Degradable radiation protection materials, methods of making and using the same

Abstract

The application relates to a degradable ray protection material and a preparation method and application thereof. In mass parts, the degradable ray protection material comprises the following components: 45-70 parts of polyvinyl alcohol, 15-35 parts of a shielding agent, 2-10 parts of a flame retardant, 2-10 parts of a plasticizer, 2-10 parts of a coupling agent and 2-10 parts of an epoxy resin, wherein the mass ratio of the polyvinyl alcohol to the shielding agent is (1.5-3.5):1. The degradable ray protection material adopts the polyvinyl alcohol, the shielding agent, the flame retardant, the plasticizer, the coupling agent and the epoxy resin in specific proportions, and the components are synergistically matched, so that the strength performance and the recyclability of the degradable ray protection material are improved.

Description

Technical Field

[0001] This application relates to the field of radiation protection materials technology, and in particular to a biodegradable radiation protection material, its preparation method, and its application. Background Technology

[0002] With the rapid development of nuclear energy and its applications, nuclear technology has permeated all aspects of people's lives, finding increasingly widespread use in military, communications, medicine, industry, and agriculture. However, while nuclear technology brings convenience, various types of radiation, such as X-rays, beta rays, and gamma rays, can also harm the human body and damage the environment. Radiation protection materials can shield against radioactive rays. Traditional radiation protection materials are mostly made of heavy metals such as lead and tungsten combined with rubber, making them non-biodegradable and environmentally unfriendly.

[0003] In recent years, engineers have developed radiation protection materials based on polylactic acid (PLA). PLA is biodegradable, thus causing less environmental pollution. However, PLA is brittle and prone to breakage, making it difficult to process and shape. Furthermore, PLA is expensive and, after biodegradation, it transforms into water and carbon dioxide, making it unrecyclable. On the other hand, the strength properties of both traditional and PLA-based radiation protection materials still need improvement.

[0004] Therefore, how to provide a biodegradable radiation protection material that can be recycled and has good strength properties has become an urgent technical problem to be solved. Summary of the Invention

[0005] Therefore, it is necessary to provide a recyclable and high-strength biodegradable radiation protection material, its preparation method, and its application.

[0006] A first aspect of this application provides a biodegradable radiation protection material, comprising the following components in parts by mass:

[0007] 45-70 parts of polyvinyl alcohol

[0008] 15 to 35 parts of shielding agent

[0009] 2 to 10 parts flame retardant

[0010] Plasticizer 2 to 10 parts

[0011] 2 to 10 parts of coupling agent, and

[0012] 2 to 10 parts epoxy resin

[0013] The mass ratio of the polyvinyl alcohol to the shielding agent is (1.5~3.5):1.

[0014] The aforementioned biodegradable radiation protection material utilizes a specific ratio of polyvinyl alcohol, shielding agent, flame retardant, plasticizer, coupling agent, and epoxy resin. The synergistic effect of these components improves the strength and recyclability of the material. Specifically, polyvinyl alcohol dissolves in hot water above 80°C. Therefore, adding used biodegradable radiation protection material to hot water yields a solution containing polyvinyl alcohol, shielding agent, and other components. Solid-liquid separation of this solution separates the polyvinyl alcohol and shielding agent, enabling their recycling and reuse. By adjusting the mass ratio of polyvinyl alcohol to shielding agent, the biodegradable radiation protection material exhibits good biodegradability and radiation shielding performance. Furthermore, an appropriate amount of flame retardant enhances the material's flame retardant properties, an appropriate amount of coupling agent improves the dispersibility of the shielding agent in polyvinyl alcohol, an appropriate amount of epoxy resin increases mechanical strength, and an appropriate amount of plasticizer improves processing performance.

[0015] In some embodiments, the biodegradable radiation protection material comprises, by weight parts:

[0016] 50-60 parts of polyvinyl alcohol

[0017] 20-30 parts of shielding agent

[0018] 5 to 8 parts flame retardant

[0019] 5 to 8 parts plasticizer

[0020] 5 to 8 parts of coupling agent, and

[0021] 5 to 8 parts epoxy resin.

[0022] In some embodiments, the mass ratio of the polyvinyl alcohol to the shielding agent is (2.0~3.0):1.

[0023] In some embodiments, the biodegradable radiation protection material satisfies at least one of the following (1) to (2):

[0024] (1) The mass ratio of the shielding agent to the coupling agent is (3.0~5.0):1;

[0025] (2) The coupling agent is coupled to the shielding agent.

[0026] In some embodiments, the polyvinyl alcohol satisfies at least one of the following (1) to (2):

[0027] (1) The degree of polymerization is 1500~2000;

[0028] (2) The degree of alcoholysis is 90%~99%.

[0029] In some embodiments, the biodegradable radiation protection material satisfies at least one of the following (1) to (4):

[0030] (1) The shielding agent includes at least one of lead powder, tungsten powder and iron powder;

[0031] (2) The flame retardant includes a halogen-free flame retardant;

[0032] (3) The plasticizer includes at least one of glycerol and ethylene glycol;

[0033] (4) The coupling agent includes at least one of γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane and γ-propyltrimethoxysilane.

[0034] In some embodiments, the particle size of the shielding agent is 600-800 mesh, and the halogen-free flame retardant includes at least one of ammonium polyphosphate and melamine.

[0035] A second aspect of this application provides a method for preparing a biodegradable radiation protection material, comprising the following steps:

[0036] Polyvinyl alcohol is placed in water for swelling treatment, followed by heating treatment to dissolve the polyvinyl alcohol and obtain a polyvinyl alcohol solution;

[0037] A modified shielding agent is prepared by adding a shielding agent, a coupling agent, and a flame retardant to water.

[0038] The modified shielding agent, plasticizer, and epoxy resin are added to the polyvinyl alcohol solution and mixed, followed by drying to remove water from the polyvinyl alcohol solution, in order to prepare the biodegradable radiation protection material.

[0039] In this embodiment, by mass parts, the polyvinyl alcohol is 45 to 70 parts, the shielding agent is 15 to 35 parts, the flame retardant is 2 to 10 parts, the plasticizer is 2 to 10 parts, the epoxy resin is 2 to 10 parts, and the mass ratio of the polyvinyl alcohol to the shielding agent is (1.5 to 3.5): 1.

[0040] In some embodiments, the preparation method satisfies at least one of the following (1) to (8):

[0041] (1) Add the shielding agent and the coupling agent to water and mix and stir so that the coupling agent is coupled to the shielding agent to prepare a modified shielding agent, and mix the flame retardant with the modified shielding agent;

[0042] (2) The swelling treatment is performed at a temperature of 50 ℃~60 ℃ for 4 h~6 h;

[0043] (3) The temperature of the heat treatment is 80 ℃~95 ℃;

[0044] (4) The mixing temperature is 50 ℃~80 ℃, and the mixing time is 0.5 h~1.5 h;

[0045] (5) The shielding agent includes at least one of lead powder, tungsten powder and iron powder;

[0046] (6) The flame retardant includes a halogen-free flame retardant;

[0047] (7) The plasticizer includes at least one of glycerol and ethylene glycol;

[0048] (8) The coupling agent includes at least one of γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane and γ-propyltrimethoxysilane.

[0049] A third aspect of this application provides a biodegradable radiation protection slurry comprising a solid component and water, wherein the solid component comprises the biodegradable radiation protection material described in the first aspect.

[0050] A fourth aspect of this application provides a biodegradable radiation protection article, comprising the biodegradable radiation protection material described in the first aspect. Detailed Implementation

[0051] To facilitate understanding of this application, a more complete description will be provided below. However, this application can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a more thorough and complete understanding of the disclosure of this application.

[0052] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0053] In the description of this application, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of indicated technical features. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one of that feature. In the description of this application, "multiple" means at least two, such as two, three, etc., unless otherwise explicitly specified.

[0054] The weights of the relevant components mentioned in the embodiments of this application can refer not only to the specific content of each component, but also to the proportional relationship between the weights of the components. Therefore, any scaling up or down of the content of the relevant components according to the embodiments of this application is within the scope disclosed in the embodiments of this application. Specifically, the weights mentioned in the embodiments of this application can be well-known units of mass in the chemical industry, such as μg, mg, g, and kg.

[0055] One embodiment of this application provides a biodegradable radiation protection material, comprising the following components by mass parts:

[0056] 45-70 parts of polyvinyl alcohol

[0057] 15 to 35 parts of shielding agent

[0058] 2 to 10 parts flame retardant

[0059] Plasticizer 2 to 10 parts

[0060] 2 to 10 parts of coupling agent, and

[0061] 2 to 10 parts epoxy resin

[0062] The mass ratio of polyvinyl alcohol to shielding agent is (1.5~3.5):1.

[0063] Optionally, the polyvinyl alcohol can be 45 parts, 47 parts, 49 parts, 51 parts, 53 parts, 55 parts, 57 parts, 59 parts, 61 parts, 63 parts, 65 parts, 67 parts, 69 parts or 70 parts, and other suitable options can also be made within the range of 45 parts to 70 parts.

[0064] Optionally, the shielding agent can be 15, 17, 19, 21, 23, 25, 27, 29, 31 or 35 parts, and other suitable selections can also be made within the range of 15 to 35 parts.

[0065] Optionally, the flame retardant can be 2, 3, 4, 5, 6, 7, 8, 9 or 10 parts, and other suitable options can also be made within the range of 2 to 10 parts.

[0066] Optionally, the plasticizer can be 2, 3, 4, 5, 6, 7, 8, 9 or 10 parts, and other suitable plasticizers can also be selected in the range of 2 to 10 parts.

[0067] Optionally, the coupling agent can be 2, 3, 4, 5, 6, 7, 8, 9 or 10 parts, and other suitable options can also be made within the range of 2 to 10 parts.

[0068] Optionally, the epoxy resin can be 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts, and other suitable options can be made within the range of 2 parts to 10 parts.

[0069] Understandably, polyvinyl alcohol (PVA) is a water-soluble polymer, and using it as the base material in the radiation protection material of this embodiment allows for better biodegradability. Furthermore, the coupling agent effectively improves the dispersion of the shielding agent and flame retardant within the PVA matrix, preventing their precipitation and aggregation. In addition, epoxy resin enhances the mechanical properties of the resulting radiation protection material. It should be noted that degradation in this text refers to a reduction in the number of carbon atoms and a decrease in molecular weight in organic compounds.

[0070] The aforementioned biodegradable radiation protection material utilizes a specific ratio of polyvinyl alcohol, shielding agent, flame retardant, plasticizer, coupling agent, and epoxy resin. The synergistic effect of these components improves the strength and recyclability of the material. Specifically, polyvinyl alcohol dissolves in hot water above 80°C. Therefore, adding used biodegradable radiation protection material to hot water yields a solution containing polyvinyl alcohol, shielding agent, and other components. Solid-liquid separation of this solution separates the polyvinyl alcohol and shielding agent, enabling their recycling and reuse. By adjusting the mass ratio of polyvinyl alcohol to shielding agent, the biodegradable radiation protection material exhibits good biodegradability and radiation shielding performance. Furthermore, an appropriate amount of flame retardant enhances the material's flame retardant properties, an appropriate amount of coupling agent improves the dispersibility of the shielding agent in polyvinyl alcohol, an appropriate amount of epoxy resin increases mechanical strength, and an appropriate amount of plasticizer improves processing performance.

[0071] In some embodiments, the biodegradable radiation protection material comprises, by weight parts, the following components:

[0072] 45-70 parts of polyvinyl alcohol

[0073] 15 to 35 parts of shielding agent

[0074] 2 to 10 parts flame retardant

[0075] Plasticizer 2 to 10 parts

[0076] 2 to 10 parts of coupling agent, and

[0077] 2 to 10 parts epoxy resin

[0078] The mass ratio of polyvinyl alcohol to shielding agent is (1.5~3.5):1.

[0079] In some embodiments, the biodegradable radiation protection material comprises, by weight parts:

[0080] 50-60 parts of polyvinyl alcohol

[0081] 20-30 parts of shielding agent

[0082] 5 to 8 parts flame retardant

[0083] 5 to 8 parts plasticizer

[0084] 5 to 8 parts of coupling agent, and

[0085] 5 to 8 parts epoxy resin.

[0086] When biodegradable radiation protection materials include the above-mentioned specific mass proportions of polyvinyl alcohol, shielding agent, flame retardant, plasticizer, coupling agent and epoxy resin, the biodegradability, recyclability, flame retardancy, mechanical properties and radiation shielding performance of the materials can be improved more effectively.

[0087] In some embodiments, the biodegradable radiation protection material comprises, by weight parts, the following components:

[0088] 50-60 parts of polyvinyl alcohol

[0089] 20-30 parts of shielding agent

[0090] 5 to 8 parts flame retardant

[0091] 5 to 8 parts plasticizer

[0092] 5 to 8 parts of coupling agent, and

[0093] 5 to 8 parts epoxy resin.

[0094] In some embodiments, the mass ratio of polyvinyl alcohol to shielding agent is (2.0~3.0):1.

[0095] Optionally, the mass ratio of polyvinyl alcohol to the shielding agent can be 2.0:1, 2.1:1, 2.2:1, 2.3:1, 2.4:1, 2.5:1, 2.6:1, 2.7:1, 2.8:1, 2.9:1, or 3.0:1. Other suitable selections within the range of (2.0~3.0):1 are also possible. By adjusting the mass ratio of polyvinyl alcohol to the shielding agent, the degradation and recycling performance and the radiation shielding performance of the biodegradable radiation protection material can be more effectively balanced.

[0096] In some embodiments, the mass ratio of the shielding agent to the coupling agent is (3.0~5.0):1.

[0097] Optionally, the mass ratio of the shielding agent to the coupling agent can be 3:1, 3.5:1, 4:1, 4.5:1, or 5:1, and other suitable selections can be made within the range of (3.0~5.0):1. By adjusting the mass ratio of the shielding agent to the coupling agent, the shielding agent can be uniformly dispersed in the polyvinyl alcohol matrix.

[0098] In some embodiments, the coupling agent is coupled to the shielding agent. Understandably, in the biodegradable radiation protection material of this embodiment, the coupling agent is combined with the shielding agent, thereby improving the dispersibility of the shielding agent in the polyvinyl alcohol matrix.

[0099] In some of these embodiments, the degree of polymerization of polyvinyl alcohol is 1500 to 2000.

[0100] In some of these embodiments, the degree of alcoholysis of polyvinyl alcohol is 90% to 99%.

[0101] In some of these embodiments, the water solubility temperature of polyvinyl alcohol is ≥80 °C.

[0102] The above embodiments use polyvinyl alcohol with specific degrees of polymerization, degrees of alcoholysis, or water solubility temperatures, which can effectively enhance the degradability and recyclability of the resulting radiation protection materials.

[0103] In some embodiments, the shielding agent includes at least one of lead powder, tungsten powder, and iron powder.

[0104] In some embodiments, the flame retardant includes a halogen-free flame retardant.

[0105] In some embodiments, the plasticizer includes at least one of glycerol and ethylene glycol.

[0106] In some embodiments, the coupling agent includes at least one of γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-propyltrimethoxysilane.

[0107] In some embodiments, the particle size of the shielding agent is 600-800 mesh.

[0108] Optionally, the particle size of the shielding agent can be 600 mesh, 650 mesh, 700 mesh, 750 mesh, or 800 mesh, and other suitable selections can be made within the range of 600 mesh to 800 mesh. When the particle size of the shielding agent is too small, local agglomeration of the shielding agent is likely to occur during the subsequent molding process, affecting the film formation effect; when the particle size of the shielding agent is too large, it is easy to lead to the deterioration of the mechanical properties after film formation.

[0109] In some embodiments, the halogen-free flame retardant includes at least one of ammonium polyphosphate and melamine. This embodiment employs a specific flame retardant, which improves the environmental performance of the resulting radiation protection material and facilitates its recycling.

[0110] Another embodiment of this application provides a method for preparing a biodegradable radiation protection material, including the following steps S12-S16.

[0111] S12. Polyvinyl alcohol is placed in water for swelling treatment, followed by heating treatment to dissolve the polyvinyl alcohol and obtain a polyvinyl alcohol solution.

[0112] S14. Add the shielding agent, coupling agent and flame retardant to water to prepare a modified shielding agent;

[0113] S16. Modified shielding agent, plasticizer and epoxy resin are added to polyvinyl alcohol solution and mixed; then dried to remove water from polyvinyl alcohol solution to prepare biodegradable radiation protection material;

[0114] The composition, by mass parts, is 45-70 parts of polyvinyl alcohol, 15-35 parts of shielding agent, 2-10 parts of flame retardant, 2-10 parts of plasticizer, and 2-10 parts of epoxy resin, with the mass ratio of polyvinyl alcohol to shielding agent being (1.5-3.5):1.

[0115] Understandably, the preparation method of this embodiment first prepares a polyvinyl alcohol solution and modifies the shielding agent. Then, the modified shielding agent, plasticizer, and epoxy resin are added to the polyvinyl alcohol solution and mixed. After drying, a biodegradable radiation protection material can be obtained. It should be noted that steps S12 and S14 can be performed sequentially or simultaneously, and this application does not impose any restrictions on this.

[0116] The above preparation method can yield radiation protection materials that are biodegradable, recyclable, and possess good flame retardant, radiation shielding, and mechanical properties. Furthermore, the method is simple and easy to implement, and has the potential for large-scale industrial production.

[0117] In some embodiments, a shielding agent, a coupling agent, and a flame retardant are added to water and mixed and stirred to couple the coupling agent to the shielding agent, thereby preparing a modified shielding agent, and the flame retardant is mixed with the modified shielding agent.

[0118] In some embodiments, the swelling treatment temperature is 50°C to 60°C, and the time is 4 h to 6 h. Optionally, the swelling treatment temperature can be 50°C, 51°C, 52°C, 53°C, 54°C, 55°C, 56°C, 57°C, 58°C, 59°C, or 60°C, and the swelling treatment time can be 4 h, 4.5 h, 5 h, 5.5 h, or 6 h.

[0119] In some embodiments, the heat treatment temperature is 80°C to 95°C. Optionally, the heat treatment temperature can be 80°C, 81°C, 82°C, 83°C, 84°C, 85°C, 86°C, 87°C, 88°C, 89°C, 90°C, or 95°C.

[0120] In some embodiments, the mixing temperature is 50 ℃ to 80 ℃, and the mixing time is 0.5 h to 1.5 h. Optionally, the mixing temperature can be 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, or 80 ℃, and the mixing time can be 0.5 h, 1 h, or 1.5 h.

[0121] In some embodiments, the shielding agent includes at least one of lead powder, tungsten powder, and iron powder.

[0122] In some embodiments, the flame retardant includes a halogen-free flame retardant. Optionally, the halogen-free flame retardant includes at least one of ammonium polyphosphate and melamine.

[0123] In some embodiments, the plasticizer includes at least one of glycerol and ethylene glycol.

[0124] In some embodiments, the coupling agent includes at least one of γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-propyltrimethoxysilane.

[0125] In some embodiments, the particle size of the shielding agent is 600-800 mesh.

[0126] In some embodiments, the mass ratio of polyvinyl alcohol to shielding agent is (2.0~3.0):1.

[0127] In some embodiments, the mass ratio of the shielding agent to the coupling agent is (3.0~5.0):1.

[0128] In some of these embodiments, the degree of polymerization of polyvinyl alcohol is 1500 to 2000.

[0129] In some of these embodiments, the degree of alcoholysis of polyvinyl alcohol is 90% to 99%.

[0130] In some of these embodiments, the water solubility temperature of polyvinyl alcohol is ≥80 °C.

[0131] In some embodiments, step S16 includes the following steps:

[0132] Modified shielding agent, plasticizer and epoxy resin are added to polyvinyl alcohol solution and mixed to obtain biodegradable radiation protection slurry;

[0133] The biodegradable radiation protection slurry is formed by casting to prepare the biodegradable radiation protection material.

[0134] Optionally, the casting process involves casting the mixture through gaps onto a dry steel belt or rotating roller, causing the water in the biodegradable radiation protection slurry to evaporate. After the slurry is fully dried, a sheet-like film is formed on the steel belt or rotating roller. This film is the biodegradable radiation protection material of this embodiment. Alternatively, the casting process can involve coating the mixture onto a dry steel belt or rotating roller and evaporating the water. This application does not limit the specific method of casting.

[0135] It should be noted that the biodegradable radiation protection material of this application can be recycled through the following methods:

[0136] The used biodegradable radiation protection material is added back into water at 80℃~95℃ and dissolved for 2h~3h to obtain a mixture to be recycled. The mixture is then subjected to solid-liquid separation; the filtrate is an aqueous solution containing polyvinyl alcohol, and the filter residue is a mixture including a modified radiation shielding agent. The filtrate is dried or concentrated to obtain a polyvinyl alcohol solution; the filter residue is rinsed and added to water, and the shielding agent with higher density can be further screened based on its density. Furthermore, using the recovered polyvinyl alcohol solution and shielding agent as raw materials, appropriate amounts of coupling agent, flame retardant, plasticizer, and epoxy resin are added again, and the biodegradable radiation protection material can be re-prepared using the above preparation method. Furthermore, experimental studies have shown that the biodegradable radiation protection material of this application can be recycled more than 10 times according to the above method, thus saving resources.

[0137] This application also provides a biodegradable radiation protection slurry, comprising a solid component and water, wherein the solid component includes the aforementioned biodegradable radiation protection material. Understandably, the biodegradable radiation protection material of this application can be obtained by drying the slurry to remove the water. It should be noted that the aforementioned biodegradable radiation protection slurry can also be used in other ways, and this application does not limit its application to such uses.

[0138] Furthermore, this application also provides a method for preparing the above-mentioned biodegradable radiation protection slurry, comprising the following steps:

[0139] Polyvinyl alcohol is placed in water for swelling treatment, followed by heating treatment to dissolve the polyvinyl alcohol and obtain a polyvinyl alcohol solution;

[0140] A modified shielding agent is prepared by adding a shielding agent, a coupling agent, and a flame retardant to water.

[0141] The modified shielding agent, plasticizer, and epoxy resin are added to the polyvinyl alcohol solution and mixed to prepare a biodegradable radiation protection slurry.

[0142] Furthermore, this application also provides a biodegradable radiation protection product, including the aforementioned biodegradable radiation protection material. Exemplarily, the biodegradable radiation protection material can be processed into a predetermined shape or size to obtain the biodegradable radiation protection product. Exemplarily, the biodegradable radiation protection product is a radiation protective suit.

[0143] The following are specific examples.

[0144] Example 1

[0145] The biodegradable radiation protection material of Example 1 comprises the following components by weight:

[0146] 55 parts of polyvinyl alcohol

[0147] 20 parts lead powder

[0148] 5 parts of ammonium polyphosphate

[0149] 5 parts glycerin

[0150] 5 parts of γ-mercaptopropyltrimethoxysilane, and

[0151] 5 parts epoxy resin.

[0152] The polyvinyl alcohol has a degree of polymerization of 1700 and a degree of alcoholysis of 99%, while the lead powder has a particle size of 700 mesh.

[0153] The specific preparation method is as follows:

[0154] Prepare raw materials according to the mass proportions of the above components. Soak polyvinyl alcohol in water at 55 °C for 5 hours to swell, then heat to 90 °C to completely dissolve the polyvinyl alcohol, obtaining a polyvinyl alcohol solution. Add lead powder, γ-mercaptopropyltrimethoxysilane, and ammonium polyphosphate to water and stir at 65 °C for 1 hour. Filter to obtain the solid, yielding a modified shielding agent. Add the modified shielding agent, glycerol, and epoxy resin to the dissolved polyvinyl alcohol solution and stir for 4 hours to obtain a biodegradable protective slurry. Cast the biodegradable protective slurry through gaps onto a dry steel strip, allowing the water to evaporate and form a sheet. Remove the sheet from the steel strip to obtain a sheet-like biodegradable radiation protection material.

[0155] Example 2

[0156] The preparation method of Example 2 is basically the same as that of Example 1, except that, by mass parts, the biodegradable radiation protection material of Example 2 comprises the following components:

[0157] 70 parts of polyvinyl alcohol

[0158] 20 parts lead powder

[0159] 5 parts of ammonium polyphosphate

[0160] 5 parts glycerin

[0161] 5 parts of γ-mercaptopropyltrimethoxysilane, and

[0162] 5 parts epoxy resin.

[0163] The polyvinyl alcohol has a degree of polymerization of 1700 and a degree of alcoholysis of 99%, while the lead powder has a particle size of 700 mesh.

[0164] Example 3

[0165] The preparation method of Example 3 is basically the same as that of Example 1, except that, by mass parts, the biodegradable radiation protection material of Example 3 includes the following components:

[0166] 45 parts of polyvinyl alcohol

[0167] 20 parts lead powder

[0168] 5 parts of ammonium polyphosphate

[0169] 5 parts glycerin

[0170] 5 parts of γ-mercaptopropyltrimethoxysilane, and

[0171] 5 parts epoxy resin.

[0172] The polyvinyl alcohol has a degree of polymerization of 1700 and a degree of alcoholysis of 99%, while the lead powder has a particle size of 700 mesh.

[0173] Example 4

[0174] The preparation method of Example 4 is basically the same as that of Example 1, except that, by mass parts, the biodegradable radiation protection material of Example 4 comprises the following components:

[0175] 55 parts of polyvinyl alcohol

[0176] 30 parts lead powder

[0177] 5 parts of ammonium polyphosphate

[0178] 5 parts glycerin

[0179] 5 parts of γ-mercaptopropyltrimethoxysilane, and

[0180] 5 parts epoxy resin.

[0181] The polyvinyl alcohol has a degree of polymerization of 1700 and a degree of alcoholysis of 99%, while the lead powder has a particle size of 700 mesh.

[0182] Example 5

[0183] The preparation method of Example 5 is basically the same as that of Example 1, except that, by mass parts, the biodegradable radiation protection material of Example 5 comprises the following components:

[0184] 55 parts of polyvinyl alcohol

[0185] 20 parts lead powder

[0186] 5 parts of ammonium polyphosphate

[0187] 5 parts glycerin

[0188] 3 parts of γ-mercaptopropyltrimethoxysilane, and

[0189] 5 parts epoxy resin.

[0190] The polyvinyl alcohol has a degree of polymerization of 1700 and a degree of alcoholysis of 99%, while the lead powder has a particle size of 700 mesh.

[0191] Example 6

[0192] The preparation method of Example 6 is basically the same as that of Example 1, except that, by mass parts, the biodegradable radiation protection material of Example 6 comprises the following components:

[0193] 55 parts of polyvinyl alcohol

[0194] 20 parts lead powder

[0195] 5 parts of ammonium polyphosphate

[0196] 5 parts glycerin

[0197] 10 parts of γ-mercaptopropyltrimethoxysilane, and

[0198] 5 parts epoxy resin.

[0199] The polyvinyl alcohol has a degree of polymerization of 1700 and a degree of alcoholysis of 99%, while the lead powder has a particle size of 700 mesh.

[0200] Example 7

[0201] The preparation method of Example 7 is basically the same as that of Example 1, except that, by mass parts, the biodegradable radiation protection material of Example 7 comprises the following components:

[0202] 55 parts of polyvinyl alcohol

[0203] 20 parts lead powder

[0204] 5 parts of ammonium polyphosphate

[0205] 5 parts glycerin

[0206] 5 parts of γ-mercaptopropyltrimethoxysilane, and

[0207] 5 parts epoxy resin.

[0208] The polyvinyl alcohol has a degree of polymerization of 2600 and a degree of alcoholysis of 99%, and the lead powder has a particle size of 700 mesh.

[0209] Comparative Example 1

[0210] The preparation method of Comparative Example 1 is basically the same as that of Example 1, except that, by mass parts, the biodegradable radiation protection material of Comparative Example 1 comprises the following components:

[0211] 80 parts of polyvinyl alcohol

[0212] 20 parts lead powder

[0213] 5 parts of ammonium polyphosphate

[0214] 5 parts glycerin

[0215] 5 parts of γ-mercaptopropyltrimethoxysilane, and

[0216] 5 parts epoxy resin.

[0217] The polyvinyl alcohol has a degree of polymerization of 1700 and a degree of alcoholysis of 99%, while the lead powder has a particle size of 700 mesh.

[0218] Comparative Example 2

[0219] The preparation method of Comparative Example 2 is basically the same as that of Example 1, except that, by mass parts, the biodegradable radiation protection material of Comparative Example 2 comprises the following components:

[0220] 35 parts of polyvinyl alcohol

[0221] 35 parts lead powder

[0222] 5 parts of ammonium polyphosphate

[0223] 5 parts glycerin

[0224] 5 parts of γ-mercaptopropyltrimethoxysilane, and

[0225] 5 parts epoxy resin.

[0226] The polyvinyl alcohol has a degree of polymerization of 1700 and a degree of alcoholysis of 99%, while the lead powder has a particle size of 700 mesh.

[0227] Comparative Example 3

[0228] The preparation method of Comparative Example 3 is basically the same as that of Example 1, except that, by mass parts, the biodegradable radiation protection material of Comparative Example 3 includes the following components:

[0229] 60 parts of polyvinyl alcohol

[0230] 15 parts lead powder

[0231] 5 parts of ammonium polyphosphate

[0232] 5 parts glycerin

[0233] 5 parts of γ-mercaptopropyltrimethoxysilane, and

[0234] 5 parts epoxy resin.

[0235] The polyvinyl alcohol has a degree of polymerization of 1700 and a degree of alcoholysis of 99%, while the lead powder has a particle size of 700 mesh.

[0236] Comparative Example 4

[0237] The preparation method of Comparative Example 4 is basically the same as that of Example 1, except that, by mass parts, the biodegradable radiation protection material of Comparative Example 4 comprises the following components:

[0238] 55 parts of polyvinyl alcohol

[0239] 20 parts lead powder

[0240] 5 parts of ammonium polyphosphate

[0241] 5 parts glycerin, and

[0242] 5 parts epoxy resin.

[0243] The polyvinyl alcohol has a degree of polymerization of 1700 and a degree of alcoholysis of 99%, while the lead powder has a particle size of 700 mesh.

[0244] The component contents of the biodegradable protective materials of Examples 1-7 and Comparative Examples 1-4 are shown in Table 1 below. The unit of each component content is parts by mass, and A / B represents the mass ratio of polyvinyl alcohol to shielding agent.

[0245] Table 1

[0246]

[0247] The biodegradable radiation protection materials prepared in Examples 1-7 and Comparative Examples 1-4 were tested for their biodegradability, recyclability, and strength. The test results are shown in Table 2 below. The specific test methods are as follows:

[0248] 1. Degradability and recyclability

[0249] The degradable radiation shielding materials of each embodiment and comparative example were weighed and denoted as M. The degradable radiation shielding materials were immersed in water at 90 °C and stirred to dissolve for 2.5 h, then filtered, and the filter residue was collected. This filter residue included shielding agents, flame retardants, and other additives; the filtrate was an aqueous solution containing polyvinyl alcohol. The mass of the filter residue was measured and denoted as m. The degradability of polyvinyl alcohol was calculated as 1 - (m / M). The test results are shown in Table 2.

[0250] The mass percentage of polyvinyl alcohol in the filtrate was determined by gas chromatography and denoted as c. The recyclability of polyvinyl alcohol is calculated as c / C, where C represents the mass percentage of polyvinyl alcohol in the degradable radiation protection material before it is immersed in hot water. This mass percentage can be calculated from the mass fractions of each component in the material.

[0251] The test results are shown in Table 2. It should be noted that this application can recover not only polyvinyl alcohol but also the shielding agent in the filter residue, but the recyclability in Table 2 refers to the recovery rate of polyvinyl alcohol.

[0252] 2. Strength performance

[0253] The longitudinal tensile strength, transverse tensile strength, and puncture strength of the degradable radiation protection materials in each embodiment and comparative example were tested using the method specified in GB / T 1040.3-2006. The test results are shown in Table 2.

[0254] Table 2

[0255]

[0256] As can be seen from Table 2 above, the biodegradable radiation protection materials of Examples 1 to 7 have good comprehensive performance, and can have good biodegradability, recyclability and strength properties. This indicates that the present application uses polyvinyl alcohol, shielding agent, flame retardant, plasticizer, coupling agent and epoxy resin in a specific ratio. The components work together synergistically to improve the flame retardancy and recyclability of the biodegradable radiation protection materials.

[0257] The mass fractions of polyvinyl alcohol in Comparative Examples 1 and 2 are outside the scope of this application. Compared to Example 1, the strength of Comparative Example 1 is reduced, and the biodegradability and recyclability of Comparative Example 2 are reduced. The mass ratio of polyvinyl alcohol to shielding agent in Comparative Example 3 is outside the scope of this application. Comparative Example 4 does not contain coupling agent, and its overall performance is not as good as that of Example 1.

[0258] Furthermore, the filter residue recovered in Example 1 was rinsed and placed in water, allowed to stand, and the solid components that settled first were collected, which was the recovered shielding agent. The filtrate containing polyvinyl alcohol was dried to remove some of the water, resulting in a concentrated polyvinyl alcohol solution. Using the recovered shielding agent and polyvinyl alcohol solution as raw materials, 5 parts of ammonium polyphosphate, 5 parts of glycerol, 5 parts of γ-mercaptopropyltrimethoxysilane, and 5 parts of epoxy resin were added, and a modified shielding agent was prepared using the same method as in Example 1. The modified shielding agent, glycerol, and epoxy resin were then added to the concentrated polyvinyl alcohol solution, and a degradable radiation protection material was prepared according to the method in Example 1. Subsequently, the mechanical properties of the obtained degradable radiation protection material were tested, and the longitudinal tensile strength was 23.1 MPa, the transverse tensile strength was 24.2 MPa, and the puncture strength was 4.26 N. This demonstrates that a high-strength radiation protection material can still be produced using the recovered material as a raw material.

[0259] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0260] The embodiments described above are merely illustrative of several implementation methods of this application, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the protection scope of this application. Therefore, the protection scope of this patent application should be determined by the appended claims.

Claims

1. A biodegradable radiation protection material, characterized in that, The biodegradable radiation protection material comprises the following components by weight: 50-60 parts of polyvinyl alcohol 20-30 parts of shielding agent 5 to 8 parts flame retardant 5 to 8 parts plasticizer 5 to 8 parts of coupling agent, and 5 to 8 parts epoxy resin; Wherein, the degree of polymerization of the polyvinyl alcohol is 1500~2000, the mass ratio of the polyvinyl alcohol to the shielding agent is (2.0~3.0):1, the mass ratio of the shielding agent to the coupling agent is (3.0~5.0):1, and the coupling agent is coupled to the shielding agent.

2. The biodegradable radiation protection material as described in claim 1, characterized in that, The degree of alcoholysis of the polyvinyl alcohol is 90%~99%.

3. The biodegradable radiation protection material as described in claim 1, characterized in that, The biodegradable radiation protection material satisfies at least one of the following (1) to (4): (1) The shielding agent includes at least one of lead powder, tungsten powder and iron powder; (2) The flame retardant includes a halogen-free flame retardant; (3) The plasticizer includes at least one of glycerol and ethylene glycol; (4) The coupling agent includes at least one of γ-mercaptopropyltrimethoxysilane and γ-aminopropyltriethoxysilane.

4. The biodegradable radiation protection material according to any one of claims 1 to 3, characterized in that, The shielding agent has a particle size of 600-800 mesh, and the flame retardant includes at least one of ammonium polyphosphate and melamine.

5. A method for preparing a biodegradable radiation protection material, characterized in that, Includes the following steps: Polyvinyl alcohol is placed in water for swelling treatment, followed by heating treatment to dissolve the polyvinyl alcohol and obtain a polyvinyl alcohol solution; A modified shielding agent is prepared by adding a shielding agent, a coupling agent, and a flame retardant to water. The modified shielding agent, plasticizer, and epoxy resin are added to the polyvinyl alcohol solution and stirred and mixed, followed by drying to remove water from the polyvinyl alcohol solution, in order to prepare the biodegradable radiation protection material. In this embodiment, by mass parts, the polyvinyl alcohol comprises 50 to 60 parts, the shielding agent comprises 20 to 30 parts, the flame retardant comprises 5 to 8 parts, the plasticizer comprises 5 to 8 parts, the coupling agent comprises 5 to 8 parts, and the epoxy resin comprises 5 to 8 parts. The degree of polymerization of the polyvinyl alcohol is 1500 to 2000. The mass ratio of the polyvinyl alcohol to the shielding agent is (2.0 to 3.0):1, and the mass ratio of the shielding agent to the coupling agent is (3.0 to 5.0):

1. The coupling agent is coupled to the shielding agent.

6. The method for preparing the biodegradable radiation protection material as described in claim 5, characterized in that, The preparation method satisfies at least one of the following (1) to (8): (1) Add the shielding agent, the coupling agent and the flame retardant to water and mix and stir so that the coupling agent is coupled to the shielding agent to prepare a modified shielding agent, and mix the flame retardant with the modified shielding agent; (2) The swelling treatment is performed at a temperature of 50 ℃~60 ℃ for 4 h~6 h; (3) The temperature of the heat treatment is 80 ℃~95 ℃; (4) The mixing temperature is 50 ℃~80 ℃, and the mixing time is 0.5 h~1.5 h; (5) The shielding agent includes at least one of lead powder, tungsten powder and iron powder; (6) The flame retardant includes a halogen-free flame retardant; (7) The plasticizer includes at least one of glycerol and ethylene glycol; (8) The coupling agent includes at least one of γ-mercaptopropyltrimethoxysilane and γ-aminopropyltriethoxysilane.

7. A biodegradable radiation protection slurry, characterized in that, It includes a solid component and water, wherein the solid component includes the biodegradable radiation protection material according to any one of claims 1 to 4.

8. A biodegradable radiation protection product, characterized in that, Includes the biodegradable radiation protection material as described in any one of claims 1 to 4.

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