Material for preventing nuclear pollution, and preparation method therefor and use thereof

Abstract

Disclosed in the present invention are a material for preventing nuclear pollution, and a preparation method therefor and the use thereof. The material for preventing nuclear pollution of the present invention comprises raw materials including a polyimide semi-interpenetrating network resin, a double-layered carbon-coated nuclear pollution shielding agent and a reinforcing agent 8121, wherein a semi-interpenetrating network of the polyimide resin is filled with the double-layered carbon-coated nuclear pollution shielding agent and the reinforcing agent 8121. The material for preventing nuclear pollution prepared in the present invention has an antibacterial function, satisfies the requirements for both γray and neutron shielding functions, and has a better nuclear shielding effect. The material for preventing nuclear pollution prepared in the present invention can effectively prevent biotoxicity caused by a lead powder that falls off of a matrix after the matrix is aged, and better protects human health. In addition, a material layer for preventing nuclear pollution of the present invention can be used for preparing clothing for preventing nuclear pollution.

Description

A nuclear pollution-proof material and its preparation method and application Technical Field

[0001] The present invention relates to the technical field of nuclear pollution prevention materials, and in particular to a nuclear pollution prevention material and a preparation method and application thereof. Background Art

[0002] Nuclear energy offers significant advantages and is widely used in numerous fields, including power generation and shipbuilding. However, nuclear operations generate significant amounts of α, β, γ, and X-rays, as well as a certain amount of neutrons, releasing energy. These radiation and neutrons pose health risks to personnel near the radiation source and can also damage nearby metal materials and electronic equipment. Therefore, shielding measures are necessary to protect against the various radiation and neutrons involved in nuclear operations. Studies have shown that α, β, and X-rays have low energy and very weak penetrating power, and can be effectively shielded by cardboard. However, γ-rays and neutrons have higher energy and strong penetrating power. Therefore, nuclear radiation shielding essentially involves shielding against γ-rays and neutrons.

[0003] Gamma rays are electromagnetic waves with a shorter wavelength than ultraviolet rays. They release energy through the photoelectric effect, the Compton effect, and the electron pair effect. Lead is abundant, inexpensive, and has a high mass attenuation coefficient for gamma rays, making it the most widely used gamma-ray shielding material in nuclear power plants. Traditional gamma-ray shielding materials typically use lead powder as a filler, added to a plastic or rubber matrix. However, as the matrix ages, the lead powder sheds from the matrix and becomes biotoxic. Wearing radiation protective clothing or skirts made of lead-based composite fabrics carries certain health risks.

[0004] Boron carbide is the most commonly used neutron absorber in neutron shielding materials. Boron carbide is characterized by its high temperature resistance, good stability, and high boron content, making it widely used in neutron shielding materials. However, boron carbide is an inorganic particle, and the commonly used base material is an organic polymer. The compatibility between the two is generally poor, which affects the uniformity of the material and, in turn, its neutron shielding capability.

[0005] Therefore, it is necessary to prepare a material with better performance in preventing nuclear pollution. Summary of the Invention

[0006] In response to the limitations of the above-mentioned prior art, the present invention provides a nuclear pollution-proof material, a preparation method thereof, and an application thereof. The nuclear pollution-proof fabric of the present invention first coats a nuclear pollution shielding agent with a carbon layer, then introduces boric acid into the intermediate agent through impregnation on the outer side of the carbon layer, and then polymerizes a layer of polydopamine. This is then calcined at high temperature to form B4C, and a carbon layer formed by polydopamine is also coated on the B4C. The protective structure of the two carbon layers not only effectively coats the nuclear pollution shielding agent, avoiding the risk of the nuclear pollution shielding agent escaping after aging of the substrate, but also has a certain volume deformation space, is not easy to rupture, and is also beneficial for preventing damage to the body caused by the escape of lead powder. Finally, the nuclear pollution shielding agent coated with the carbon layer has better compatibility with the resin matrix than the pure nuclear pollution shielding agent, which is beneficial for the dispersion of the nuclear pollution shielding agent in the resin matrix and improves the nuclear pollution shielding effect.

[0007] To achieve the above object, the present invention adopts the following technical solutions:

[0008] One of the purposes of the present invention is to provide a nuclear pollution prevention material, which includes raw materials such as polyimide semi-interpenetrating network resin, double-layer carbon-coated nuclear pollution shielding agent, and reinforcer 8121, wherein the double-layer carbon-coated nuclear pollution shielding agent and reinforcer 8121 are filled in the semi-interpenetrating network of polyimide resin.

[0009] In a preferred embodiment, the structure of the double-layer carbon-coated nuclear pollution shielding agent is nuclear pollution shielding agent 1, inner carbon layer, nuclear pollution shielding agent 2, outer carbon layer;

[0010] Wherein, the nuclear pollution shielding agent is selected from at least one of lead or lead oxide particles;

[0011] The second nuclear pollution shielding agent is selected from B4C;

[0012] The reinforcing agent 8121 is polyimide-based 8121.

[0013] In a preferred embodiment, the anti-nuclear pollution material comprises, by weight, 100 parts of polyimide semi-interpenetrating network resin; 10-30 parts of double-layer carbon-coated nuclear pollution shielding agent; and 1-5 parts of reinforcing agent 8121.

[0014] In a preferred embodiment, the preparation method of the double-layer carbon-coated nuclear pollution shielding agent is:

[0015] Step 1) adding a nuclear pollution shielding agent 1 to a molten phenolic resin and mixing them uniformly, and then calcining them once in an inert atmosphere to obtain an intermediate 1;

[0016] Step 2) adding the intermediate 1 into boric acid for impregnation, taking it out after impregnation, and coating it with dopamine by in-situ polymerization to obtain the intermediate 2;

[0017] Step 3) The intermediate 2 is subjected to secondary calcination in an inert atmosphere to obtain the double-layer carbon-coated nuclear pollution shielding agent.

[0018] In a preferred embodiment, in step 1),

[0019] The mass ratio of nuclear pollution shielding agent 1 to phenolic resin is 3-5:1;

[0020] The primary calcination temperature is 800-1000 degrees, and the primary calcination time is 2-4 hours.

[0021] In a further preferred embodiment, in step 2),

[0022] The mass ratio of the intermediate 1 to the boric acid solution is 1:4-6; the concentration of the boric acid solution is 1-2 mol / L;

[0023] The soaking time is 2-5 hours;

[0024] The method of in-situ polymerization of dopamine is as follows: adding the intermediate 1 impregnated with boric acid to deionized water at pH=8.5-9.0, adding dopamine hydrochloride, stirring, solid-liquid separation, and drying the solid to obtain the intermediate 2; and / or,

[0025] In step 3),

[0026] The temperature of the secondary calcination is 1200-1400 degrees, and the time of the secondary calcination is 2-4 hours.

[0027] In a further preferred embodiment, in step 2), the method of in-situ polymerization of dopamine is adopted.

[0028] The mass ratio of the intermediate 1 to dopamine hydrochloride is 0.6-1:1; and the stirring time is 3h to 6h.

[0029] The anti-nuclear pollution material of the present invention first coats a carbon layer on a nuclear pollution shielding agent, then forms a polydopamine layer on the outer side of the carbon layer through self-polymerization, introduces boric acid into the intermediate through impregnation, and then polymerizes a layer of polydopamine. The intermediate is calcined at high temperature to form B4C, and a carbon layer formed by polydopamine is also coated on the B4C. The protective structure of the two carbon layers can not only effectively coat the nuclear pollution shielding agent, avoiding the risk of the nuclear pollution shielding agent falling out after aging of the substrate, but also has a certain volume deformation space, is not easy to break, and is also conducive to avoiding physical damage caused by the escape of lead powder. Finally, the nuclear pollution shielding agent coated with the carbon layer has better compatibility with the rubber substrate than the pure nuclear pollution shielding agent, which is conducive to the dispersion of the nuclear pollution shielding agent in the substrate and improves the nuclear pollution shielding effect.

[0030] A second object of the present invention is to provide a method for preparing the nuclear pollution prevention material as described in any one of the objects of the present invention, wherein a certain proportion of triphenyl ether dianhydride type thermoplastic polyimide powder and bismaleimide powder are mixed in a high-plastic mixer, and then a double-layer carbon-coated nuclear pollution shielding agent and a reinforcing agent 8121 are added and mixed. After mixing, the mixture is loaded into a mold and molded to obtain the nuclear pollution prevention material.

[0031] In a preferred embodiment, the amount of the triphenyl ether dianhydride type thermoplastic polyimide powder added is 70-80 parts based on the total weight of the triphenyl ether dianhydride type thermoplastic polyimide powder and the bismaleimide powder as 100 parts; and / or,

[0032] The molding temperature is 370-390°C; and / or,

[0033] The molding pressure is 15-25Mpa;

[0034] The third object of the present invention is to provide an application of the anti-nuclear pollution material as described in any one of the objects of the present invention in the preparation of anti-nuclear pollution clothing.

[0035] The nuclear pollution prevention clothing of the present invention comprises the nuclear pollution prevention material layer prepared as described above. The nuclear pollution prevention material layer can be prepared by laminating with other multi-layer materials. The nuclear pollution prevention clothing product prepared by the present invention is shown in FIG1 .

[0036] Compared with the prior art, the present invention has at least the following advantages:

[0037] 1. The anti-nuclear pollution material prepared by the present invention has antibacterial function and meets the requirements of gamma ray and neutron shielding function, and has better nuclear shielding effect.

[0038] 2. The nuclear pollution-proof material prepared by the present invention can effectively prevent the biological toxicity caused by lead powder falling off the matrix after aging, thereby better protecting human health. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] FIG1 is a schematic diagram of the nuclear pollution prevention clothing of the present invention. DETAILED DESCRIPTION

[0040] The present invention will be described in detail below with reference to specific embodiments. It is necessary to point out that the following embodiments are only used to further illustrate the present invention and are not to be construed as limiting the scope of protection of the present invention. Non-essential improvements and adjustments made by those skilled in the art to the present invention based on the contents of the present invention still fall within the scope of protection of the present invention.

[0041] The reinforcing agent 8121 in the embodiment of the present invention is polyimide-based 8121, which was purchased from Shenyang Puli Textile New Materials Co., Ltd.

[0042] Preparation Example 1

[0043] Preparation of double-layer carbon-coated nuclear pollution shielding agent materials:

[0044] Step 1) adding a nuclear pollution shielding agent 1 to a molten phenolic resin and mixing them uniformly, and then calcining them once in an inert atmosphere (nitrogen) to obtain an intermediate 1; wherein the mass ratio of the nuclear pollution shielding agent 1 to the phenolic resin is 3:1; the primary calcination temperature is 1000 degrees, and the primary calcination time is 2.5 hours.

[0045] Step 2) adding the intermediate 1 to boric acid for immersion, taking it out after immersion, and coating it with dopamine by in-situ polymerization to obtain the intermediate 2; wherein the mass ratio of the intermediate 1 to the boric acid solution is 1:5; the concentration of the boric acid solution is 1.5 mol / L; and the immersion time is 3 hours;

[0046] The method of in-situ polymerization of dopamine is as follows: intermediate 1 impregnated with boric acid is added to deionized water with a pH of 8.5, dopamine hydrochloride is added, stirred, solid-liquid separated, and the solid is dried to obtain intermediate 2; the mass ratio of intermediate 1 to dopamine hydrochloride is 0.8:1; and the stirring time is 4 hours.

[0047] Step 3) The intermediate 2 is subjected to a secondary calcination in an inert atmosphere (nitrogen) to obtain the double-layer carbon-coated nuclear pollution shielding agent. The secondary calcination temperature is 1300 degrees and the secondary calcination time is 3 hours.

[0048] Preparation Example 2

[0049] Preparation of double-layer carbon-coated nuclear pollution shielding agent materials:

[0050] Step 1) adding a nuclear pollution shielding agent 1 to a molten phenolic resin and mixing them uniformly, and then calcining them once in an inert atmosphere (nitrogen) to obtain an intermediate 1; wherein the mass ratio of the nuclear pollution shielding agent 1 to the phenolic resin is 4:1; the primary calcination temperature is 900 degrees, and the primary calcination time is 3 hours.

[0051] Step 2) adding the intermediate 1 to boric acid for immersion, taking it out after immersion, and coating it with dopamine by in-situ polymerization to obtain the intermediate 2; wherein the mass ratio of the intermediate 1 to the boric acid solution is 1:4; the concentration of the boric acid solution is 2 mol / L; and the immersion time is 4 hours;

[0052] The intermediate 1 impregnated with boric acid was added to deionized water at pH = 9.0, and dopamine hydrochloride was added. After stirring, the solid-liquid separation was performed, and the solid was dried to obtain the intermediate 2; the mass ratio of the intermediate 1 to dopamine hydrochloride was 0.9:1; and the stirring time was 3.5 h.

[0053] Step 3) The intermediate 2 is subjected to a secondary calcination in an inert atmosphere (nitrogen) to obtain the double-layer carbon-coated nuclear pollution shielding agent. The secondary calcination temperature is 1400 degrees and the secondary calcination time is 2 hours.

[0054] Example 1

[0055] The preparation method of the anti-nuclear pollution material is:

[0056] A certain proportion of triphenyl ether dianhydride type thermoplastic polyimide powder and bismaleimide powder are mixed in a high-pressure plastic mixer, and then a double-layer carbon-coated nuclear pollution shielding agent and a reinforcing agent 8121 are added and mixed. After mixing, the mixture is put into a mold for molding, and the molding is performed at 285° C. and 22 MPa to obtain the anti-nuclear pollution material;

[0057] Among them, based on the total weight of triphenyl ether dianhydride type thermoplastic polyimide powder and bismaleimide powder as 100 parts (that is, the polyimide semi-interpenetrating network resin formed by the two is 100 parts), the added amount of triphenyl ether dianhydride type thermoplastic polyimide powder is 68 parts; 20 parts of the double-layer carbon-coated nuclear pollution shielding agent prepared in Preparation Example 1; 81213 parts of the reinforcing agent;

[0058] The structure of triphenyl ether dianhydride type thermoplastic polyimide is:

[0059] Among them, Ar is

[0060] The structure of bismaleimide is:

[0061] The nuclear pollution prevention material of the present invention comprises a polyimide semi-interpenetrating network resin, a double-layer carbon-coated nuclear pollution shielding agent, and a reinforcing agent 8121, wherein the double-layer carbon-coated nuclear pollution shielding agent and the reinforcing agent 8121 are filled within the polyimide semi-interpenetrating network. The performance of the nuclear pollution prevention material prepared above was tested, and the specific data are shown in Table 1.

[0062] Example 2

[0063] The preparation method of the anti-nuclear pollution material is:

[0064] A certain proportion of triphenyl ether dianhydride type thermoplastic polyimide powder and bismaleimide powder are mixed in a high-pressure plastic mixer, and then a double-layer carbon-coated nuclear pollution shielding agent and a reinforcing agent 8121 are added and mixed. After mixing, the mixture is put into a mold for molding, and the molding is performed at 288° C. and 23 MPa to obtain the anti-nuclear pollution material.

[0065] Among them, based on the total weight of triphenyl ether dianhydride type thermoplastic polyimide powder and bismaleimide powder as 100 parts (that is, the polyimide semi-interpenetrating network resin formed by the two is 100 parts), the added amount of triphenyl ether dianhydride type thermoplastic polyimide powder is 72 parts; 26 parts of the double-layer carbon-coated nuclear pollution shielding agent prepared in Preparation Example 1; 81214 parts of the reinforcing agent.

[0066] The structure of triphenyl ether dianhydride type thermoplastic polyimide is:

[0067] Among them, Ar is

[0068] The structure of bismaleimide is:

[0069] The nuclear pollution prevention material of the present invention comprises a polyimide semi-interpenetrating network resin, a double-layer carbon-coated nuclear pollution shielding agent, and a reinforcing agent 8121, wherein the double-layer carbon-coated nuclear pollution shielding agent and the reinforcing agent 8121 are filled within the polyimide semi-interpenetrating network. The performance of the nuclear pollution prevention material prepared above was tested, and the specific data are shown in Table 1.

[0070] Example 3

[0071] The preparation method of the anti-nuclear pollution material is:

[0072] A certain proportion of triphenyl ether dianhydride type thermoplastic polyimide powder and bismaleimide powder are mixed in a high-pressure plastic mixer, and then a double-layer carbon-coated nuclear pollution shielding agent and a reinforcing agent 8121 are added and mixed. After mixing, the mixture is put into a mold for molding, and the molding is performed at 285° C. and 22 MPa to obtain the anti-nuclear pollution material;

[0073] Among them, based on the total weight of triphenyl ether dianhydride type thermoplastic polyimide powder and bismaleimide powder as 100 parts (that is, the polyimide semi-interpenetrating network resin formed by the two is 100 parts), the added amount of triphenyl ether dianhydride type thermoplastic polyimide powder is 80 parts; the double-layer carbon-coated nuclear pollution shielding agent prepared in Preparation Example 1 is 12 parts; the reinforcing agent is 81211 parts;

[0074] The structure of triphenyl ether dianhydride type thermoplastic polyimide is:

[0075] Among them, Ar is

[0076] The structure of bismaleimide is:

[0077] The nuclear pollution prevention material of the present invention comprises a polyimide semi-interpenetrating network resin, a double-layer carbon-coated nuclear pollution shielding agent, and a reinforcing agent 8121, wherein the double-layer carbon-coated nuclear pollution shielding agent and the reinforcing agent 8121 are filled within the polyimide semi-interpenetrating network. The performance of the nuclear pollution prevention material prepared above was tested, and the specific data are shown in Table 1.

[0078] Comparative Example 1

[0079] In the preparation of the double-layer carbon-coated nuclear pollution shielding agent, the preparation method is basically the same as that of Preparation Example 1, with the only difference being that the in-situ polymerization of dopamine is not performed.

[0080] The preparation method of the nuclear pollution prevention material is the same as that of Example 1. The performance of the nuclear pollution prevention material prepared above was tested, and the specific data are shown in Table 1.

[0081] Comparative Example 2

[0082] The preparation method is substantially the same as that of Example 1, except that the enhancer 8121 is not added. The performance of the nuclear pollution prevention material prepared above was tested, and the specific data are shown in Table 1.

[0083] The performance tests of the anti-nuclear pollution material layers prepared in the examples and comparative examples were carried out, and the specific results are shown in Table 1.

[0084] Table 1 Performance test data of different anti-nuclear pollution material layers

[0085] The results in Table 1 indicate that the nuclear pollution prevention material prepared by the present invention meets both gamma-ray and neutron shielding requirements, achieving enhanced nuclear shielding effectiveness. Furthermore, the nuclear pollution prevention material prepared by the present invention effectively prevents the biotoxicity caused by lead powder shedding from the substrate after aging, thereby better protecting human health.

[0086] It will be understood that the above embodiments are merely exemplary embodiments for illustrating the principles of the present invention, and the present invention is not limited thereto. Those skilled in the art will appreciate that various modifications and improvements can be made without departing from the spirit and substance of the present invention, and such modifications and improvements are also considered to be within the scope of protection of the present invention.

Claims

1. A material for preventing nuclear pollution, characterized in that: The anti-nuclear pollution material includes raw materials including polyimide semi-interpenetrating network resin, double-layer carbon-coated nuclear pollution shielding agent, and reinforcing agent 8121, wherein the double-layer carbon-coated nuclear pollution shielding agent and reinforcing agent 8121 are filled in the semi-interpenetrating network of polyimide resin; The structure of the double-layer carbon-coated nuclear pollution shielding agent is nuclear pollution shielding agent 1, inner carbon layer, nuclear pollution shielding agent 2, outer carbon layer in sequence; wherein the nuclear pollution shielding agent 1 is selected from at least one of lead or lead oxide particles; the nuclear pollution shielding agent 2 is selected from B4C; the reinforcing agent 8121 is polyimide-based 8121; The anti-nuclear pollution materials include, by weight: 100 parts of polyimide semi-interpenetrating network resin; 10-30 parts of double-layer carbon-coated nuclear pollution shielding agent; Enhancer 8121 1-5 parts; The preparation method of the double-layer carbon-coated nuclear pollution shielding agent is as follows: Step 1) adding a nuclear pollution shielding agent 1 to a molten phenolic resin and mixing them evenly, and then calcining them once in an inert atmosphere to obtain an intermediate 1; Step 2) adding the intermediate 1 into boric acid for dipping, taking it out after dipping, and coating it by in-situ polymerization of dopamine to obtain the intermediate 2; Step 3) The intermediate 2 is subjected to secondary calcination in an inert atmosphere to obtain the double-layer carbon-coated nuclear pollution shielding agent; Method for preparing material for preventing nuclear pollution, A certain proportion of triphenyl ether dianhydride type thermoplastic polyimide powder and bismaleimide powder are mixed in a high-plastic mixer, and then double-layer carbon-coated nuclear pollution shielding agent and reinforcing agent 8121 are added and mixed, and after mixing, the mixture is loaded into a mold for molding to obtain the anti-nuclear pollution material; Based on the total weight of the triphenyl ether dianhydride type thermoplastic polyimide powder and the bismaleimide powder as 100 parts, the amount of the triphenyl ether dianhydride type thermoplastic polyimide powder added is 60-80 parts; The structure of triphenyl ether dianhydride type thermoplastic polyimide is: Among them, Ar is or The structure of bismaleimide is:

2. The anti-nuclear pollution material according to claim 1, characterized in that: In step 1), The mass ratio of nuclear pollution shielding agent 1 to phenolic resin is 3-5:1; The temperature of a calcination is 800-1000 degrees, and the time of a calcination is 2-4 hours.

3. The anti-nuclear pollution material according to claim 1, characterized in that: In step 2), The mass ratio of the intermediate 1 to the boric acid solution is 1:4-6; the concentration of the boric acid solution is 1-2 mol / L; The soaking time is 2-5 hours; The method of in-situ polymerization of dopamine is as follows: adding the intermediate 1 impregnated with boric acid into deionized water with a pH of 8.5-9.0, adding dopamine hydrochloride, stirring, separating the solid from the liquid, and drying the solid to obtain the intermediate 2; and / or, In step 3), The temperature of the secondary calcination is 1200-1400 degrees, and the time of the secondary calcination is 2-4 hours.

4. The anti-nuclear pollution material according to claim 3, characterized in that: In step 2), in the method of in-situ polymerization of dopamine, The mass ratio of the intermediate 1 to dopamine hydrochloride is 0.6-1:1; and the stirring time is 3h to 6h.

5. A method for preparing the anti-nuclear pollution material according to any one of claims 1 to 4, characterized in that: A certain proportion of triphenyl ether dianhydride type thermoplastic polyimide powder and bismaleimide powder are mixed in a high-plastic mixer, and then double-layer carbon-coated nuclear pollution shielding agent and reinforcing agent 8121 are added and mixed. After mixing, the mixture is loaded into a mold for molding to obtain the anti-nuclear pollution material.

6. The method for preparing the anti-nuclear pollution material according to claim 5, characterized in that: Based on 100 parts by total weight of the triphenyl ether dianhydride type thermoplastic polyimide powder and the bismaleimide powder, the amount of the triphenyl ether dianhydride type thermoplastic polyimide powder added is 60-80 parts; and / or, The molding temperature is 370-390°C; and / or, The molding pressure is 15-25Mpa.

7. Use of the anti-nuclear pollution material as claimed in any one of claims 1 to 4 in the preparation of anti-nuclear pollution clothing.

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