, stir for 30 min, add 25 wt% ammonia water to adjust the pH value to 10, react at 180 °C for 12 h. After the reaction, cool to room temperature to obtain the reaction crude product, filter, take the precipitate, wash it twice with 5 times the mass of the precipitate of water, and dry it at 60 °C for 24 h to obtain the composite additive;

[0135] Among them, the mass ratio of graphene oxide, water, nickel nitrate, and iron nitrate is 0.2:180:0.3:0.8;

[0136] Mix the composite additive with waterborne polyurethane acrylate, add 2,2 - dimethoxy - 2 - phenylacetophenone, and stir at 600 rpm for 50 min under light - shielding conditions. After the stirring is completed, a modified coating is obtained;

[0137] Among them, the mass ratio of the composite additive, waterborne polyurethane acrylate, and 2,2 - dimethoxy - 2 - phenylacetophenone is 0.5:100:0.5; The preparation method of waterborne polyurethane acrylate is the same as that in Example 1;

[0138] Step (2): Mix nylon 66 fabric, 3 - mercaptopropyltriethoxysilane (MPTES) with a mixed solvent of ethanol and water, add 0.5 mol / L acetic acid aqueous solution to adjust the pH value to 4, react at 60 °C for 3 h. After the reaction is completed, take it out, wash it twice with ethanol, and dry it in a forced - air oven at 100 °C for 50 min to obtain modified nylon 66 fabric;

[0139] Among them, the mass ratio of nylon 66 fabric, 3 - mercaptopropyltriethoxysilane (MPTES), and the mixed solvent is 1:8:160; The volume ratio of ethanol to water in the mixed solvent is 9:1;

[0140] Coat the two sides of the modified nylon 66 fabric with the modified coating, react under 350 nm ultraviolet light irradiation for 50 min, and after the reaction is completed, dry it in a forced - air oven at 80 °C for 50 min to obtain a modified fabric;

[0141] Among them, the single - side coating amount of the modified coating is 25 g / m 2 ;

[0142] Step (3): Use the modified fabric as the inner layer, aluminum rolled material as the outer layer, and polyester film as the intermediate layer. Coat polyurethane hot - melt adhesive on both sides, place the modified fabric and the aluminum rolled material on both sides of the intermediate layer respectively, and hot - press at 125 °C and 2 N·cm -2 pressure for 80 s to obtain a composite fabric;

[0143] Among them, the sizing amount of the inner - layer modified fabric and the intermediate - layer polyester film, as well as the sizing amount of the outer - layer aluminum rolled material and the intermediate - layer polyester film, are both 15 g / m 2 .

[0144] Comparative Example 2: This comparative example discloses a preparation method of a composite fabric, including the following steps:

[0145] Step (1): Prepare a modified coating;

[0146] S11. Mix 2-(chloromethyl)-2,3-dihydro-thieno[3,4-b]-1,4-dioxin, potassium thioacetate and N,N-dimethylformamide, and react at 45 °C for 16 h. After the reaction is completed, obtain the crude reaction product. Add dichloromethane accounting for 30% of the volume of the crude reaction product for extraction. Take the lower-layer liquid, add anhydrous magnesium sulfate accounting for 5% of the mass of the lower-layer liquid for drying for 15 min, filter, take the liquid component, and rotary evaporate at 25 °C for 6 h to obtain the intermediate product;

[0147] Among them, the mass ratio of 2-(chloromethyl)-2,3-dihydro-thieno[3,4-b]-1,4-dioxin, potassium thioacetate, and N,N-dimethylformamide is 5:5:25;

[0148] Mix the intermediate product, 30 wt% sodium methoxide methanol solution and tetrahydrofuran, and react in a nitrogen atmosphere at room temperature for 4 h. After the reaction is completed, add 0.1 mol / L hydrochloric acid aqueous solution to neutralize to pH 7 to obtain the crude reaction product. Add dichloromethane and water 5 times the volume of the crude reaction product in sequence for washing 2 times. Take the organic phase, add anhydrous magnesium sulfate accounting for 5% of the mass of the organic phase for drying for 15 min, filter, take the liquid component, and rotary evaporate at 25 °C for 6 h to obtain the modified thiophene monomer;

[0149] Among them, the mass ratio of the intermediate product, 30 wt% sodium methoxide methanol solution, and tetrahydrofuran is 2:4:140;

[0150] S12. Mix graphene oxide and 1 mol / L sulfuric acid aqueous solution, ultrasonically disperse for 4 h, add the modified thiophene monomer, ultrasonically disperse for 2 h, stir at 5 °C for 50 min, add ammonium persulfate, and react at 5 °C for 24 h. After the reaction is completed, obtain the crude reaction product, filter, take the precipitate, add ethanol and water 5 times the mass of the precipitate in sequence for washing 2 times, and dry at 60 °C for 24 h to obtain the graphene oxide / modified polythiophene composite material;

[0151] Among them, the mass ratio of graphene oxide, 1 mol / L sulfuric acid aqueous solution, modified thiophene monomer, and ammonium persulfate is 0.1:120:0.25:0.8;

[0152] S13. Mix the graphene oxide / modified polythiophene composite material and waterborne polyurethane acrylate, add 2,2-dimethoxy-2-phenylacetophenone, and stir at 600 rpm in the dark for 50 min. After stirring is completed, obtain the modified coating;

[0153] Among them, the mass ratio of the graphene oxide / modified polythiophene composite material, waterborne polyurethane acrylate, and 2,2-dimethoxy-2-phenylacetophenone is 0.5:100:0.5; The preparation method of waterborne polyurethane acrylate is the same as that in Example 1;

[0154] Step (2): Mix nylon 66 fabric, 3-mercaptopropyltriethoxysilane (MPTES) with a mixed solvent of ethanol and water, add 0.5 mol / L acetic acid aqueous solution to adjust the pH value to 4, react at 60 °C for 3 h. After the reaction, take it out, wash it twice with ethanol, and dry it in a forced-air oven at 100 °C for 50 min to obtain the modified nylon 66 fabric;

[0155] Among them, the mass ratio of nylon 66 fabric, 3-mercaptopropyltriethoxysilane (MPTES), and the mixed solvent is 1:8:160; the volume ratio of ethanol and water in the mixed solvent is 9:1;

[0156] Coat the two sides of the modified nylon 66 fabric with the modified coating, react under 350 nm ultraviolet light irradiation for 50 min. After the reaction, dry it in a forced-air oven at 80 °C for 50 min to obtain the modified fabric;

[0157] Among them, the single-sided coating amount of the modified coating is 25 g / m 2 ;

[0158] Step (3): Use the modified fabric as the inner layer, aluminum rolled material as the outer layer, and polyester film as the intermediate layer. Coat polyurethane hot melt adhesive on both sides, place the modified fabric and aluminum rolled material on both sides of the intermediate layer respectively, and hot press at 125 °C and 2 N·cm -2 pressure for 80 s to obtain the composite fabric;

[0159] Among them, the sizing amount of the inner layer modified fabric and the intermediate layer polyester film, as well as the sizing amount of the outer layer aluminum rolled material and the intermediate layer polyester film, are both 15 g / m 2 .

[0160] Comparative Example 3: This comparative example discloses a preparation method of a composite fabric, including the following steps:

[0161] Step (1): Use nylon 66 fabric as the inner layer, aluminum rolled material as the outer layer, and polyester film as the intermediate layer. Coat polyurethane hot melt adhesive on both sides, place the nylon 66 fabric and aluminum rolled material on both sides of the intermediate layer respectively, and hot press at 125 °C and 2 N·cm -2 pressure for 80 s to obtain the composite fabric;

[0162] Among them, the sizing amount of the inner layer nylon 66 fabric and the intermediate layer polyester film, as well as the sizing amount of the outer layer aluminum rolled material and the intermediate layer polyester film, are both 15 g / m 2 .

[0163] In the above-mentioned examples and comparative examples: 2-(chloromethyl)-2,3-dihydrothieno[3,4-b]-1,4-dioxin was from Wuxi Jiehua Pharmaceutical Technology Co., Ltd., CAS No.: 857419-46-6; potassium thioacetate was from Tianjin Xinbote Chemical Co., Ltd., CAS No.: 10387-40-3; N,N-dimethylformamide was from Tianjin Xinbote Chemical Co., Ltd., CAS No.: 68-12-2; dichloromethane was from Tianjin Xinbote Chemical Co., Ltd., CAS No.: 75-09-2; anhydrous magnesium sulfate was from Laizhou Guangcheng Chemical Co., Ltd., CAS No.: 7487-88-9; sodium methoxide methanol solution was from, CAS No.: 124-41-4; tetrahydrofuran was from Jinzhou Boyi Chemical Technology Co., Ltd., CAS No.: 109-99-9; graphene oxide was from Angxing New Carbon Materials Changzhou Co., Ltd., oxygen content 50wt%, model: GO1211; ammonium persulfate was from Sinopharm Chemical Reagent Co., Ltd., CAS No.: 7727-54-0; nickel nitrate was from Sinopharm Chemical Reagent Co., Ltd., molecular formula: Ni(NO3)2·6H2O; iron nitrate was from Sinopharm Chemical Reagent Co., Ltd., molecular formula: Fe(NO3)3·9H2O; isophorone diisocyanate (IPDI) was from Shanghai Macklin Biochemical Co., Ltd., CAS No.: 4098-71-9; polyethylene glycol was from TCI (Shanghai) Chemical Industry Development Co., Ltd., Mw = 300 g / mol, model: H0543, CAS No.: 25322-68-3; dibutyltin dilaurate was from Shanghai Institute of Organic Pharmaceutical Chemistry Co., Ltd., CAS No.: 77-58-7; 2,2-dimethylolpropionic acid (DMPA) was from TCI (Shanghai) Chemical Industry Development Co., Ltd., CAS No.: 4767-03-7; 2-hydroxyethyl methacrylate (HEMA) was from TCI (Shanghai) Chemical Industry Development Co., Ltd., CAS No.: 868-77-9; triethylamine was from Sinopharm Chemical Reagent Co., Ltd., CAS No.: 121-44-8; 2,2-dimethoxy-2-phenylacetophenone was from Shanghai Adamas Reagent Co., Ltd., CAS No.: 24650-42-8; nylon 66 fabric was from Hangzhou Xinsheng Printing and Dyeing Co., Ltd., gram weight 40 g / m 2 , thickness 50 μm; polyester film was from Tianjin Deli Film Co., Ltd., product name: BOPET biaxially oriented polyester film, thickness 25 μm; aluminum rolled material was from Shanghai Xingnuo Industry Co., Ltd., product name: 8079 aluminum foil, thickness 50 μm; polyurethane hot melt adhesive was from Huate Adhesive Materials Co., Ltd., model: HT-9260.

[0164] Test examples:

[0165] (1) Comprehensive performance test

[0166] The mechanical properties of the inner fabric in the composite fabrics prepared in Examples 1-5 and Comparative Examples 1-3 were tested. The specific test results are shown in Table 1; the comprehensive properties of the composite fabrics prepared in Examples 1-5 and Comparative Examples 1-3 were tested. The specific test results are shown in Table 2:

[0167] Table 1

[0168]

[0169] Table 2

[0170]

[0171] The detection of each index in Table 1 and Table 2 was based on the following standards respectively: the breaking elongation was determined by GB / T 3923.1-2013 "Textiles - Tensile properties of fabrics - Part 1: Determination of breaking force and breaking elongation (strip method)"; the total electromagnetic shielding effectiveness and absorption electromagnetic shielding effectiveness were determined by SJ20524-1995 "Test method for shielding effectiveness of materials".

[0172] According to the test results in Table 2, it can be seen that the composite fabric prepared by the present invention has electromagnetic shielding effectiveness of low reflection and high absorption.

[0173] In Comparative Example 1, the thiophene monomer was not modified and grafted on the surface of graphene oxide to form conductive modified polythiophene, which reduced the electrical components in the additive and could not synergistically interact with graphene oxide, reducing the dielectric loss effect of the additive, and thus reducing the electromagnetic shielding effect of the modified fabric. Therefore, the total electromagnetic shielding effectiveness and absorption electromagnetic shielding effectiveness of Comparative Example 1 are smaller than those of the examples.

[0174] In Comparative Example 2, magnetic nickel ferrite was not hydrothermally generated on the surface of the graphene oxide / modified polythiophene composite material, and the modified coating obtained by mixing it with waterborne polyurethane acrylate lacked magnetic components, reducing the interfacial polarization and multiple scattering effects on electromagnetic waves, and thus reducing the electromagnetic shielding effect of the modified fabric. Therefore, the total electromagnetic shielding effectiveness and absorption electromagnetic shielding effectiveness of Comparative Example 2 are smaller than those of the examples.

[0175] In Comparative Example 3, an electromagnetic shielding coating was not prepared, and only nylon 66 fabric was used as the inner fabric. Since the construction of the functional layer coating was lacking outside the fabric, its mechanical properties were reduced, affecting the breaking elongation of the inner fabric. Therefore, the breaking elongation of the inner fabric in Comparative Example 3 is smaller than that of the examples. At the same time, although the aluminum rolled material has electrical conductivity and shielding performance, due to the lack of the synergistic effect of the electrical component graphene, modified polythiophene and magnetic component nickel ferrite, its electromagnetic shielding effect is not sufficient and perfect. Therefore, the total electromagnetic shielding effectiveness and absorption electromagnetic shielding effectiveness of Comparative Example 3 are smaller than those of the examples.

[0176] Although embodiments of the present invention have been shown and described, it will be understood by those of ordinary skill in the art that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principles and spirit of the present invention, and the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A preparation method of a composite fabric with electromagnetic shielding effectiveness, characterized in that, It includes the following steps: Step (1), preparing an electromagnetic shielding coating; Mix 2-(chloromethyl)-2,3-dihydro-thieno[3,4-b]-1,4-dioxin, potassium thioacetate and N,N-dimethylformamide, react, after the reaction ends, extract, dry, filter to obtain an intermediate product; Mix the intermediate product, sodium methoxide methanol solution and tetrahydrofuran, react, after the reaction ends, neutralize the pH, wash, dry, filter to obtain a modified thiophene monomer; Mix graphene oxide and sulfuric acid aqueous solution, add the modified thiophene monomer, stir, add ammonium persulfate, react, after the reaction ends, perform post-treatment to obtain a graphene oxide / modified polythiophene composite material; Among them, the mass ratio of graphene oxide, sulfuric acid aqueous solution, modified thiophene monomer, and ammonium persulfate is 0.1:(120 - 160):(0.25 - 0.45):(0.8 - 1); Mix the graphene oxide / modified polythiophene composite material and water, add nickel nitrate and iron nitrate, stir, react, after the reaction ends, perform post-treatment to obtain an electromagnetic shielding additive; Among them, the mass ratio of graphene oxide / modified polythiophene composite material, water, nickel nitrate, and iron nitrate is 0.2:(180 - 200):(0.3 - 0.5):(0.8 - 1.2); Mix the electromagnetic shielding additive and waterborne polyurethane acrylate, add 2,2-dimethoxy-2-phenylacetophenone, stir, after the stirring ends, obtain an electromagnetic shielding coating; Step (2), coat the electromagnetic shielding coating on both sides of the modified nylon 66 fabric, react, after the reaction ends, dry to obtain an electromagnetic shielding fabric; Step (3), composite the electromagnetic shielding fabric, polyester film, and aluminum rolling material through polyurethane hot melt adhesive, and hot press to obtain a composite fabric with electromagnetic shielding effectiveness.

2. The preparation method of a composite fabric with electromagnetic shielding effectiveness according to claim 1, characterized in that, In the said step (1): the concentration of the sulfuric acid aqueous solution is 1 mol / L; when preparing the graphene oxide / modified polythiophene composite material, the reaction conditions are: react at a temperature of 0 - 5 °C for 20 - 24 h.

3. The preparation method of a composite fabric with electromagnetic shielding performance according to claim 1, characterized in that, In the said step (1): the mass ratio of 2-(chloromethyl)-2,3-dihydro-thieno[3,4-b]-1,4-dioxin, potassium thioacetate, and N,N-dimethylformamide is 5:(5 - 6):(25 - 35); when preparing the intermediate product, the reaction conditions are: react at a temperature of 45 - 55 °C for 14 - 16 h; the concentration of the sodium methoxide methanol solution is 30 wt%; the mass ratio of the intermediate product, 30 wt% sodium methoxide methanol solution, and tetrahydrofuran is 2:(4 - 8):(140 - 160); when preparing the modified thiophene monomer, the reaction conditions are: react in a nitrogen atmosphere at room temperature for 4 - 6 h.

4. The preparation method of a composite fabric with electromagnetic shielding effectiveness according to claim 1, characterized in that, In the said step (1): when preparing the electromagnetic shielding additive, the reaction conditions are: react at pH = 10 - 11 and a temperature of 180 - 200 °C for 10 - 12 h.

5. The preparation method of a composite fabric with electromagnetic shielding efficacy according to claim 1, characterized in that, In the step (1): the mass ratio of the electromagnetic shielding additive, waterborne polyurethane acrylate, and 2,2-dimethoxy-2-phenylacetophenone is (0.5 - 2):100:(0.5 - 0.7); when preparing the electromagnetic shielding coating, the stirring conditions are: stirring for 30 - 50 min under light-shielding conditions at a rotation speed of 600 - 700 rpm.

6. The preparation method of a composite fabric with electromagnetic shielding effectiveness according to claim 5, characterized in that, The waterborne polyurethane acrylate in the step (1) is prepared through the following steps: Mix isophorone diisocyanate and polyethylene glycol, stir, add dibutyltin dilaurate, react, after the reaction ends, add 2,2-dimethylolpropionic acid, continue to react, after the reaction ends, add 2-hydroxyethyl methacrylate, react again, after the reaction ends, add triethylamine, conduct a neutralization reaction, emulsify, and stir to obtain waterborne polyurethane acrylate; Among them, the mass ratio of isophorone diisocyanate, polyethylene glycol, dibutyltin dilaurate, 2,2-dimethylolpropionic acid, 2-hydroxyethyl methacrylate, and triethylamine is 7:(5.5 - 6.5):(0.05 - 0.1):(1.1 - 1.3):(1.8 - 2):(0.8 - 1); the reaction conditions are: reacting at a temperature of 60 - 70 °C for 1 - 2 h; the conditions for the continued reaction are: continuing to react at a temperature of 80 - 90 °C for 3 - 5 h; the conditions for the re-reaction are: reacting again at a temperature of 70 - 80 °C for 4 - 6 h; the conditions for the neutralization reaction are: conducting a neutralization reaction at room temperature for 0.5 - 1 h; the solid content after emulsification is controlled at 40 - 50 wt%.

7. The preparation method of a composite fabric with electromagnetic shielding efficacy according to claim 1, characterized in that In the step (2), the single-side coating amount of the electromagnetic shielding coating is 25-45 g / m 2 ; the reaction conditions are: reacting for 30-50 min under the irradiation of ultraviolet light at 350-370 nm; The modified nylon 66 fabric is prepared through the following steps: mix the nylon 66 fabric, 3-mercaptopropyltriethoxysilane, and a mixed solvent of ethanol and water, adjust the pH, react, after the reaction ends, wash and dry to obtain the modified nylon 66 fabric; the mass ratio of the nylon 66 fabric, 3-mercaptopropyltriethoxysilane, and the mixed solvent is 1:(8 - 12):(160 - 200), and the volume ratio of ethanol to water in the mixed solvent is 9:1; the reaction conditions are: reacting at pH = 4 - 5 and a temperature of 60 - 80 °C for 2 - 3 h.

8. The preparation method of a composite fabric with electromagnetic shielding effectiveness according to claim 1, characterized in that, In the step (3), the sizing amount of the inner electromagnetic shielding fabric and the middle polyester film, as well as the sizing amount of the surface aluminum rolled material and the middle polyester film, are both 15 - 25 g / m 2 ; The hot pressing conditions are: at a temperature of 125 - 135 °C and a pressure of 2 - 2.5 N·cm -2 for hot pressing for 60 - 80 s.

9. A composite fabric with electromagnetic shielding effectiveness, characterized in that, It is prepared by using the preparation method of a composite fabric with electromagnetic shielding efficacy described in any one of claims 1 - 8.

10. Application of a composite fabric with electromagnetic shielding efficacy as described in claim 9 in a tent.

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