Shielding material containing graphene and preparation method thereof

Abstract

The present invention relates to the technical field of shielding materials, and discloses a shielding material containing graphene and a preparation method. The present invention obtains a shielding material containing graphene by mixing silane-modified graphene oxide, hexachlorophosphazene-modified polyaniline, bisphenol A-type epoxy resin, and triethylenetetramine, drying, and curing after compression molding. The free radicals released by 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in the silane-modified graphene oxide react with the free radicals in the flame to interrupt the combustion chain reaction; the silicon dioxide produced by the decomposition of silane forms a protective layer on the surface of the material to prevent the spread of flames; the phosphorus-containing quaternary ammonium salt-modified silane coupling agent improves the dispersibility of graphene and improves the shielding effect; the compound produced by the decomposition of hexachlorophosphazene forms a protective layer on the surface of the material, which has a flame retardant effect; phosphorus, nitrogen, silicon, and boron elements produce a synergistic flame retardant effect; graphene oxide is blended and compounded with polyaniline, and the electrochemical performance is enhanced, thereby improving the electromagnetic shielding performance.

Description

Technical Field

[0001] The present invention relates to the technical field of shielding materials, and in particular to a shielding material containing graphene and a preparation method thereof. Background Art

[0002] With the development of scientific information technology, the electromagnetic pollution and electromagnetic interference problems caused by the application of electromagnetic wave technology will not only interfere with the operation of electronic equipment, but also cause harm to human health and the environment. Therefore, it is of great significance to explore high-performance electromagnetic shielding materials. At present, electromagnetic shielding materials mainly include metals and their alloy materials, conductive polymers and carbon materials, but many shielding materials have poor flame retardant and electromagnetic shielding properties, which limits their further development and application. For example, patent application CN113174132A discloses a composite electromagnetic shielding material with the advantages of high frequency efficiency, wide frequency band, light weight and thin thickness, but its flame retardant and electromagnetic shielding properties need to be improved. Summary of the invention

[0003] 1. Technical issues to be resolved

[0004] In view of the deficiencies in the prior art, the present invention provides a shielding material containing graphene and a preparation method thereof, which improves the flame retardant properties and electromagnetic shielding properties of the shielding material.

[0005] (II) Technical solution

[0006] To achieve the above-mentioned purpose, the present invention provides the following technical solution: a shielding material containing graphene, comprising the following weight components: 20-22 parts by weight of silane-modified graphene oxide, 15-18 parts by weight of hexachlorophosphazene-modified polyaniline, 8-10 parts by weight of bisphenol A epoxy resin, and 2-5 parts by weight of triethylenetetramine.

[0007] Preferably, the method for preparing silane-modified graphene oxide comprises the following steps:

[0008] (1) Add 8-10 parts by weight of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to tetrahydrofuran solvent, stir and dissolve, add 0.2-0.4 parts by weight of initiator and 9-12 parts by weight of dimethylallylamine, introduce nitrogen protection, react at 62-68° C. for 17-20 hours, and after the reaction is completed, distill under reduced pressure and dry in vacuum to obtain intermediate 1;

[0009] (2) Dissolve the intermediate 1 in anhydrous ethanol, add 3-chloropropyltrimethoxysilane dropwise thereto, and reflux heat at 75-80° C. for 8-10 hours. After the reaction is completed, cool, wash and dry to obtain a phosphorus-containing quaternary ammonium salt modified silane coupling agent;

[0010] (3) Add 12-15 parts by weight of graphene oxide powder to deionized water and stir to dissolve, then dissolve 5-7 parts by weight of a phosphorus-containing quaternary ammonium salt-modified silane coupling agent in anhydrous ethanol, add it to the graphene oxide, ultrasonically treat and stir, add hydrochloric acid solution and adjust to weak acidity, heat in a water bath at 50-55° C. for 45-55 minutes, then raise the temperature to 70-78° C. and continue to react for 2.5-3.5 hours. After the reaction is completed, cool to room temperature, centrifuge, wash and dry to obtain silane-modified graphene oxide.

[0011] Preferably, the initiator in step (1) is azobisisobutyronitrile.

[0012] Preferably, in step (2), the mass ratio of the intermediate 1:3-chloropropyltrimethoxysilane is 1:1.05-1.1.

[0013] Preferably, the mass fraction of the hydrochloric acid solution in step (3) is 2.5%-3.2%.

[0014] Preferably, the method for preparing the hexachlorophosphazene-modified polyaniline comprises the following steps:

[0015] S1. Dissolve 7-9 parts by weight of 4-(2-methylpropenyl)carbonyloxyphenylboronic acid in deionized water, add 5-8 parts by weight of hexachlorophosphazene to an acetone solvent, stir to dissolve, add 4-(2-methylpropenyl)carbonyloxyphenylboronic acid dropwise under a nitrogen atmosphere, react at 56-60° C. for 2-4 hours, and then rotary evaporate to obtain boron-modified hexachlorophosphazene;

[0016] S2. Add boron-modified hexachlorophosphazene, aniline, and sodium ethoxide catalyst to N,N-dimethylformamide solvent, stir and mix, and react at 25-30°C for 1.5-2h. After the reaction is completed, filter, wash, and dry to obtain intermediate 2;

[0017] S3. Add 8-12 parts by weight of intermediate 2 and 0.2-0.5 parts by weight of sodium dodecylbenzene sulfonate emulsifier to deionized water, add 5%-10% hydrochloric acid solution to adjust the pH, stir until it becomes emulsified, add 0.6-0.8 parts by weight of ammonium persulfate oxidant dropwise thereto, react at 25-30°C for 4-5h, after the reaction is completed, add acetone to break the emulsion, filter and dry to obtain hexachlorophosphazene modified polyaniline.

[0018] Preferably, the dropping time of 4-(2-methylpropenyl)carbonyloxyphenylboronic acid in S1 is 55-60 min.

[0019] Preferably, the mass ratio of boron-modified hexachlorophosphazene, aniline and sodium ethoxide in S2 is 1:1.4-1.5:0.04-0.05.

[0020] Preferably, the pH value in S3 is 1-2.

[0021] Preferably, the preparation method of the shielding material containing graphene is: adding silane-modified graphene oxide, hexachlorophosphazene-modified polyaniline, bisphenol A epoxy resin, and triethylenetetramine into a reactor, stirring at a speed of 1800-2000 rpm for 12-15 minutes to obtain a blended solution, then drying under vacuum, compression molding, and curing the obtained sheet to obtain the shielding material containing graphene.

[0022] 3. Beneficial technical effects

[0023] The invention adds silane-modified graphene oxide, hexachlorophosphazene-modified polyaniline, bisphenol A epoxy resin and triethylenetetramine into a reactor, stirs to obtain a blended solution, then dries under vacuum, performs compression molding, and solidifies the obtained sheet to obtain a shielding material containing graphene.

[0024] 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide reacts with the alkenyl group in dimethylallylamine to obtain intermediate 1 and introduce tertiary amine. The tertiary amine in intermediate 1 reacts with 3-chloropropyltrimethoxysilane to quaternize to obtain a phosphorus-containing quaternary ammonium salt-modified silane coupling agent. The phosphorus-containing quaternary ammonium salt-modified silane coupling agent reacts with the hydroxyl group in graphene oxide to obtain silane-modified graphene oxide. The boron hydroxyl group in 4-(2-methylpropylene)carbonyloxyphenylboronic acid reacts with the chlorine in hexachlorophosphazene to obtain boron-modified hexachlorophosphazene and introduce alkenyl group. The alkenyl group in the boron-modified hexachlorophosphazene reacts with the primary amine in aniline to obtain intermediate 2 containing secondary amine. Intermediate 2 undergoes oxidative polymerization under the action of ammonium persulfate to obtain hexachlorophosphazene-modified polyaniline.

[0025] In silane-modified graphene oxide, the phosphorus-containing free radicals or compounds released by 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide during the combustion process react with hydrogen free radicals and hydroxyl free radicals in the flame, thereby interrupting the combustion chain reaction and slowing down or terminating the combustion process; the nitrogen element in the quaternary ammonium salt molecule will decompose into non-combustible gases such as nitrogen and ammonia when burned, which can dilute the oxygen concentration in the air, thereby reducing the combustion intensity of the flame and playing a flame retardant role; at high temperatures, the non-combustible or flame-retardant substances such as silicon dioxide produced by the decomposition of silane will form a dense protective layer on the surface of the shielding material, thereby preventing the spread of flames and playing a flame retardant role; by grafting a phosphorus-containing quaternary ammonium salt-modified silane coupling agent on graphene oxide, the dispersibility of graphene oxide in the shielding material is improved, thereby improving the The electromagnetic shielding effect of the material is improved; in hexachlorophosphazene modified polyaniline, the glassy molten covering formed by the boron element during thermal decomposition can cover the surface of the material to isolate heat and air, thereby achieving a flame retardant effect; the phosphorus- and nitrogen-containing compounds produced by hexachlorophosphazene during thermal decomposition can form a dense protective layer on the surface of the material, isolating oxygen from contact with the combustion products, and have a flame retardant effect; the common use of phosphorus, nitrogen, silicon, and boron elements produces a synergistic flame retardant effect, which significantly improves the flame retardancy of the material; the synergistic effect produced by the blending of graphene oxide and polyaniline further enhances the electrochemical properties of the material, the introduction of graphene can improve the mechanical properties of polyaniline, and at the same time, polyaniline can increase the spacing between graphene sheets and reduce the occurrence of agglomeration between graphene sheets, thereby further improving the electromagnetic shielding performance of the material. DETAILED DESCRIPTION Example 1

[0026] (1) Add 8 parts by weight of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to tetrahydrofuran solvent, stir and dissolve, add 0.2 parts by weight of azobisisobutyronitrile initiator and 9 parts by weight of dimethylallylamine, introduce nitrogen protection, react at 62° C. for 17 hours, and after the reaction is completed, distill under reduced pressure and dry in vacuum to obtain intermediate 1;

[0027] (2) Dissolving the intermediate 1 in anhydrous ethanol, adding 3-chloropropyltrimethoxysilane dropwise thereto, wherein the mass ratio of the intermediate 1 to 3-chloropropyltrimethoxysilane is 1:1.05, heating under reflux at 75° C. for 8 h, cooling after the reaction, washing and drying to obtain a phosphorus-containing quaternary ammonium salt modified silane coupling agent;

[0028] (3) Add 12 parts by weight of graphene oxide powder to deionized water and stir to dissolve, then dissolve 5 parts by weight of a phosphorus-containing quaternary ammonium salt-modified silane coupling agent in anhydrous ethanol, add it to the graphene oxide, ultrasonically treat and stir, add a 2.5% hydrochloric acid solution and adjust it to weak acidity, heat in a water bath at 50°C for 45 minutes, then raise the temperature to 70°C and continue the reaction for 2.5 hours. After the reaction is completed, cool to room temperature, centrifuge, wash and dry to obtain silane-modified graphene oxide;

[0029] (4) Dissolve 7 parts by weight of 4-(2-methylpropenyl)carbonyloxyphenylboronic acid in deionized water, add 5 parts by weight of hexachlorophosphazene to acetone solvent, stir to dissolve, add 4-(2-methylpropenyl)carbonyloxyphenylboronic acid dropwise under nitrogen atmosphere for 55 min, react at 56° C. for 2 h, and then rotary evaporate to obtain boron-modified hexachlorophosphazene;

[0030] (5) Adding boron-modified hexachlorophosphazene, aniline, and sodium ethoxide catalyst to N,N-dimethylformamide solvent, wherein the mass ratio of boron-modified hexachlorophosphazene, aniline, and sodium ethoxide is 1:1.4:0.04, stirring and mixing, reacting at 25°C for 1.5 hours, and filtering, washing, and drying after the reaction to obtain intermediate 2;

[0031] (6) Add 8 parts by weight of the intermediate 2 and 0.2 parts by weight of sodium dodecylbenzene sulfonate emulsifier to deionized water, add 5% by weight hydrochloric acid solution to adjust the pH value to 1, stir until it becomes emulsified, add 0.6 parts by weight of ammonium persulfate oxidant dropwise thereto, react at 25° C. for 4 hours, add acetone to demulsify after the reaction is completed, filter and dry to obtain hexachlorophosphazene modified polyaniline;

[0032] (7) 20 parts by weight of silane-modified graphene oxide, 15 parts by weight of hexachlorophosphazene-modified polyaniline, 8 parts by weight of bisphenol A epoxy resin, and 2 parts by weight of triethylenetetramine are added into a reactor, stirred at 1800 rpm for 12 min to obtain a blended solution, which is then dried under vacuum, compression molded, and the obtained sheet is cured to obtain a shielding material containing graphene. Example 2

[0033] (1) Add 10 parts by weight of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to tetrahydrofuran solvent, stir and dissolve, add 0.4 parts by weight of azobisisobutyronitrile initiator and 12 parts by weight of dimethylallylamine, introduce nitrogen protection, react at 68° C. for 20 hours, and after the reaction is completed, distill under reduced pressure and dry in vacuum to obtain intermediate 1;

[0034] (2) Dissolving the intermediate 1 in anhydrous ethanol, adding 3-chloropropyltrimethoxysilane dropwise thereto, wherein the mass ratio of the intermediate 1 to 3-chloropropyltrimethoxysilane is 1:1.1, reflux heating at 80° C. for 10 h, cooling after the reaction, washing and drying to obtain a phosphorus-containing quaternary ammonium salt modified silane coupling agent;

[0035] (3) adding 15 parts by weight of graphene oxide powder to deionized water and stirring to dissolve, then dissolving 7 parts by weight of a phosphorus-containing quaternary ammonium salt-modified silane coupling agent in anhydrous ethanol, adding the silane coupling agent to the graphene oxide, ultrasonically treating and stirring, adding a 3.2% hydrochloric acid solution and adjusting it to weak acidity, heating in a water bath at 55°C for 55 minutes, then heating to 78°C and continuing the reaction for 3.5 hours. After the reaction is completed, cooling to room temperature, centrifuging, washing and drying to obtain silane-modified graphene oxide;

[0036] (4) 9 parts by weight of 4-(2-methylpropenyl)carbonyloxyphenylboronic acid was dissolved in deionized water, 8 parts by weight of hexachlorophosphazene was added to acetone solvent, and the mixture was stirred to dissolve. 4-(2-methylpropenyl)carbonyloxyphenylboronic acid was added dropwise under nitrogen atmosphere for 60 min. After the addition was completed, the mixture was reacted at 60 °C for 4 h. After the reaction was completed, the mixture was rotary evaporated to obtain boron-modified hexachlorophosphazene.

[0037] (5) Adding boron-modified hexachlorophosphazene, aniline, and sodium ethoxide catalyst to N,N-dimethylformamide solvent, wherein the mass ratio of boron-modified hexachlorophosphazene, aniline, and sodium ethoxide is 1:1.5:0.05, stirring and mixing, reacting at 30°C for 2h, filtering, washing, and drying after the reaction to obtain intermediate 2;

[0038] (6) Add 12 parts by weight of the intermediate 2 and 0.5 parts by weight of sodium dodecylbenzene sulfonate emulsifier to deionized water, add 10% by weight hydrochloric acid solution to adjust the pH value to 2, stir until emulsified, add 0.8 parts by weight of ammonium persulfate oxidant dropwise thereto, react at 30° C. for 5 h, add acetone to demulsify after the reaction is completed, filter and dry to obtain hexachlorophosphazene modified polyaniline;

[0039] (7) 22 parts by weight of silane-modified graphene oxide, 18 parts by weight of hexachlorophosphazene-modified polyaniline, 10 parts by weight of bisphenol A epoxy resin, and 5 parts by weight of triethylenetetramine are added into a reactor, stirred at 2000 rpm for 15 min to obtain a blended solution, which is then dried under vacuum, compression molded, and the obtained sheet is cured to obtain a shielding material containing graphene. Example 3

[0040] (1) Add 9 parts by weight of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to tetrahydrofuran solvent, stir and dissolve, add 0.3 parts by weight of azobisisobutyronitrile initiator and 10 parts by weight of dimethylallylamine, introduce nitrogen protection, react at 65° C. for 18.5 hours, and after the reaction is completed, distill under reduced pressure and dry in vacuum to obtain intermediate 1;

[0041] (2) Dissolving the intermediate 1 in anhydrous ethanol, adding 3-chloropropyltrimethoxysilane dropwise thereto, wherein the mass ratio of the intermediate 1 to 3-chloropropyltrimethoxysilane is 1:1.08, and reflux heating at 78° C. for 9 h. After the reaction is completed, cooling, washing and drying are performed to obtain a phosphorus-containing quaternary ammonium salt modified silane coupling agent;

[0042] (3) adding 13 parts by weight of graphene oxide powder to deionized water and stirring to dissolve, then dissolving 6 parts by weight of a phosphorus-containing quaternary ammonium salt-modified silane coupling agent in anhydrous ethanol, adding the silane coupling agent to the graphene oxide, ultrasonically treating and stirring, adding a 2.8% hydrochloric acid solution and adjusting it to weak acidity, heating in a water bath at 52° C. for 50 min, then heating to 74° C. and continuing the reaction for 3 h. After the reaction is completed, cooling to room temperature, centrifuging, washing and drying to obtain silane-modified graphene oxide;

[0043] (4) 8 parts by weight of 4-(2-methylpropenyl)carbonyloxyphenylboronic acid was dissolved in deionized water, 6 parts by weight of hexachlorophosphazene was added to acetone solvent, and the mixture was stirred to dissolve. 4-(2-methylpropenyl)carbonyloxyphenylboronic acid was added dropwise under nitrogen atmosphere for 58 min. After the addition was completed, the mixture was reacted at 58 °C for 3 h. After the reaction was completed, the mixture was rotary evaporated to obtain boron-modified hexachlorophosphazene.

[0044] (5) Adding boron-modified hexachlorophosphazene, aniline, and sodium ethoxide catalyst to N,N-dimethylformamide solvent, wherein the mass ratio of boron-modified hexachlorophosphazene, aniline, and sodium ethoxide is 1:1.45:0.045, stirring and mixing, reacting at 28°C for 1.8 hours, filtering, washing, and drying after the reaction to obtain intermediate 2;

[0045] (6) Add 10 parts by weight of the intermediate 2 and 0.3 parts by weight of sodium dodecylbenzene sulfonate emulsifier to deionized water, add 7% by weight hydrochloric acid solution to adjust the pH value to 1.5, stir until emulsified, add 0.7 parts by weight of ammonium persulfate oxidant dropwise thereto, react at 28° C. for 4.5 hours, add acetone to demulsify after the reaction, filter and dry to obtain hexachlorophosphazene modified polyaniline;

[0046] (7) 21 parts by weight of silane-modified graphene oxide, 17 parts by weight of hexachlorophosphazene-modified polyaniline, 9 parts by weight of bisphenol A epoxy resin, and 3 parts by weight of triethylenetetramine are added into a reactor, stirred at 1900 rpm for 13 min to obtain a blended solution, which is then dried under vacuum, compression molded, and the obtained sheet is cured to obtain a shielding material containing graphene. Example 4

[0047] (1) Add 8 parts by weight of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to tetrahydrofuran solvent, stir and dissolve, add 0.2 parts by weight of azobisisobutyronitrile initiator and 9 parts by weight of dimethylallylamine, introduce nitrogen protection, react at 62° C. for 17 hours, and after the reaction is completed, distill under reduced pressure and dry in vacuum to obtain intermediate 1;

[0048] (2) Dissolving the intermediate 1 in anhydrous ethanol, adding 3-chloropropyltrimethoxysilane dropwise thereto, wherein the mass ratio of the intermediate 1 to 3-chloropropyltrimethoxysilane is 1:1.05, heating under reflux at 75° C. for 8 h, cooling after the reaction, washing and drying to obtain a phosphorus-containing quaternary ammonium salt modified silane coupling agent;

[0049] (3) Add 12 parts by weight of graphene oxide powder to deionized water and stir to dissolve, then dissolve 5 parts by weight of a phosphorus-containing quaternary ammonium salt-modified silane coupling agent in anhydrous ethanol, add it to the graphene oxide, ultrasonically treat and stir, add a 2.5% hydrochloric acid solution and adjust it to weak acidity, heat in a water bath at 50°C for 45 minutes, then raise the temperature to 70°C and continue the reaction for 2.5 hours. After the reaction is completed, cool to room temperature, centrifuge, wash and dry to obtain silane-modified graphene oxide;

[0050] (4) 9 parts by weight of 4-(2-methylpropenyl)carbonyloxyphenylboronic acid was dissolved in deionized water, 8 parts by weight of hexachlorophosphazene was added to acetone solvent, and the mixture was stirred to dissolve. 4-(2-methylpropenyl)carbonyloxyphenylboronic acid was added dropwise under nitrogen atmosphere for 60 min. After the addition was completed, the mixture was reacted at 60 °C for 4 h. After the reaction was completed, the mixture was rotary evaporated to obtain boron-modified hexachlorophosphazene.

[0051] (5) Adding boron-modified hexachlorophosphazene, aniline, and sodium ethoxide catalyst to N,N-dimethylformamide solvent, wherein the mass ratio of boron-modified hexachlorophosphazene, aniline, and sodium ethoxide is 1:1.5:0.05, stirring and mixing, reacting at 30°C for 2h, filtering, washing, and drying after the reaction to obtain intermediate 2;

[0052] (6) Add 10 parts by weight of the intermediate 2 and 0.3 parts by weight of sodium dodecylbenzene sulfonate emulsifier to deionized water, add 7% by weight hydrochloric acid solution to adjust the pH value to 1.5, stir until emulsified, add 0.7 parts by weight of ammonium persulfate oxidant dropwise thereto, react at 28° C. for 4.5 hours, add acetone to demulsify after the reaction, filter and dry to obtain hexachlorophosphazene modified polyaniline;

[0053] (7) 21 parts by weight of silane-modified graphene oxide, 17 parts by weight of hexachlorophosphazene-modified polyaniline, 9 parts by weight of bisphenol A epoxy resin, and 3 parts by weight of triethylenetetramine are added into a reactor, stirred at 1900 rpm for 13 min to obtain a blended solution, which is then dried under vacuum, compression molded, and the obtained sheet is cured to obtain a shielding material containing graphene.

[0054] Comparative Example 1

[0055] Compared with Example 4, this comparative example is different in that no silane-modified graphene oxide is added.

[0056] Comparative Example 2

[0057] Compared with Example 4, the difference between this comparative example and Example 4 is that hexachlorophosphazene-modified polyaniline is not added.

[0058] The limiting oxygen index of the shielding material was tested using an oxygen index meter, and the combustion level of the shielding material was tested using a horizontal and vertical combustion instrument. The test results are shown in Table 1.

[0059] Table 1: Flame retardant performance test.

[0060] project Limiting oxygen index (%) Combustion level Example 1 36 V-0 Example 2 38 V-0 Example 3 35 V-0 Example 4 37 V-0 Comparative Example 1 25 V-1 Comparative Example 2 24 V-1

[0061] It can be seen from Table 1 that Examples 1-4 of the present invention have better flame retardant effects than Comparative Examples 1-2.

[0062] The electromagnetic shielding performance of the shielding material was tested using a vector network analyzer. The test specimen was a circular specimen with an inner diameter of 3 mm, an outer diameter of 6 mm, and a thickness of 2 mm. The test results are shown in Table 2.

[0063] Table 2: Electromagnetic shielding performance test.

[0064]

[0065] It can be seen from Table 2 that Examples 1-4 of the present invention have better electromagnetic shielding effects than Comparative Examples 1-2.

[0066] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific implementation methods described. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A shielding material containing graphene, characterized in that: The invention comprises the following components by weight: 20-22 parts by weight of silane-modified graphene oxide, 15-18 parts by weight of hexachlorophosphazene-modified polyaniline, 8-10 parts by weight of bisphenol A epoxy resin, and 2-5 parts by weight of triethylenetetramine; The method for preparing silane-modified graphene oxide comprises the following steps: (1) Add 8-10 parts by weight of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to tetrahydrofuran solvent, stir and dissolve, add 0.2-0.4 parts by weight of initiator and 9-12 parts by weight of dimethylallylamine, introduce nitrogen protection, react at 62-68° C. for 17-20 hours, and after the reaction is completed, distill under reduced pressure and dry in vacuum to obtain intermediate 1; (2) Dissolve the intermediate 1 in anhydrous ethanol, add 3-chloropropyltrimethoxysilane dropwise thereto, and reflux heat at 75-80° C. for 8-10 hours. After the reaction is completed, cool, wash and dry to obtain a phosphorus-containing quaternary ammonium salt modified silane coupling agent; (3) adding 12-15 parts by weight of graphene oxide powder to deionized water, stirring to dissolve, then dissolving 5-7 parts by weight of a phosphorus-containing quaternary ammonium salt-modified silane coupling agent in anhydrous ethanol, adding the silane coupling agent to the graphene oxide, ultrasonically treating and stirring, adding a hydrochloric acid solution and adjusting to weak acidity, heating in a water bath at 50-55° C. for 45-55 minutes, then heating to 70-78° C. and continuing the reaction for 2.5-3.5 hours, and after the reaction is completed, cooling to room temperature, centrifuging, washing and drying to obtain silane-modified graphene oxide; The method for preparing the hexachlorophosphazene-modified polyaniline comprises the following steps: S1. Dissolve 7-9 parts by weight of 4-(2-methylpropenyl)carbonyloxyphenylboronic acid in deionized water, add 5-8 parts by weight of hexachlorophosphazene to an acetone solvent, stir to dissolve, add 4-(2-methylpropenyl)carbonyloxyphenylboronic acid dropwise under a nitrogen atmosphere, react at 56-60° C. for 2-4 hours, and then rotary evaporate to obtain boron-modified hexachlorophosphazene; S2. Add boron-modified hexachlorophosphazene, aniline, and sodium ethoxide catalyst to N,N-dimethylformamide solvent, stir and mix, and react at 25-30°C for 1.5-2h. After the reaction is completed, filter, wash, and dry to obtain intermediate 2; S3. Add 8-12 parts by weight of intermediate 2 and 0.2-0.5 parts by weight of sodium dodecylbenzene sulfonate emulsifier to deionized water, add 5%-10% hydrochloric acid solution to adjust the pH, stir until it becomes emulsified, add 0.6-0.8 parts by weight of ammonium persulfate oxidant dropwise thereto, react at 25-30°C for 4-5h, after the reaction is completed, add acetone to break the emulsion, filter and dry to obtain hexachlorophosphazene modified polyaniline.

2. The shielding material containing graphene according to claim 1, characterized in that: The initiator in step (1) is azobisisobutyronitrile.

3. The shielding material containing graphene according to claim 1, characterized in that: In the step (2), the mass ratio of the intermediate 1 to 3-chloropropyltrimethoxysilane is 1:1.05-1.

1.

4. The shielding material containing graphene according to claim 1, characterized in that: The mass fraction of the hydrochloric acid solution in step (3) is 2.5%-3.2%.

5. The shielding material containing graphene according to claim 1, characterized in that: The dropping time of 4-(2-methylpropenyl)carbonyloxyphenylboronic acid in S1 is 55-60 min.

6. The shielding material containing graphene according to claim 1, characterized in that: The mass ratio of boron-modified hexachlorophosphazene, aniline and sodium ethoxide in S2 is 1:1.4-1.5:0.04-0.

05.

7. The shielding material containing graphene according to claim 1, characterized in that: The pH value of S3 is 1-2.

8. A method for preparing a shielding material containing graphene according to any one of claims 1 to 7, characterized in that: The preparation method of the shielding material containing graphene is as follows: adding silane-modified graphene oxide, hexachlorophosphazene-modified polyaniline, bisphenol A epoxy resin and triethylenetetramine into a reactor, stirring at a speed of 1800-2000 rpm for 12-15 minutes to obtain a blended solution, then drying under vacuum, compression molding, and curing the obtained sheet to obtain the shielding material containing graphene.

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