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

Abstract

The present invention discloses a nuclear pollution prevention material and its preparation method and application. The nuclear pollution prevention material of the present invention comprises raw materials including 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 in the semi-interpenetrating network of the polyimide resin. The nuclear pollution prevention material prepared by the present invention has an antibacterial function, and at the same time meets the requirements of the gamma-ray and neutron shielding functions, and has a better nuclear shielding effect. The nuclear pollution prevention material prepared by the present invention can effectively prevent the biological toxicity that exists after the lead powder falls off from the matrix after the matrix ages, and better protect human health. And the nuclear pollution prevention material layer of the present invention can be used to prepare nuclear pollution prevention clothing.

Description

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] The huge advantages of nuclear energy are widely used in many fields such as power generation and ships. However, a large amount of α, β, γ, X-rays and certain neutrons will be generated during nuclear operation, and energy will be released. The radiated rays and neutrons will not only harm the health of people near the radiation source, but also damage nearby metal materials and electronic equipment. Therefore, it is necessary to take shielding measures for various rays and neutrons in nuclear operation. Studies have shown that: α, β, and X-rays have low energy and very weak penetration ability, and general cardboard can achieve effective shielding, while γ rays and neutrons have high energy and strong penetration ability. Therefore, nuclear radiation shielding is essentially shielding against γ rays and neutrons.

[0003] Gamma rays are electromagnetic waves with a shorter wavelength than ultraviolet rays, and release energy through the photoelectric effect, Compton effect, and electron pair effect. Lead is abundant, cheap, and has a high mass attenuation coefficient for gamma rays. It is currently the most widely used gamma ray shielding material in nuclear power plants. Traditional gamma ray radiation protection materials usually use lead powder as a filler and add it to a plastic or rubber matrix. However, after the matrix ages, the lead powder will fall off the matrix and become biologically toxic. Wearing radiation protective clothing and protective skirts made of lead composite fabrics poses certain health risks.

[0004] The most commonly used neutron absorber in neutron shielding materials is boron carbide, which has the characteristics of high temperature resistance, good stability, and high boron content, and is widely used in neutron shielding materials. However, boron carbide is an inorganic particle, and the commonly used substrate is an organic polymer material. The compatibility of the two is usually poor, which will affect the uniformity of the material and further affect the neutron shielding ability of the material.

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

[0006] In view of the limitations of the above-mentioned prior art, the present invention provides a nuclear pollution prevention material and its preparation method and application. The nuclear pollution prevention fabric of the present invention first coats a carbon layer on the nuclear pollution shielding agent, then introduces boric acid into the intermediate by impregnation on the outside of the carbon layer, and then polymerizes a layer of polydopamine, forms B4C by high-temperature calcination, and can also coat a carbon layer formed by polydopamine on 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 escaping after the substrate ages, but also the double-layer protective structure has a certain volume deformation space, is not easy to break, and is also conducive to avoiding the body damage caused by the escape of lead powder; finally, the compatibility of the nuclear pollution shielding agent coated with the carbon layer with the resin matrix is ​​better than that of the pure nuclear pollution shielding agent, which is conducive to 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 comprises raw materials including 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 in the semi-interpenetrating network of the 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 contamination 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 includes, by weight, 100 parts of polyimide semi-interpenetrating network resin;

[0014] 10-30 parts of double-layer carbon-coated nuclear pollution shielding agent;

[0015] Enhancer 8121 1-5 parts.

[0016] In a preferred embodiment, the preparation method of the double-layer carbon-coated nuclear pollution shielding agent is:

[0017] 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;

[0018] 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;

[0019] 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.

[0020] In a preferred embodiment, in step 1),

[0021] The mass ratio of nuclear pollution shielding agent 1 to phenolic resin is 3-5:1;

[0022] The temperature of a calcination is 800-1000 degrees, and the time of a calcination is 2-4 hours.

[0023] In a further preferred embodiment, in step 2),

[0024] 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;

[0025] The soaking time is 2-5 hours;

[0026] 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,

[0027] In step 3),

[0028] The temperature of the secondary calcination is 1200-1400 degrees, and the time of the secondary calcination is 2-4 hours.

[0029] In a further preferred embodiment, in step 2), in the method of in-situ polymerization of dopamine,

[0030] The mass ratio of the intermediate 1 to dopamine hydrochloride is 0.6-1:1; and the stirring time is 3h to 6h.

[0031] The anti-nuclear pollution material of the 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 an intermediate through impregnation, then polymerizes a layer of polydopamine, forms B4C through high-temperature calcination, and can also coat a carbon layer formed by polydopamine on the B4C; the protective structure of the two carbon layers can not only effectively coat the nuclear pollution shielding agent to avoid the risk of the nuclear pollution shielding agent falling out after the substrate is aged, but also the double-layer protective structure has a certain volume deformation space, is not easy to break, and is also conducive to avoiding the body 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.

[0032] The second object of the present invention is to provide a method for preparing the anti-nuclear pollution 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, and after mixing, the mixture is loaded into a mold and molded to obtain the anti-nuclear pollution material.

[0033] 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,

[0034] The molding temperature is 370-390°C; and / or,

[0035] The molding pressure is 15-25Mpa;

[0036] 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.

[0037] The anti-nuclear pollution clothing of the present invention comprises the anti-nuclear pollution material layer prepared above, and the anti-nuclear pollution material layer can be prepared by laminating with other multi-layer materials. The anti-nuclear pollution clothing product prepared by the present invention is as follows Figure 1 shown.

[0038] Compared with the prior art, the present invention has at least the following advantages:

[0039] 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.

[0040] 2. The nuclear pollution-proof material prepared by the present invention can effectively prevent the biological toxicity of lead powder that falls off from the matrix after aging, thereby better protecting human health. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1 It is a schematic diagram of the anti-nuclear pollution clothing of the present invention. DETAILED DESCRIPTION

[0042] The present invention is described in detail below in conjunction with specific embodiments. It is necessary to point out that the following embodiments are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made to the present invention by those skilled in the art based on the contents of the present invention still fall within the scope of protection of the present invention.

[0043] The reinforcing agent 8121 in the embodiment of the present invention is polyimide-based 8121, which is purchased from Shenyang Puli Textile New Materials Co., Ltd.

[0044] Preparation Example 1

[0045] Preparation of double-layer carbon-coated nuclear pollution shielding agent materials:

[0046] 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 (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 temperature of the first calcination is 1000 degrees, and the time of the first calcination is 2.5 hours.

[0047] Step 2) adding the intermediate 1 to boric acid for immersion, taking it out after immersion, and coating it by in-situ polymerization of dopamine 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;

[0048] The method of in-situ polymerization of dopamine is as follows: adding intermediate 1 impregnated with boric acid into deionized water at pH=8.5, adding dopamine hydrochloride, stirring, separating the solid and the liquid, and drying the solid to obtain intermediate 2; the mass ratio of intermediate 1 to dopamine hydrochloride is 0.8:1; and the stirring time is 4 hours.

[0049] Step 3) The intermediate 2 is subjected to 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.

[0050] Preparation Example 2

[0051] Preparation of double-layer carbon-coated nuclear pollution shielding agent materials:

[0052] 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 (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 temperature of the first calcination is 900 degrees, and the time of the first calcination is 3 hours.

[0053] Step 2) adding the intermediate 1 to boric acid for immersion, taking it out after immersion, and coating it by in-situ polymerization of dopamine 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;

[0054] 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 hours.

[0055] Step 3) The intermediate 2 is subjected to 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.

[0056] Example 1

[0057] The preparation method of the material for preventing nuclear pollution is as follows:

[0058] 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, and after mixing, the mixture is loaded into a mold for molding, and the anti-nuclear pollution material is obtained by molding at 285° C. and 22 MPa;

[0059] Wherein, based on the total weight of the triphenyl ether dianhydride thermoplastic polyimide powder and the bismaleimide powder as 100 parts (i.e., the polyimide semi-interpenetrating network resin formed by the two as 100 parts), the addition amount of the triphenyl ether dianhydride thermoplastic polyimide powder is 68 parts; the double-layer carbon-coated nuclear pollution shielding agent prepared in Preparation Example 1 is 20 parts; the reinforcing agent 8121 3 parts;

[0060] The structure of triphenyl ether dianhydride type thermoplastic polyimide is:

[0061] Among them, Ar is

[0062] The structure of bismaleimide is:

[0063]

[0064] The anti-nuclear pollution material of the present invention comprises 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 performance of the anti-nuclear pollution material prepared above is tested, and the specific data are shown in Table 1.

[0065] Example 2

[0066] The preparation method of the material for preventing nuclear pollution is as follows:

[0067] 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, and after mixing, the mixture is loaded into a mold for molding, and the anti-nuclear pollution material is obtained by molding at 288° C. and 23 MPa;

[0068] Among them, based on the total weight of triphenyl ether dianhydride 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 thermoplastic polyimide powder is 72 parts; the double-layer carbon-coated nuclear pollution shielding agent prepared in Preparation Example 1 is 26 parts; and the reinforcing agent is 8121 4 parts.

[0069] The structure of triphenyl ether dianhydride type thermoplastic polyimide is:

[0070] Among them, Ar is

[0071] The structure of bismaleimide is:

[0072]

[0073] The anti-nuclear pollution material of the present invention comprises 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 performance of the anti-nuclear pollution material prepared above is tested, and the specific data are shown in Table 1.

[0074] Example 3

[0075] The preparation method of the material for preventing nuclear pollution is as follows:

[0076] 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, and after mixing, the mixture is loaded into a mold for molding, and the anti-nuclear pollution material is obtained by molding at 285° C. and 22 MPa;

[0077] Wherein, based on the total weight of the triphenyl ether dianhydride thermoplastic polyimide powder and the bismaleimide powder as 100 parts (i.e., the polyimide semi-interpenetrating network resin formed by the two as 100 parts), the addition amount of the triphenyl ether dianhydride 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 8121 is 1 part;

[0078] The structure of triphenyl ether dianhydride type thermoplastic polyimide is:

[0079] Among them, Ar is

[0080] The structure of bismaleimide is:

[0081]

[0082] The anti-nuclear pollution material of the present invention comprises 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 performance of the anti-nuclear pollution material prepared above is tested, and the specific data are shown in Table 1.

[0083] Comparative Example 1

[0084] In the preparation of the double-layer carbon-coated nuclear pollution shielding agent, the preparation method is basically the same as that in Preparation Example 1, except that the in-situ polymerization of dopamine is not performed.

[0085] The preparation method of the anti-nuclear pollution material is the same as that of Example 1. The performance of the anti-nuclear pollution material prepared above was tested, and the specific data are shown in Table 1.

[0086] Comparative Example 2

[0087] The preparation method is basically 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 is tested, and the specific data are shown in Table 1.

[0088] The performance tests were conducted on the nuclear pollution prevention material layers prepared in the examples and comparative examples. The specific results are shown in Table 1.

[0089] Table 1 Performance test data of different anti-nuclear pollution material layers

[0090]

[0091]

[0092] The results in Table 1 show that the anti-nuclear pollution material prepared by the present invention meets the requirements of gamma ray and neutron shielding functions, and has a better nuclear shielding effect. In addition, the anti-nuclear pollution material prepared by the present invention can effectively prevent the biological toxicity of lead powder that falls off from the matrix after aging, and better protect human health.

[0093] It is to be understood that the above embodiments are merely exemplary embodiments used to illustrate the principles of the present invention, but the present invention is not limited thereto. For those of ordinary skill in the art, various modifications and improvements can be made without departing from the spirit and essence of the present invention, and these 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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