Preparation method of polydopamine modified boron carbide-zinc methacrylate coordination reinforced rubber-based radiation protection composite material and polydopamine modified boron carbide-zinc methacrylate coordination reinforced rubber-based radiation protection composite material

Abstract

The invention discloses a preparation method of a polydopamine modified boron carbide-zinc methacrylate coordination reinforced rubber-based radiation protection composite material, and relates to the technical field of radiation protection materials. The method comprises the following steps: dispersing boron carbide in a triaminomethane buffer solution containing dopamine, and carrying out surface polymerization reaction to obtain polydopamine modified boron carbide; and mixing the polydopamine modified boron carbide, zinc methacrylate and a rubber matrix, and vulcanizing to obtain the polydopamine modified boron carbide-zinc methacrylate coordination enhanced (zinc is coordinated with nitrogen / oxygen and the like on the surface of the modified boron carbide) rubber-based radiation protection composite material. Through multiple effects of coordination enhancement, chemical crosslinking and the like, the material has excellent neutron shielding performance and tensile property, the preparation method is simple, the cost is low, and the material has a wide application prospect in the field of nuclear radiation protection.

Description

Technical Field

[0001] The invention relates to the field of radiation shielding materials, in particular to a preparation method and material of a polydopamine modified boron carbide-zinc methacrylate coordination reinforced rubber-based radiation protection composite material. Background Art

[0002] As an energy form that is both economical, efficient, low-carbon and environmentally friendly, nuclear energy has demonstrated its unique value in the fields of national defense, medical care and scientific research. At the same time, the safe use of nuclear energy has attracted much attention, and radiation protection is of vital importance. In order to reduce radiation hazards, enhance protection effectiveness, and ensure that personnel and equipment are protected from harm, high-performance radiation protection materials are essential. Flexible materials are key materials for radiation protection of special-shaped components and personnel, among which rubber-based composite materials are the most studied. The shielding performance and mechanical strength of single rubber raw rubber itself are poor, and various functional fillers (such as shielding functional fillers, reinforcing fillers, etc.) are usually required to enhance the comprehensive performance of rubber. However, due to the low neutron action cross-section of the reinforcing filler and the large amount of addition, the effective content of the shielding functional filler is diluted, resulting in the improvement of its mechanical properties at the expense of the loss of radiation protection performance. Some researchers have prepared hexagonal boron nitride / rubber composites (Radiation Physics and Chemistry, 2021, 180: 109316). In order to ensure the mechanical strength of the composite material, too much reinforcing filler carbon black is added, resulting in a decrease in the mass fraction of the shielding filler, making the shielding effect of the composite material worse. At the same time, some researchers have prepared boron oxide / rubber composites (Radiation Physics and Chemistry, 2017, 131: 7-12) and boron carbide / rubber composites (MRS Communications, 2023, 13: 1449-1454), adding carbon black to improve the tensile strength and tensile modulus of the material. However, since the reinforcing filler and shielding filler are added directly without any treatment, the two cannot have a beneficial effect on each other. When a certain amount of shielding filler is added, it will be poorly distributed in the matrix and affect the performance.

[0003] Patent CN 116574335 A discloses a gamma ray and neutron radiation protection rubber material based on rare earth materials, which uses graphene oxide and boron carbide grafting modification to improve the mechanical properties and shielding properties of the composite protective material. However, its process is relatively complicated and involves two-stage vulcanization, and the main shielding filler gadolinium hydride used is expensive and irritating, which is not friendly to the human body, so it is difficult to promote and apply. Therefore, how to prepare a radiation protection material with high neutron shielding efficiency, strong mechanical properties and good wearing comfort through a simple and easy process is a technical problem that needs to be solved in this field. Summary of the invention

[0004] In view of the above technical problems, the purpose of the present invention is to provide a method for preparing a polydopamine modified boron carbide-zinc methacrylate coordination reinforced rubber-based radiation protection composite material, which is functionalized by coating boron carbide with polydopamine, and the rubber is reinforced with unsaturated carboxylate ZDMA (zinc methacrylate), and the hydroxyl and amino functional groups on ZDMA and functionalized boron carbide can undergo metal ion complexation to achieve coordination and effectively improve the dispersibility of the filler. The functionalized boron carbide-ZDMA coordination reinforced rubber-based radiation protection composite material with a double cross-linked network of metal coordination bonds and chemical bonds is obtained by hot pressing vulcanization, and the material size and thickness can be regulated and industrialized through simple and easy open refining technology and vulcanization process.

[0005] To achieve the above object, the present invention provides the following technical solutions:

[0006] First, the present application provides a method for preparing a polydopamine modified boron carbide-zinc methacrylate coordinated reinforced rubber-based radiation protection composite material, and the specific steps are as follows:

[0007] (1) 1.26 g of tris(hydroxymethyl)aminomethane was added to deionized water and stirred to dissolve completely. A certain amount of dilute hydrochloric acid was added to adjust the pH to 8.5. Deionized water was then added to adjust the volume to 1 L to prepare a 10 mM tris(hydroxymethyl)aminomethane buffer solution.

[0008] Add micron boron carbide powder (particle size 1-5 microns) into tris(hydroxymethylaminomethane) buffer, ultrasonically disperse for 30-60 minutes, and then add dopamine hydrochloride (C8H 11 NO2·HCl), react with stirring at 25-35°C for 24 hours to obtain a mixed liquid; the mixed liquid is vacuum filtered, and the precipitate is washed several times with deionized water until the washing liquid is neutral, and the washed precipitate is taken out and dried at 60°C for 24 hours to obtain polydopamine modified boron carbide.

[0009] This step utilizes dopamine hydrochloride to polymerize in an alkaline tris(hydroxymethyl)aminomethane buffer solution, and forms polydopamine through its self-polymerization. Because polydopamine has strong adhesion, it can adhere to the surface of boron carbide, realize the preparation of polydopamine-modified boron carbide, significantly improve the content of active groups on the surface of modified boron carbide, overcome the problem that the chemical inertness of boron carbide is strong and conventional chemical coupling modification means are difficult to modify. The polydopamine-modified boron carbide obtained in this step has abundant hydroxyl groups (containing O atoms) and amino groups (containing N atoms) adhered to its surface, and the Zn atoms in ZMDA (zinc methacrylate) can form Zn-O and Zn-N coordination bonds with O atoms and N atoms, which is beneficial to improve the dispersibility of boron carbide in composite materials, thereby improving neutron shielding performance; on the other hand, the coordination effect also helps to improve the mechanical properties of the material.

[0010] (2) Plasticizing EPDM, adjusting the roller distance to 0.6 mm, then sequentially adding paraffin oil, polydopamine-modified boron carbide, zinc methacrylate (ZDMA), zinc oxide, stearic acid, di-tert-butyl peroxide isopropylbenzene (BIPB), triallyl isocyanurate (TAIC), and finally making triangle packages 3-5 times, mixing evenly, and then producing sheets; after standing for 24h to 48h, placing the rubber in a hot pressing mold and hot pressing vulcanizing at a temperature of 165 to 175°C, crosslinking it by vulcanization, and obtaining the polydopamine-modified boron carbide-zinc methacrylate coordination reinforced rubber-based radiation protection composite material. In this step, the purpose of standing for 24h to 48h is to restore the rubber material to fatigue, relax the mechanical stress during mixing, and fully mix and disperse the rubber material.

[0011] Preferably, in step 1, the mass ratio of boron carbide to dopamine hydrochloride is 5:1 to 10:1; in the obtained mixed liquid, the concentration of dopamine hydrochloride is 1.8 to 2.3 g / L, and the concentration of boron carbide is 9 to 23 g / L.

[0012] Preferably, in step 2, the thickness of the prepared polydopamine modified boron carbide-zinc methacrylate coordinated reinforced rubber-based radiation protection composite material is 2 to 10 mm.

[0013] Preferably, in step 2, the added EPDM, paraffin oil, polydopamine-modified boron carbide, ZDMA, zinc oxide, stearic acid, BIPB, and TAIC are 100 phr, 10-15 phr, 20-100 phr, 10-30 phr, 5 phr, 1 phr, 1-2 phr, and 0.5-1 phr, respectively, calculated by mass fraction (taking 100 phr by mass fraction of EPDM rubber as the measurement basis).

[0014] Secondly, the present application provides a polydopamine modified boron carbide-zinc methacrylate coordination reinforced rubber-based radiation protection composite material prepared according to the above method.

[0015] Compared with the prior art, the present invention has the following beneficial effects:

[0016] (1) The present application utilizes polydopamine to modify the surface of boron carbide, thereby converting the chemically inert surface of boron carbide into a chemically active surface rich in nitrogen atoms and oxygen atoms, which can coordinate with zinc methacrylate to enhance the coordination between zinc and nitrogen / oxygen on the surface of the modified boron carbide, and enhance the radiation protection performance and mechanical properties of the composite material under the condition of low dosage of zinc methacrylate.

[0017] (2) Zinc methacrylate has the dual functions of coordinating with polydopamine-modified boron carbide and chemically crosslinking with the rubber matrix, which helps to improve the dispersibility of radiation shielding functional fillers and further improve the overall performance of the composite material.

[0018] (3) The filler modification method and composite material preparation method used in this application are simple, the process is easy to scale up, and it is easy to realize the batch preparation of rubber-based radiation protection composite materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 Flow chart for the preparation of polydopamine modified boron carbide-zinc methacrylate coordination reinforced rubber-based radiation protection composites.

[0020] Figure 2 XRD patterns of polydopamine-modified boron carbide and unmodified boron carbide.

[0021] Figure 3 This is the EDS Mapping element distribution diagram of unmodified boron carbide.

[0022] Figure 4 This is the EDS Mapping element distribution diagram of polydopamine modified boron carbide. DETAILED DESCRIPTION

[0023] The present invention is further described below in conjunction with the examples, which include but are not limited to the following examples. The reagents and preparation instruments used in the examples and their manufacturers are as follows:

[0024] Micron boron carbide (B4C, particle size 1-5 microns, Nangong Xindun Alloy Welding Material Spraying Co., Ltd.), EPDM rubber (Jilin Petrochemical Branch of China National Petroleum Corporation, model: J-4045), dopamine hydrochloride (Shanghai McLean Biochemical Technology Co., Ltd.), trihydroxyaminomethane (Shanghai Aladdin Biochemical Technology Co., Ltd.), hydrochloric acid (Nanjing Chemical Reagent Co., Ltd.), zinc methyl propylate (Nanjing Youhao Auxiliary Chemical Co., Ltd.), paraffin oil sunpar2280 (Sun Oil Co., Ltd. of the United States), zinc oxide (Tianjin Hengxing Chemical Reagent Manufacturing Co., Ltd.), stearic acid (Shanghai McLean Biochemical Technology Co., Ltd.), BIPB (di-tert-butyl peroxide isopropylbenzene, Changsha Zhongyi Chemical Co., Ltd.), TAIC (triallyl isocyanurate, Changsha Zhongyi Chemical Co., Ltd.), double-roll open rubber mixer (Yangzhou Yuanfeng Testing Equipment Co., Ltd., model: YF-8018), flat vulcanizer (Yangzhou Derui Instrument Equipment Co., Ltd., model: DRB-50).

[0025] Ultrapure water was prepared using an E2-10TF ultrapure water machine from Nanjing Yeeper E-Tech Technology Development Co., Ltd.

[0026] Example 1

[0027] (1) Preparation of polydopamine-modified boron carbide

[0028] 1.26 g of tris(hydroxymethylaminomethane) was added to 600 ml of deionized water, and the mixture was stirred evenly to completely dissolve. Dilute hydrochloric acid (0.5 mol / L) was added to adjust the pH to 8.5. Finally, deionized water was added to adjust the volume to 1 L to prepare a 10 mM tris(hydroxymethylaminomethane) buffer solution.

[0029] 20 g of micron boron carbide powder was added to 1 L of buffer solution, ultrasonically dispersed (450 W) for 30 min, 2 g of dopamine hydrochloride was added, and the mixture was stirred at 600 rpm for 24 h at room temperature (about 25 ° C) to obtain a mixed liquid; the mixed liquid was vacuum filtered, and the precipitate was washed several times with deionized water until the washing liquid was neutral, and the washed precipitate was taken out and dried at 60 ° C for 24 h to obtain polydopamine modified boron carbide (B4C@PDA).

[0030] (2) Preparation of polydopamine modified boron carbide-zinc methacrylate coordination reinforced rubber-based radiation protection composites

[0031] Take 20g of ethylene propylene diene monomer rubber (EPDM) and plasticize it for 2min at a roller temperature of 35°C, adjust the roller distance to 0.6mm, then add 2g of paraffin oil, 4g of polydopamine modified boron carbide (obtained in step 1), 6g of zinc methacrylate, 1g of zinc oxide, 0.2g of stearic acid, 0.2g of di-tert-butyl peroxide isopropylbenzene (BIPB), and 0.1g of triallyl isocyanurate (TAIC) in sequence, and finally make a triangle package several times, then take out the sheet, and after standing for 24h, place the rubber in a hot pressing mold with a depth of 2mm, and hot press vulcanize it for 15min at 170°C and 15MPa using a flat vulcanizer to obtain a polydopamine modified boron carbide-zinc methacrylate coordination reinforced rubber-based radiation protection composite material with a thickness of 2mm.

[0032] The above preparation process is as follows Figure 1 shown.

[0033] Figure 2 XRD diagram of polydopamine-modified boron carbide (B4C@PDA) prepared in step (1) and raw material boron carbide (unmodified). The diffraction peaks at 19.7°, 22.0°, 23.5°, 31.9°, 34.9°, and 35.9° correspond to the (101), (003), (012), (110), (104), and (021) crystal plane structures of boron carbide, respectively, and are observed before and after modification, indicating that the modification does not change the crystal structure of boron carbide, providing a basis for it to play a neutron shielding function. In addition, the diffraction peak intensity of polydopamine-modified boron carbide is lower than that of unmodified boron carbide, indicating that the surface of boron carbide is successfully coated with polydopamine.

[0034] Figure 3The EDS Mapping element distribution diagram of boron carbide (unmodified). Among them, (1) is the SEM image of boron carbide, (2)-(4) are the EDS Mapping images of B element, C element and O element obtained by element scanning of the SEM image; Figure 3 The B and C elements can be clearly identified, and there is almost no O element (the trace amount of O element comes from a small amount of hydroxyl groups remaining on the surface during the production process).

[0035] Figure 4 The EDS Mapping element distribution diagram of polydopamine modified boron carbide. Among them, (1) is the SEM image of polydopamine modified boron carbide, (2)-(4) are the EDS Mapping images of B element, C element and O element obtained by element scanning of the SEM image. Figure 4 It can be seen that the B element, C element, and O element (derived from the large amount of oxygen contained in polydopamine) can be clearly identified and evenly distributed, which can further prove that boron carbide has been successfully modified.

[0036] Example 2

[0037] Preparation of polydopamine modified boron carbide-zinc methacrylate coordination reinforced rubber-based radiation protection composites

[0038] Take 20g of ethylene propylene diene monomer rubber (EPDM) and plasticize it for 2min at a roller temperature of 35°C, adjust the roller distance to 0.6mm, and then add 2g of paraffin oil, 8g of polydopamine-modified boron carbide (the preparation method is the same as step 1 in Example 1), 6g of zinc methacrylate, 1g of zinc oxide, 0.2g of stearic acid, 0.2g of di-tert-butyl peroxide isopropylbenzene (BIPB), and 0.1g of TAIC in sequence, and finally make a triangle package several times, then take out the sheet, and after standing for 24h, place the rubber in a hot pressing mold with a depth of 2mm, and hot press vulcanize it for 15min at 170°C and 15MPa using a flat vulcanizer to obtain a flexible neutron protection composite material with a thickness of 2mm.

[0039] Example 3

[0040] Preparation of polydopamine modified boron carbide-zinc methacrylate coordination reinforced rubber-based radiation protection composites

[0041] Take 20g of ethylene propylene diene monomer rubber (EPDM) and plasticize it for 2min at a roller temperature of 35°C, adjust the roller distance to 0.6mm, then add 2g of paraffin oil, 12g of polydopamine modified boron carbide (preparation method is the same as step 1 in Example 1), 6g of zinc methacrylate, 1g of zinc oxide, 0.2g of stearic acid, 0.2g of di-tert-butyl peroxide isopropylbenzene (BIPB), and 0.1g of triallyl isocyanurate (TAIC) in sequence, and finally make a triangle package several times, then take out the sheet, and after standing for 24h, place the rubber in a hot pressing mold with a depth of 2mm, and hot press vulcanize it for 15min at 170°C and 15MPa using a flat vulcanizer to obtain a polydopamine modified boron carbide-zinc methacrylate coordination reinforced rubber-based radiation protection composite material with a thickness of 2mm.

[0042] Example 4

[0043] Preparation of polydopamine modified boron carbide-zinc methacrylate coordination reinforced rubber-based radiation protection composites

[0044] Take 20g of ethylene propylene diene monomer rubber (EPDM) and plasticize it for 2min at a roller temperature of 35°C, adjust the roller distance to 0.6mm, then add 2g of paraffin oil, 16g of polydopamine modified boron carbide (preparation method is the same as step 1 in Example 1), 6g of zinc methacrylate, 1g of zinc oxide, 0.2g of stearic acid, 0.2g of di-tert-butyl peroxide isopropylbenzene (BIPB), and 0.1g of triallyl isocyanurate (TAIC) in sequence, and finally make a triangle package several times, then take out the sheet, and after standing for 24h, place the rubber in a hot pressing mold with a depth of 2mm, and hot press vulcanize it for 15min at 170°C and 15MPa using a flat vulcanizer to obtain a polydopamine modified boron carbide-zinc methacrylate coordination reinforced rubber-based radiation protection composite material with a thickness of 2mm.

[0045] Example 5

[0046] Preparation of polydopamine modified boron carbide-zinc methacrylate coordination reinforced rubber-based radiation protection composites

[0047] Take 20g of ethylene propylene diene monomer rubber (EPDM) and plasticize it for 2min at a roller temperature of 35°C, adjust the roller distance to 0.6mm, then add 2g of paraffin oil, 20g of polydopamine modified boron carbide (preparation method is the same as step 1 in Example 1), 6g of zinc methacrylate, 1g of zinc oxide, 0.2g of stearic acid, 0.2g of di-tert-butyl peroxide isopropylbenzene (BIPB), and 0.1g of triallyl isocyanurate (TAIC) in sequence, and finally make a triangle package several times, then take out the sheet, and after standing for 24h, place the rubber in a hot pressing mold with a depth of 2mm, and hot press vulcanize it for 15min at 170°C and 15MPa using a flat vulcanizer to obtain a polydopamine modified boron carbide-zinc methacrylate coordination reinforced rubber-based radiation protection composite material with a thickness of 2mm.

[0048] Comparative Example 1

[0049] Take 20g of ethylene propylene diene monomer rubber (EPDM) and plasticize it for 2min at a roller temperature of 35℃, adjust the roller distance to 0.6mm, then add 2g of paraffin oil, 4g of micron boron carbide powder, 6g of zinc methacrylate, 1g of zinc oxide, 0.2g of stearic acid, 0.2g of di-tert-butyl peroxide isopropylbenzene (BIPB), and 0.1g of triallyl isocyanurate (TAIC) in sequence, finally make a triangle package several times, then take the sheet off and let it stand for 24h; place the rubber in a hot pressing mold with a depth of 2mm, and use a flat vulcanizer for hot pressing and vulcanization for 15min at 170℃ and 15MPa to obtain a flexible composite material with a thickness of 2mm.

[0050] Comparative Example 2

[0051] Take 20g of ethylene propylene diene monomer rubber (EPDM) and plasticize it for 2min at a roller temperature of 35℃, adjust the roller distance to 0.6mm, then add 2g of paraffin oil, 8g of micron boron carbide powder, 6g of zinc methacrylate, 1g of zinc oxide, 0.2g of stearic acid, 0.2g of di-tert-butyl peroxide isopropylbenzene (BIPB), and 0.1g of triallyl isocyanurate (TAIC) in sequence, finally make a triangle package several times, then take the sheet off and let it stand for 24h; place the rubber in a hot pressing mold with a depth of 2mm, and use a flat vulcanizer for hot pressing and vulcanization for 15min at 170℃ and 15MPa to obtain a flexible composite material with a thickness of 2mm.

[0052] Comparative Example 3

[0053] Take 20g of ethylene propylene diene monomer rubber (EPDM) and plasticize it for 2min at a roller temperature of 35℃, adjust the roller distance to 0.6mm, then add 2g of paraffin oil, 12g of micron boron carbide powder, 6g of zinc methacrylate, 1g of zinc oxide, 0.2g of stearic acid, 0.2g of di-tert-butyl peroxide isopropylbenzene (BIPB), and 0.1g of triallyl isocyanurate (TAIC) in sequence, finally make a triangle package several times, then take the sheet off and let it stand for 24h; place the rubber in a hot pressing mold with a depth of 2mm, and use a flat vulcanizer for hot pressing and vulcanization for 15min at 170℃ and 15MPa to obtain a flexible composite material with a thickness of 2mm.

[0054] Comparative Example 4

[0055] Take 20g of ethylene propylene diene monomer rubber (EPDM) and plasticize it for 2min at a roller temperature of 35℃, adjust the roller distance to 0.6mm, then add 2g of paraffin oil, 16g of micron boron carbide powder, 6g of zinc methacrylate, 1g of zinc oxide, 0.2g of stearic acid, 0.2g of di-tert-butyl peroxide isopropylbenzene (BIPB), and 0.1g of triallyl isocyanurate (TAIC) in sequence, finally make a triangle package several times, then take the sheet off and let it stand for 24h; place the rubber in a hot pressing mold with a depth of 2mm, and hot-press and vulcanize it for 15min at 170℃ and 15MPa using a flat vulcanizer to obtain a flexible composite material with a thickness of 2mm.

[0056] Comparative Example 5

[0057] Take 20g of ethylene propylene diene monomer rubber (EPDM) and plasticize it for 2min at a roller temperature of 35℃, adjust the roller distance to 0.6mm, then add 2g of paraffin oil, 20g of micron boron carbide powder, 6g of zinc methacrylate, 1g of zinc oxide, 0.2g of stearic acid, 0.2g of di-tert-butyl peroxide isopropylbenzene (BIPB), and 0.1g of triallyl isocyanurate (TAIC) in sequence, finally make a triangle package several times, then take the sheet off and let it stand for 24h; place the rubber in a hot pressing mold with a depth of 2mm, and use a flat vulcanizer for hot pressing and vulcanization for 15min at 170℃ and 15MPa to obtain a flexible composite material with a thickness of 2mm.

[0058] The mechanical properties and neutron shielding properties of the composite materials prepared in Examples 1 to 5 and Comparative Examples 1 to 5 were tested. The tensile properties were tested according to the standard GB / T 528-2009, and the neutron shielding properties of the materials were tested using an Am-Be neutron source (moderated) and a He-3 detector. The test results are shown in Table 1 below.

[0059] Table 1 Test results of tensile properties and neutron shielding properties of composite materials

[0060]

[0061]

[0062] Table 1 is a comparison of the tensile properties and neutron shielding properties of the composite materials obtained in Examples 1 to 5 and Comparative Examples 1 to 5. Since the polydopamine-modified boron carbide contains -OH and -NH2 functional groups, after zinc methacrylate is added to the rubber, the zinc ions therein will form Zn-O and Zn-N metal coordination bonds with these functional groups. At the same time, since the unsaturated carboxylate undergoes a "dissolution-diffusion-polymerization-phase separation" reaction process inside the rubber, the dispersibility of the modified boron carbide in the rubber is improved under the condition of continuous phase separation of polymethacrylate zinc. Under the condition of the same amount of boron carbide and ZDMA, the tensile strength, elongation at break and thermal neutron shielding properties of the composite materials obtained in Examples 1 to 5 are all better than those of Comparative Examples 1 to 5, indicating that the use of polydopamine to modify the boron carbide can coordinately enhance the tensile properties and neutron shielding properties of the composite material when the unsaturated carboxylate ZDMA is added at the same time.

Claims

1. A method for preparing a polydopamine modified boron carbide-zinc methacrylate coordinated reinforced rubber-based radiation protection composite material, characterized in that: The specific steps are as follows: 1) Adding boron carbide and dopamine hydrochloride to tris(hydroxymethylaminomethane) buffer in sequence, stirring for reaction, and obtaining a mixed liquid; then vacuum filtering, washing and drying the precipitate, and obtaining polydopamine-modified boron carbide; 2) The EPDM rubber is plasticized, and then paraffin oil, polydopamine-modified boron carbide, zinc methacrylate, zinc oxide, stearic acid, di-tert-butyl peroxide isopropylbenzene, and triallyl isocyanurate are added in sequence, mixed evenly, and allowed to stand for 24 hours; then hot-pressed and vulcanized at 165-175° C. to obtain the polydopamine-modified boron carbide-zinc methacrylate coordination reinforced rubber-based radiation protection composite material.

2. The method according to claim 1, characterized in that Step 1) The concentration of the Tris buffer is 10 mM.

3. The method according to claim 1, characterized in that In step 1), the mass ratio of boron carbide to dopamine hydrochloride is 5:1 to 10:

1.

4. The method according to claim 1, characterized in that: In the mixed liquid in step 1), the concentration of dopamine hydrochloride is 1.8-2.3 g / L.

5. The method according to claim 1, characterized in that In step 2), the added EPDM rubber is plasticized, and then paraffin oil, polydopamine-modified boron carbide, zinc methacrylate, zinc oxide, stearic acid, di-tert-butyl peroxide isopropylbenzene, and triallyl isocyanurate are added in proportions of 100phr, 10-15phr, 20-100phr, 10-30phr, 5phr, 1phr, 1-2phr, and 0.5-1phr, respectively, by mass.

6. The method according to claim 1, characterized in that In step 2), the vulcanization time is 15-20 min, and the vulcanization pressure is 13-16 MPa.

7. The method according to claim 1, characterized in that In step 2), the thickness of the composite material is 2-10 mm.

8. The polydopamine modified boron carbide-zinc methacrylate coordinated reinforced rubber-based radiation protection composite material prepared by any method of claims 1-7.

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