Multipurpose anti-radiation material and preparation method thereof

Abstract

The invention discloses a multi-purpose anti-radiation material and a preparation method thereof, and relates to the technical field of anti-radiation materials, the multi-purpose anti-radiation material comprises the following raw materials by weight: 30-50 parts of gadolinium polymethacrylate, 25-40 parts of a multi-element hybrid filler, 40-70 parts of chloroprene rubber, and 50-80 parts of paraffin. According to the multi-purpose anti-radiation material and the preparation method thereof, in the preparation process of gadolinium polymethacrylate, molecular chains are connected through covalent bonds to form a stable three-dimensional network structure, so that the chemical stability is improved, the stability of the anti-radiation material is improved, the service life of the anti-radiation material is prolonged, gadolinium ions are uniformly distributed in polymer chains, and the anti-radiation effect is improved. The effective concentration and the distribution uniformity of gadolinium ions are increased, so that the anti-radiation effect of the material is improved, meanwhile, the molecular chain structure of the polymer can also generate a synergistic effect with the gadolinium ions, and the absorption capacity to rays is further enhanced.

Description

Technical Field

[0001] The invention relates to the technical field of radiation protection materials, in particular to a multi-purpose radiation protection material and a preparation method thereof. Background Art

[0002] Referring to a Chinese patent for a radiation-proof composite material (Announcement No.: CN103275417B), it is mainly prepared from 60-68 parts by weight of radiation-proof filler and 32-40 parts by weight of matrix. The processing of the radiation-proof composite material does not require vulcanization, wherein the radiation-proof filler includes the following three components mixed in any ratio: a single rare earth oxide and / or its salt, tungsten oxide, antimony oxide, and the matrix is ​​selected from polyvinyl chloride or EPDM; the invention uses rubber or polyvinyl chloride as raw materials, and adopts lead-free radiation-proof filler, and uses a melt processing method that does not require vulcanization to make a radiation-proof composite material with the same or better performance as the existing vulcanization process radiation-proof lead rubber. Since its processing and preparation process does not require vulcanization, it is more environmentally friendly. In the preparation process of the above-mentioned radiation-proof material, it is easy to have uneven distribution of fillers, thereby affecting the radiation-proof performance of the material; for this reason, the present invention proposes a multi-purpose radiation-proof material and a preparation method thereof to solve the above-mentioned problems. Summary of the invention 1. Technical issues to be resolved In view of the deficiencies in the prior art, the present invention provides a multi-purpose radiation protection material and a preparation method thereof, which solves the problems mentioned in the above background technology.

[0003] (II) Technical solution To achieve the above objectives, the present invention is implemented through the following technical scheme: a multi-purpose radiation protection material, comprising the following raw materials in parts by weight: 30-50 parts of polygadolinium methacrylate, 25-40 parts of multi-component hybrid filler, 40-70 parts of chloroprene rubber, and 50-80 parts of paraffin.

[0004] A method for preparing a multi-purpose radiation protection material comprises the following preparation steps: Step 1, dissolving gadolinium methacrylate in deionized water at 70-80° C., then filtering, dropping ammonium sulfate, stirring and reacting for 2 hours, and drying the product to constant weight to obtain polygadolinium methacrylate; Step 2: Pour the boron carbide / dopamine complex and polyethylene glycol into a mixed solution of ferric chloride hexahydrate and ethylene glycol, perform ultrasonic treatment for 25-40 minutes, then add sodium acetate, heat to 55-65° C., stir to react for 2-2.5 hours, cool to room temperature, centrifuge, wash, and dry to obtain a multi-component hybrid filler; Step 3, pour poly(gadolinium methacrylate), multi-component hybrid filler, chloroprene rubber and paraffin into a high-speed blender, and mix at 50-70° C. for 30-40 minutes; Step 4: Extruding the mixed raw materials through a twin-screw extruder to granulate them to produce a multi-purpose radiation protection material Preferably, in the step 1, the mass of ammonium sulfate is 5%-8% of the mass of gadolinium methacrylate; the preparation method of gadolinium methacrylate is: add methacrylic acid and deionized water into a reaction bottle, then slowly add gadolinium hydroxide, heat the oil bath to 70-80°C, stir and react for 6-8h, filter while hot, distill the filtrate under reduced pressure, then add anhydrous ethanol, continue distillation under reduced pressure, cool to room temperature, stand, filter, and dry to constant weight to obtain gadolinium methacrylate.

[0005] Preferably, the mass of the methacrylic acid is 90%-96% of the mass of the gadolinium hydroxide.

[0006] Preferably, in step 2, the preparation method of the boron carbide / dopamine complex is: pouring boron carbide powder into a mixed solution of Tris buffer and anhydrous ethanol, stirring for 5-10 minutes, adding dopamine hydrochloride, stirring and reacting at room temperature for 5-7 hours, and centrifuging, washing and drying after the reaction is completed to obtain the boron carbide / dopamine complex.

[0007] Preferably, the volume ratio of the Tris buffer to anhydrous ethanol is 3-3.5:1; and the mass of the dopamine hydrochloride is 35%-45% of the mass of the boron carbide powder.

[0008] Preferably, in step 2, the masses of ferric chloride hexahydrate, polyethylene glycol and sodium acetate are 90%-110%, 800%-1000% and 2800%-3200% of the mass of the boron carbide / dopamine complex, respectively.

[0009] Preferably, in step 4, the screw temperatures of the twin-screw extruder are: zone 1 temperature 40-50°C, zone 2 temperature 50-70°C, zone 3 temperature 70-90°C.

[0010] (III) Beneficial effects The present invention provides a multi-purpose radiation protection material and a preparation method thereof. Compared with the prior art, the present invention has the following beneficial effects: (1) The multi-purpose radiation protection material and its preparation method. During the preparation process of poly(gadolinium methacrylate), the molecular chains are connected by covalent bonds to form a stable three-dimensional network structure, thereby improving its chemical stability, helping to improve the stability of the radiation protection material and extend its service life. The gadolinium ions are evenly distributed in the polymer chains, increasing the effective concentration and distribution uniformity of the gadolinium ions, thereby improving the radiation protection effect of the material. At the same time, the molecular chain structure of the polymer may also produce a synergistic effect with the gadolinium ions, further enhancing the ability to absorb radiation.

[0011] (2) The multi-purpose radiation protection material and its preparation method prepare gadolinium methacrylate by reacting gadolinium hydroxide with methacrylic acid. Since gadolinium hydroxide has a certain alkalinity, when reacting with methacrylic acid, the reaction process is relatively mild and the reaction conditions are easier to control. At the same time, the reaction between gadolinium hydroxide and methacrylic acid is relatively thorough, and relatively few impurities are generated, which is beneficial to improving the selectivity of the reaction and the purity of the product. The operation steps are simple, which can not only reduce the difficulty of experimental operation, but also reduce the possibility of introducing impurities due to too many operation steps.

[0012] (3) The multi-purpose radiation protection material and its preparation method, dopamine hydrochloride forms a uniform coating on the surface of boron carbide, which not only improves the interface bonding between boron carbide and other components, but also increases the stability and compatibility of the multi-component hybrid filler. Good interface bonding is conducive to stress transmission and energy transfer, so that when the matrix is ​​irradiated, it can dissipate energy more effectively and reduce the damage caused by radiation, so that the radiation protection material maintains good radiation protection performance; at the same time, the addition of polyethylene glycol makes the internal structure of the multi-component hybrid filler more dense and uniform, which helps to reduce the pores and defects inside the matrix, reduce the possibility of radiation penetrating the matrix through the pores, and thus improve the overall radiation protection performance of the radiation protection material. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Figure 1 SEM images of gadolinium methacrylate prepared in Comparative Example 1 and Example 1 provided by the present invention. DETAILED DESCRIPTION

[0014] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0015] Example 1 Step 1: Add 0.9 g of methacrylic acid and 40 mL of deionized water to a reaction bottle, then slowly add 1 g of gadolinium hydroxide, heat the oil bath to 70°C, stir and react for 6 hours, filter while hot, distill the filtrate under reduced pressure, then add 20 mL of anhydrous ethanol, and after the reaction product is completely dissolved, continue to distill under reduced pressure, let stand for 20 hours, filter and dry to constant weight to obtain gadolinium methacrylate, dissolve 1 g of gadolinium methacrylate in 25 mL of deionized water at 70°C, then filter, dropwise add 0.05 g of ammonium sulfate, stir and react for 2 hours, and then dry the product to constant weight to obtain polygadolinium methacrylate; Step 2: Pour 1 g of boron carbide powder into a mixed solution of 150 mL of Tris buffer and 50 mL of anhydrous ethanol, stir for 5 min, add 0.35 g of dopamine hydrochloride, stir and react for 5 h at room temperature, centrifuge, wash and dry after the reaction is completed to obtain a boron carbide / dopamine complex, pour 0.2 g of the boron carbide / dopamine complex and 0.18 g of polyethylene glycol into a mixed solution of 1.6 g of ferric chloride hexahydrate and 80 mL of ethylene glycol, ultrasonically treat for 250 min, then add 5.6 g of sodium acetate, heat to 55 ° C, stir and react for 2 h, then cool to room temperature, centrifuge, wash and dry to obtain a multi-hybrid filler; Step 3: Pour 30 g of poly(gadolinium methacrylate), 25 g of multi-component hybrid filler, 40 g of chloroprene rubber and 50 g of paraffin into a high-speed blender and mix at 50° C. for 30 min. Step 4: Extruding the mixed raw materials into granules through a twin-screw extruder, wherein the temperature of zone 1 is 40° C., the temperature of zone 2 is 500° C., and the temperature of zone 3 is 70° C., to obtain a multi-purpose radiation protection material.

[0016] Example 2 Step 1: Add 0.93 g of methacrylic acid and 40 mL of deionized water to a reaction bottle, then slowly add 1 g of gadolinium hydroxide, heat the oil bath to 75° C., stir and react for 7 hours, filter while hot, distill the filtrate under reduced pressure, then add 25 mL of anhydrous ethanol, and after the reaction product is completely dissolved, continue to distill under reduced pressure, let stand for 22 hours, filter, and dry to constant weight to obtain gadolinium methacrylate. Dissolve 1 g of gadolinium methacrylate in 30 mL of deionized water at 75° C., then filter, dropwise add 0.06 g of ammonium sulfate, stir and react for 2 hours, and then dry the product to constant weight to obtain polygadolinium methacrylate; Step 2: Pour 1 g of boron carbide powder into a mixed solution of 165 mL of Tris buffer and 50 mL of anhydrous ethanol, stir for 8 min, add 0.4 g of dopamine hydrochloride, stir and react for 6 h at room temperature, centrifuge, wash and dry after the reaction is completed to obtain a boron carbide / dopamine complex, pour 0.2 g of the boron carbide / dopamine complex and 0.2 g of polyethylene glycol into a mixed solution of 1.8 g of ferric chloride hexahydrate and 80 mL of ethylene glycol, ultrasonically treat for 30 min, then add 5.8 g of sodium acetate, heat to 60 ° C, stir and react for 2.2 h, then cool to room temperature, centrifuge, wash and dry to obtain a multi-hybrid filler; Step 3: Pour 40g of poly(gadolinium methacrylate), 30g of multi-component hybrid filler, 50g of chloroprene rubber and 60g of paraffin into a high-speed blender and mix at 60°C for 35min; Step 4: Extruding the mixed raw materials into granules through a twin-screw extruder, wherein the temperature of zone 1 is 45° C., the temperature of zone 2 is 60° C., and the temperature of zone 3 is 80° C., to obtain a multi-purpose radiation protection material.

[0017] Example 3 Step 1: Add 0.96 g of methacrylic acid and 40 mL of deionized water to a reaction bottle, then slowly add 1 g of gadolinium hydroxide, heat the oil bath to 80°C, stir and react for 8 hours, filter while hot, distill the filtrate under reduced pressure, then add 30 mL of anhydrous ethanol, and after the reaction product is completely dissolved, continue to distill under reduced pressure, let stand for 24 hours, filter and dry to constant weight to obtain gadolinium methacrylate, dissolve 1 g of gadolinium methacrylate in 40 mL of deionized water at 80°C, then filter, dropwise add 0.08 g of ammonium sulfate, stir and react for 2 hours, and then dry the product to constant weight to obtain polygadolinium methacrylate; Step 2: Pour 1 g of boron carbide powder into a mixed solution of 175 mL of Tris buffer and 50 mL of anhydrous ethanol, stir for 10 min, add 0.45 g of dopamine hydrochloride, stir and react for 7 h at room temperature, centrifuge, wash and dry after the reaction is completed to obtain a boron carbide / dopamine complex, pour 0.2 g of the boron carbide / dopamine complex and 0.22 g of polyethylene glycol into a mixed solution of 2 g of ferric chloride hexahydrate and 80 mL of ethylene glycol, ultrasonically treat for 40 min, then add 6 g of sodium acetate, heat to 65 ° C, stir and react for 2.5 h, then cool to room temperature, centrifuge, wash and dry to obtain a multi-hybrid filler; Step 3: Pour 50 g of poly(gadolinium methacrylate), 40 g of multi-component hybrid filler, 70 g of chloroprene rubber and 80 g of paraffin into a high-speed blender and mix at 70° C. for 40 min; Step 4: Extruding the mixed raw materials into granules through a twin-screw extruder, wherein the temperature of zone 1 is 50° C., the temperature of zone 2 is 70° C., and the temperature of zone 3 is 90° C., to obtain a multi-purpose radiation protection material.

[0018] Comparative Example 1 Compared with Example 1, the difference is that the preparation method of gadolinium methacrylate is replaced: 14 mL of methacrylic acid and 40 mL of deionized water are added to the reaction bottle, and then 6.95 g of gadolinium oxide is slowly added, the oil bath is heated to 70° C., and the reaction is stirred for 6 hours, and then filtered while hot, the filtrate is distilled under reduced pressure, and then 20 mL of anhydrous ethanol is added, and the distillation under reduced pressure is continued, cooled to room temperature, allowed to stand, suction filtered, and dried to constant weight to obtain gadolinium methacrylate.

[0019] Comparative Example 2 Compared with Example 1, the difference lies in that polygadolinium methacrylate is replaced by gadolinium methacrylate.

[0020] Comparative Example 3 Compared with Example 1, the difference is that the multi-component hybrid filler is replaced by boron carbide.

[0021] Electromagnetic shielding performance: Tested in accordance with the national standard IEC 61000-5-7; Calculation of electromagnetic interference shielding effectiveness: ; In the formula, is the electric field intensity at the time of incidence, is the electric field strength after shielding; is the magnetic field intensity at the time of incidence, is the magnetic field strength after shielding; is the input power at the time of incidence, is the output power after shielding.

[0022] Linear attenuation coefficient test: using photon energy of 0.662MeV 137 Cs was used as the γ-ray radiation source; five repeated tests were performed with a timer of 30 seconds and the average value was taken; the linear attenuation coefficient of the composite material was obtained according to the Lambert-Beer law: ; In the formula, is the linear attenuation coefficient of the sample; is the specimen thickness; is the photon fluence rate value measured without sample shielding; It is the photon fluence rate value measured after adding sample shielding.

[0023] X-ray shielding rate: Use an X-ray generator to emit 120kV, 13mA X-rays (average energy 100keV), and under the condition that the geometric center of the ray emitter and the center of the detector remain unchanged, obtain the air kerma rate without sample ( ), and then place the sample between the radiation source and the detector to obtain the air kerma rate with the sample ( ), calculate the shielding rate n of the sample to X-rays, the calculation formula is: 00%.

[0024] Figure 1 In the figure, (a) is a SEM image of gadolinium methacrylate prepared in Comparative Example 1, and (b) is a SEM image of gadolinium methacrylate prepared in Example 1. Figure 1 It can be seen that the particles in (b) are finer than those in (a), and the particle size distribution in (b) is more uniform, the crystal form is rod-shaped, and there is a secondary microstructure.

[0025] Meanwhile, the contents not described in detail in this specification belong to the prior art known to those skilled in the art.

[0026] It should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device.

[0027] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A multi-purpose radiation protection material, characterized in that: The invention comprises the following raw materials in parts by weight: 30-50 parts of poly(gadolinium methacrylate), 25-40 parts of multi-component hybrid filler, 40-70 parts of chloroprene rubber and 50-80 parts of paraffin.

2. A method for preparing the multi-purpose radiation protection material according to claim 1, characterized in that: The method comprises the following preparation steps: Step 1, dissolving gadolinium methacrylate in deionized water at 70-80° C., then filtering, dropping ammonium sulfate, stirring and reacting for 2 hours, and drying the product to constant weight to obtain polygadolinium methacrylate; Step 2: Pour the boron carbide / dopamine complex and polyethylene glycol into a mixed solution of ferric chloride hexahydrate and ethylene glycol, perform ultrasonic treatment for 25-40 minutes, then add sodium acetate, heat to 55-65° C., stir to react for 2-2.5 hours, cool to room temperature, centrifuge, wash, and dry to obtain a multi-component hybrid filler; Step 3, pour poly(gadolinium methacrylate), multi-component hybrid filler, chloroprene rubber and paraffin into a high-speed blender, and mix at 50-70° C. for 30-40 minutes; Step 4: Extruding the mixed raw materials into granules through a twin-screw extruder to prepare a multi-purpose radiation protection material.

3. The method for preparing a multi-purpose radiation protection material according to claim 2, characterized in that: In the step 1, the mass of ammonium sulfate is 5%-8% of the mass of gadolinium methacrylate; the preparation method of gadolinium methacrylate is: add methacrylic acid and deionized water into a reaction bottle, then slowly add gadolinium hydroxide, heat the oil bath to 70-80°C, stir and react for 6-8h, filter while hot, distill the filtrate under reduced pressure, then add anhydrous ethanol, and after the reaction product is completely dissolved, continue to distill under reduced pressure, let stand for 20-24h, filter, and dry to constant weight to obtain gadolinium methacrylate.

4. The method for preparing a multi-purpose radiation protection material according to claim 3, characterized in that: The mass of the methacrylic acid is 90%-96% of the mass of the gadolinium hydroxide.

5. The method for preparing a multi-purpose radiation protection material according to claim 2, characterized in that: In the step 2, the preparation method of the boron carbide / dopamine complex is as follows: pouring boron carbide powder into a mixed solution of Tris buffer and anhydrous ethanol, stirring for 5-10 minutes, adding dopamine hydrochloride, stirring and reacting at room temperature for 5-7 hours, and centrifuging, washing and drying after the reaction is completed to obtain the boron carbide / dopamine complex.

6. The method for preparing a multi-purpose radiation protection material according to claim 5, characterized in that: The volume ratio of the Tris buffer to anhydrous ethanol is 3-3.5:1; the mass of the dopamine hydrochloride is 35%-45% of the mass of the boron carbide powder.

7. The method for preparing a multi-purpose radiation protection material according to claim 2, characterized in that: In the step 2, the masses of ferric chloride hexahydrate, polyethylene glycol and sodium acetate are 90%-110%, 800%-1000% and 2800%-3200% of the mass of the boron carbide / dopamine complex, respectively.

8. The method for preparing a multi-purpose radiation protection material according to claim 2, characterized in that: In the step 4, the screw temperatures of the twin-screw extruder are: zone 1 temperature 40-50°C, zone 2 temperature 50-70°C, zone 3 temperature 70-90°C.

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