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

Abstract

The application discloses a preparation method of a polydopamine modified boron carbide-zinc methacrylate coordination enhanced 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 trisaminomethane buffer containing dopamine, and obtaining polydopamine modified boron carbide through a surface polymerization reaction; and then mixing the polydopamine modified boron carbide, zinc methacrylate and a rubber matrix, and vulcanizing to obtain a polydopamine modified boron carbide-zinc methacrylate coordination enhanced (zinc and nitrogen / oxygen on the surface of the modified boron carbide are coordinated) rubber-based radiation protection composite material; through multiple actions such as coordination enhancement and chemical crosslinking, the material has excellent neutron shielding performance and tensile performance, 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] This invention relates to the field of radiation shielding materials, and in particular to the preparation method and materials of polydopamine-modified boron carbide-zinc methacrylate coordination-reinforced rubber-based radiation protection composite materials. Background Technology

[0002] Nuclear energy, as an economical, efficient, low-carbon, and environmentally friendly energy source, demonstrates its unique value in defense, medical, and scientific research fields. Meanwhile, the safe use of nuclear energy is of paramount concern, making radiation protection crucial. To reduce radiation hazards, enhance protective effectiveness, and ensure the safety of personnel and equipment, high-performance radiation protection materials are essential. Flexible materials are key materials for radiation protection of irregularly shaped components and personnel, with rubber-based composites being the most researched. Raw rubber itself has poor shielding performance and mechanical strength, typically requiring the addition of various functional fillers (such as shielding fillers and reinforcing fillers) to enhance its overall performance. However, due to the low neutron interaction cross-section and large addition amount of reinforcing fillers, the effective content of the shielding filler is diluted, resulting in improved mechanical properties at the expense of radiation protection performance. Researchers have prepared hexagonal boron nitride / rubber composites (Radiation Physics and Chemistry, 2021, 180:109316). However, in order to ensure the mechanical strength of the composite material, excessive amounts of reinforcing filler carbon black were added, leading to a decrease in the mass fraction of the shielding filler and a deterioration in the shielding effect of the composite material. Meanwhile, 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 improves the tensile strength and tensile modulus of the materials. However, since the reinforcing filler and the shielding filler are added directly without any treatment, they cannot produce a beneficial effect on each other. When the shielding filler is added in a certain amount, it will be poorly distributed in the matrix and affect the performance.

[0003] Patent CN 116574335 A discloses a gamma-ray and neutron radiation shielding rubber material based on rare-earth materials. It employs graphene oxide and boron carbide graft modification to improve the mechanical and shielding properties of the composite shielding material. However, its process is complex, involving two-stage vulcanization, and the main shielding filler, gadolinium hydride, is expensive, irritating, and unfriendly to the human body, thus hindering its widespread application. Therefore, how to prepare a radiation shielding material with high neutron shielding effectiveness, strong mechanical properties, and good wearing comfort through a simple and easy-to-implement process is a pressing technical challenge in this field. Summary of the Invention

[0004] To address the aforementioned technical problems, the present invention aims to provide a method for preparing a polydopamine-modified boron carbide-zinc methacrylate coordination-reinforced rubber-based radiation protection composite material. This method involves functionalizing boron carbide by coating it with polydopamine, and reinforcing the rubber with unsaturated carboxylate ZDMA (zinc methacrylate). The hydroxyl and amino functional groups on ZDMA and functionalized boron carbide can undergo metal ion complexation, achieving coordination and effectively improving the dispersibility of the filler. Hot-press vulcanization yields a functionalized boron carbide-ZDMA coordination-reinforced rubber-based radiation protection composite material with a dual crosslinked network of metal coordination bonds and chemical bonds. The simple and easy-to-implement open-milling technology and vulcanization process allow for the control of material size and thickness, as well as industrial-scale production.

[0005] To achieve the above objectives, the present invention provides the following technical solution:

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

[0007] (1) Add 1.26g of trihydroxymethylaminomethane to deionized water, stir until completely dissolved, add a certain amount of dilute hydrochloric acid to adjust the pH to 8.5, and then add deionized water to make up to 1L to prepare a 10mM trihydroxymethylaminomethane buffer solution.

[0008] Add micron-sized boron carbide powder (particle size 1-5 microns) to tris(hydroxymethyl)aminomethane buffer and sonicate for 30-60 minutes. Then add dopamine hydrochloride (C8H2O). 11 NO2·HCl) was stirred and reacted at 25-35℃ for 24 hours 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. The washed precipitate was then dried at 60℃ for 24 hours to obtain polydopamine-modified boron carbide.

[0009] This step utilizes the polymerization reaction of dopamine hydrochloride in an alkaline tris(hydroxymethyl)aminomethane buffer solution to form polydopamine through self-polymerization. Due to the strong adhesiveness of polydopamine, it can adhere to the surface of boron carbide, thus achieving the preparation of polydopamine-modified boron carbide. This significantly increases the content of active groups on the surface of the modified boron carbide, overcoming the problem that boron carbide is chemically inert and difficult to modify using conventional chemical coupling methods. The polydopamine-modified boron carbide obtained in this step has abundant hydroxyl groups (containing O atoms) and amino groups (containing N atoms) on its surface. The Zn atoms in ZMDA (zinc methacrylate) can form Zn-O and Zn-N coordination bonds with O and N atoms, which is beneficial to improving the dispersibility of boron carbide in the composite material, thereby enhancing neutron shielding performance. On the other hand, the coordination effect also helps to improve the mechanical properties of the material.

[0010] (2) Pulverize ethylene propylene diene monomer (EPDM) rubber, adjust the roller gap to 0.6 mm, and then add paraffin oil, polydopamine-modified boron carbide, zinc methacrylate (ZDMA), zinc oxide, stearic acid, bis(tert-butylperoxyisopropylbenzene) (BIPB), and triallyl isocyanurate (TAIC) in sequence. Finally, mix in a triangular shape 3-5 times until uniform, and then sheet it out. After standing for 24-48 hours, place the rubber in a hot press mold and hot press vulcanize it at 165-175°C. Through vulcanization, it crosslinks to obtain the polydopamine-modified boron carbide-zinc methacrylate coordination-reinforced rubber-based radiation protection composite material. In this step, the purpose of standing for 24-48 hours is to allow the rubber compound to recover from fatigue, relax the mechanical stress during mixing, and ensure that the rubber compound is fully mixed and dispersed.

[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 polydopamine-modified boron carbide-zinc methacrylate coordination-reinforced rubber-based radiation protection composite material is 2–10 mm.

[0013] Preferably, in step 2, the amounts of EPDM, paraffin oil, polydopamine-modified boron carbide, ZDMA, zinc oxide, stearic acid, BIPB, and TAIC added 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, based on mass parts (using 100 phr of EPDM rubber as the measurement standard).

[0014] Secondly, this 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) This application utilizes polydopamine to modify the surface of boron carbide, transforming the chemically inert boron carbide surface into a chemically active surface rich in nitrogen and oxygen atoms. This surface can coordinate with zinc methacrylate, enhancing the coordination of zinc with nitrogen / oxygen on the modified boron carbide surface. Under the condition of low zinc methacrylate dosage, the radiation protection performance and mechanical properties of the composite material are enhanced.

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

[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 mass production of rubber-based radiation protection composite materials. Attached Figure Description

[0019] Figure 1 Flowchart for the preparation of polydopamine-modified boron carbide-zinc methacrylate coordination-reinforced rubber-based radiation protection composite material.

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

[0021] Figure 3 This is an EDS mapping of the elemental distribution of unmodified boron carbide.

[0022] Figure 4 This is an EDS mapping of elemental distribution of polydopamine-modified boron carbide. Detailed Implementation

[0023] The present invention will be further described below with reference to the embodiments, which include, but are not limited to, the following embodiments. The reagents, preparation instruments, and manufacturers used in the embodiments are as follows:

[0024] Micron-sized boron carbide (B4C, particle size 1-5 microns, Nangong Xindun Alloy Welding Material Spraying Co., Ltd.), EPDM rubber (China National Petroleum Corporation Jilin Petrochemical Branch, model: J-4045), dopamine hydrochloride (Shanghai Maclean Biochemical Technology Co., Ltd.), trihydroxyaminomethane (Shanghai Aladdin Biochemical Technology Co., Ltd.), hydrochloric acid (Nanjing Chemical Reagent Co., Ltd.), zinc methylpropionate (Nanjing Youhao Additives Chemical Co., Ltd.), paraffin oil Sunpar 2280 (American Sun Petroleum Co., Ltd.), zinc oxide (Tianjin Hengxing Chemical Reagent Manufacturing Co., Ltd.), stearic acid (Shanghai Maclean Biochemical Technology Co., Ltd.), BIPB (di-tert-butyl peroxide isopropylbenzene, Changsha Zhongyi Chemical Co., Ltd.), TAIC (traceryl isocyanate, Changsha Zhongyi Chemical Co., Ltd.), two-roll open mixing mill (Yangzhou Yuanfeng Testing Equipment Co., Ltd., model: YF-8018), flat vulcanizing mill (Yangzhou Derui Instrument Equipment Co., Ltd., model: DRB-50).

[0025] Ultrapure water was prepared using an E2-10TF ultrapure water system from Nanjing Yipu Yida Technology Development Co., Ltd.

[0026] Example 1

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

[0028] Add 1.26g of trihydroxymethylaminomethane to 600ml of deionized water, stir until completely dissolved, add dilute hydrochloric acid (0.5mol / L) to adjust the pH to 8.5, and finally add deionized water to make up to 1L to prepare a 10mM trihydroxymethylaminomethane buffer solution.

[0029] 20g of micron-sized boron carbide powder was added to 1L of buffer solution and dispersed by sonication (450W) for 30min. 2g of dopamine hydrochloride was added, and the mixture was stirred at 600rpm for 24h at room temperature (about 25℃) 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. The washed precipitate was dried in a forced-air dryer at 60℃ for 24h to obtain polydopamine-modified boron carbide (B4C@PDA).

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

[0031] Take 20g of ethylene propylene diene monomer (EPDM) rubber and plasticize it for 2 minutes at a roller temperature of 35℃. Adjust the roller gap 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 isocyanate (TAIC). Finally, make triangular wraps several times, then sheet it out. After standing for 24 hours, place the rubber in a hot press mold with a depth of 2mm and hot press it at 170℃ and 15MPa for 15 minutes using a flat vulcanizing machine to obtain polydopamine-modified boron carbide-zinc methacrylate coordination-reinforced rubber-based radiation protection composite material with a thickness of 2mm.

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

[0033] Figure 2 The XRD patterns are shown for the polydopamine-modified boron carbide (B4C@PDA) prepared in step (1) and the raw 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 planes of boron carbide, respectively. These peaks were observed both before and after modification, indicating that the modification did not alter the crystal structure of boron carbide, thus providing a basis for its neutron shielding function. Furthermore, the diffraction peak intensity of the polydopamine-modified boron carbide was lower than that of the unmodified boron carbide, indicating that the surface of boron carbide was successfully coated with polydopamine.

[0034] Figure 3This is an EDS mapping of the elemental distribution of boron carbide (unmodified). (1) is the SEM image of boron carbide, and (2)-(4) are EDS mappings of elements B, C, and O obtained by elemental scanning of the SEM image. Figure 3 B and C elements can be clearly identified, while O element is almost completely absent (the trace O element originates from a small amount of hydroxyl groups remaining on its surface during the production process).

[0035] Figure 4 This is an EDS mapping of elemental distribution of polydopamine-modified boron carbide. Specifically, (1) is the SEM image of polydopamine-modified boron carbide, and (2)-(4) are EDS mapping images of elements B, C, and O obtained by elemental scanning of the SEM image. Figure 4 It is evident that elements B, C, and O (derived from the abundant oxygen in polydopamine) can be clearly identified and are evenly distributed, further proving 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 composite materials

[0038] Take 20g of ethylene propylene diene monomer (EPDM) rubber and plasticize it for 2 minutes at a roller temperature of 35℃. Adjust the roller gap to 0.6mm, then add 2g of paraffin oil, 8g 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 TAIC in sequence. Finally, make triangular wraps several times, then sheet it out. After standing for 24 hours, place the rubber in a hot press mold with a depth of 2mm and hot press it at 170℃ and 15MPa for 15 minutes using a flat vulcanizing machine 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 composite materials

[0041] Take 20g of ethylene propylene diene monomer (EPDM) rubber and plasticize it for 2 minutes at a roller temperature of 35℃. Adjust the roller gap 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 isocyanate (TAIC). Finally, make triangular wraps several times, then sheet it out. After standing for 24 hours, place the rubber in a hot press mold with a depth of 2mm and hot press it at 170℃ and 15MPa for 15 minutes using a flat vulcanizing machine to obtain 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 composite materials

[0044] Take 20g of ethylene propylene diene monomer (EPDM) rubber and plasticize it for 2 minutes at a roller temperature of 35℃. Adjust the roller gap 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 isocyanate (TAIC). Finally, make triangular wraps several times, then sheet it out. After standing for 24 hours, place the rubber in a hot press mold with a depth of 2mm and hot press it at 170℃ and 15MPa for 15 minutes using a flat vulcanizing machine to obtain 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 composite materials

[0047] Take 20g of ethylene propylene diene monomer (EPDM) rubber and plasticize it for 2 minutes at a roller temperature of 35℃. Adjust the roller gap 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 isocyanate (TAIC). Finally, make triangular wraps several times, then sheet it out. After standing for 24 hours, place the rubber in a hot press mold with a depth of 2mm and hot press it at 170℃ and 15MPa for 15 minutes using a flat vulcanizing machine to obtain 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 (EPDM) rubber and plasticize it for 2 minutes at a roller temperature of 35℃. Adjust the roller gap 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 peroxyisopropylbenzene (BIPB), and 0.1g of triallyl isocyanate (TAIC) in sequence. Finally, make triangular wraps several times, then sheet it and let it stand for 24 hours. Place the rubber in a hot press mold with a depth of 2mm and hot press it at 170℃ and 15MPa for 15 minutes using a flat vulcanizing machine to obtain a flexible composite material with a thickness of 2mm.

[0050] Comparative Example 2

[0051] Take 20g of ethylene propylene diene monomer (EPDM) rubber and plasticize it for 2 minutes at a roller temperature of 35℃. Adjust the roller gap 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 peroxyisopropylbenzene (BIPB), and 0.1g of triallyl isocyanate (TAIC) in sequence. Finally, make triangular wraps several times, then sheet the rubber and let it stand for 24 hours. Place the rubber in a hot press mold with a depth of 2mm and hot press it at 170℃ and 15MPa for 15 minutes using a flat vulcanizing machine to obtain a flexible composite material with a thickness of 2mm.

[0052] Comparative Example 3

[0053] Take 20g of ethylene propylene diene monomer (EPDM) rubber and plasticize it for 2 minutes at a roller temperature of 35℃. Adjust the roller gap 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 peroxyisopropylbenzene (BIPB), and 0.1g of triallyl isocyanate (TAIC) in sequence. Finally, make triangular wraps several times, then sheet it and let it stand for 24 hours. Place the rubber in a hot press mold with a depth of 2mm and hot press it at 170℃ and 15MPa for 15 minutes using a flat vulcanizing machine to obtain a flexible composite material with a thickness of 2mm.

[0054] Comparative Example 4

[0055] Take 20g of ethylene propylene diene monomer (EPDM) rubber and plasticize it for 2 minutes at a roller temperature of 35℃. Adjust the roller gap 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 peroxyisopropylbenzene (BIPB), and 0.1g of triallyl isocyanate (TAIC) in sequence. Finally, make triangular wraps several times, then sheet it and let it stand for 24 hours. Place the rubber in a hot press mold with a depth of 2mm and hot press it at 170℃ and 15MPa for 15 minutes using a flat vulcanizing machine to obtain a flexible composite material with a thickness of 2mm.

[0056] Comparative Example 5

[0057] Take 20g of ethylene propylene diene monomer (EPDM) rubber and plasticize it for 2 minutes at a roller temperature of 35℃. Adjust the roller gap 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 peroxyisopropylbenzene (BIPB), and 0.1g of triallyl isocyanate (TAIC) in sequence. Finally, make triangular wraps several times, then sheet the rubber and let it stand for 24 hours. Place the rubber in a hot press mold with a depth of 2mm and hot press it at 170℃ and 15MPa for 15 minutes using a flat vulcanizing machine to obtain a flexible composite material with a thickness of 2mm.

[0058] The mechanical properties and neutron shielding performance of the composite materials prepared in Examples 1-5 and Comparative Examples 1-5 were tested. Tensile properties were tested according to standard GB / T 528-2009, and the neutron shielding performance of the materials was 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 performance of composite materials.

[0060]

[0061]

[0062] Table 1 compares the tensile properties and neutron shielding performance of the composite materials obtained in Examples 1-5 and Comparative Examples 1-5. Since polydopamine-modified boron carbide contains -OH and -NH2 functional groups, after zinc methacrylate is added to the rubber, zinc ions form Zn-O and Zn-N metal coordination bonds with these functional groups. Simultaneously, due to the "dissolution-diffusion-polymerization-phase separation" reaction process of the unsaturated carboxylate within the rubber, the dispersibility of modified boron carbide in the rubber is improved under the continuous phase separation of polymethacrylate. With the same amount of boron carbide and ZDMA, the tensile strength, elongation at break, and thermal neutron shielding performance of the composite materials obtained in Examples 1-5 are all superior to those in Comparative Examples 1-5, indicating that modifying boron carbide with polydopamine, while simultaneously adding the unsaturated carboxylate ZDMA, can coordinate and enhance the tensile properties and neutron shielding performance of the composite material.

Claims

1. A method for preparing a polydopamine modified boron carbide-zinc methacrylate coordination enhanced rubber based radiation shielding composite material, characterized in that, The specific steps are as follows: 1) sequentially adding micron boron carbide powder and dopamine hydrochloride into a tris-hydroxymethyl aminomethane buffer solution, stirring and reacting to obtain a mixed liquid; then vacuum filtering, washing and drying the precipitate to obtain polydopamine modified boron carbide; 2) plasticizing the ethylene-propylene-diene rubber, then sequentially adding paraffin oil, polydopamine modified boron carbide, zinc methacrylate, zinc oxide, stearic acid, di-tert-butyl peroxide isopropyl benzene and triallyl isocyanurate, uniformly mixing and then standing for 24 hours; then hot pressing and vulcanizing at 165-175°C to obtain the polydopamine modified boron carbide-zinc methacrylate coordination enhanced rubber-based radiation protection composite material; the proportions of the added ethylene-propylene-diene rubber, paraffin oil, polydopamine modified boron carbide, zinc methacrylate, zinc oxide, stearic acid, di-tert-butyl peroxide isopropyl benzene and triallyl isocyanurate 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.

2. The method of claim 1, wherein, In step 1), the tris-hydroxymethyl aminomethane buffer solution has a concentration of 10 mM.

3. The method of claim 1, wherein, In step 1), the mass ratio of boron carbide to dopamine hydrochloride is 5:1-10:

1.

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

5. The method of claim 1, wherein, In step 2), the vulcanization time is 15-20 min and the vulcanization pressure is 13-16 MPa.

6. The method of claim 1, wherein, In step 2), the thickness of the composite material is 2-10 mm.

7. The polydopamine modified boron carbide-zinc methacrylate coordination enhanced rubber-based radiation protection composite material prepared by any one of the methods of claims 1-6.

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