Radiation-proof material as well as preparation method and application thereof

Abstract

The invention relates to the technical field of anti-radiation materials, and provides an anti-radiation material and a preparation method and application thereof, the anti-radiation material comprises the following components by weight: 15-60 parts of a modified polymer, 40-80 parts of modified functional particles, and 6.5-15 parts of an additive; the preparation method comprises the following steps: uniformly mixing dried modified functional particles, boron and / or a compound thereof, adding a coupling agent solution, mixing, and drying to obtain a shield pretreatment material; mixing the shield pretreatment material with a modified polymer and an antioxidant, adding the mixture into an internal mixer, heating for a period of time, and performing hot press molding in a mold to obtain the anti-radiation material. The invention also provides an application of the anti-radiation material as a protective product in the fields of medicine and chemical industry. The anti-radiation material disclosed by the invention has good X-ray absorption and anti-radiation performance, is lead-free, and has the advantages of environment friendliness and no toxicity.

Description

Technical Field

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

[0002] Interventional surgeries are widely used due to their minimal trauma and rapid recovery. During these procedures, X-rays and other imaging techniques are often used to assist doctors in accurately locating the lesion and guiding surgical instruments.

[0003] Currently, lead gowns, lead caps, and lead neckbands are available for medical personnel to protect during interventional surgery. However, the overall protection for medical personnel's hands and areas that come into direct contact with patients is insufficient. Traditional interventional surgical kits primarily focus on providing a sterile environment and storing the instruments and dressings required for surgery. They have relatively simple functions and are not specifically designed for radiation protection during interventional surgery. Therefore, existing interventional surgical protective measures have the problem of insufficient radiation protection. It is necessary to develop a new type of interventional surgical kit with radiation protection function to improve the level of radiation protection during surgery and ensure the safety of medical personnel and patients. Summary of the Invention

[0004] The purpose of the present invention is to provide a radiation-proof material and its preparation method and application, which has good absorption and radiation-proof properties for X-rays and is lead-free and environmentally friendly and non-toxic.

[0005] The embodiments of the present invention are achieved through the following technical solutions:

[0006] A radiation protection material, comprising the following components by weight: 15 to 60 parts of a modified polymer, 40 to 80 parts of modified functional particles, and 6.5 to 15 parts of an additive;

[0007] wherein the polymer is polyurethane;

[0008] Functional particles include: one or more of bismuth, samarium, barium, lanthanum, gadolinium, tantalum, tungsten and their compounds;

[0009] The additives include: 5 to 10 parts of boron and its compounds (such as boron element or boron-containing compounds), 1 to 3 parts of antioxidants and 0.5 to 2 parts of coupling agents. Specifically, the boron and its compounds can be boron element, boron carbide or boron nitride, the antioxidant can be Irganox 1010, and the coupling agent can be silane coupling agent KH-550.

[0010] Furthermore, the modified functional particles are prepared as follows: 100 mL of an ethanol-water solution (ethanol to ultrapure water volume ratio of 4:1) is placed in a beaker, the pH is adjusted to 3-4 with a 0.1-0.5 mol / L dilute hydrochloric acid solution, an appropriate amount of KH570 silane coupling agent is added, and hydrolysis is carried out at room temperature with stirring for 30-60 minutes. Then, 4 g of the dried functional particles are added, and the mixture is ultrasonically treated in an ice bath for 30-60 minutes. Then, the mixture is heated in an oil bath to 70-90°C and stirred at this constant temperature for 2-4 hours. After the reaction is completed, the mixture is centrifuged, washed, and finally dried in an oven at 70-90°C to constant weight to obtain the modified functional particles.

[0011] By modifying the functional particles with silane coupling agents, the agglomerations and voids inside the material are filled, and a cross-linked network is formed with the material matrix, which significantly improves the compatibility between the functional particles and the polymer; and the doping of modified functional particles is beneficial to increase the thermal decomposition temperature of the radiation-proof material, that is, enhance the thermal stability of the material, greatly improving the stability during mixing and hot pressing during the preparation of the radiation-proof material.

[0012] Furthermore, the preparation method of the modified polyurethane is as follows:

[0013] (1) adding the porous graphene suspension into DMF and ultrasonically dispersing for 1-2 h to obtain a dispersion;

[0014] (2) pre-oxidizing the surface of the polyurethane prepolymer: adding concentrated sulfuric acid, sodium chromate and deionized water to the polyurethane prepolymer, fully impregnating, reacting for 10-30 minutes, and then washing with deionized water for 5-10 minutes to obtain a pre-oxidized polyurethane prepolymer; wherein the mass ratio of concentrated sulfuric acid, sodium chromate and deionized water is 100-200:5-15:10-30;

[0015] (3) slowly adding the dispersion obtained in step (1) dropwise to the pre-oxidized polyurethane prepolymer obtained in step (2) in multiple portions, reacting at 80° C. for 1 to 2 hours, adding polyvinyl pyrrolidone, mixing evenly, continuing the reaction for 1 to 2 hours, then cooling to below 40° C., slowly adding an appropriate amount of deionized water under high-speed stirring conditions for emulsification, with the addition of deionized water, the prepolymer is gradually dispersed in the water to form an emulsion; then, adding a certain amount of chain extender (such as ethylenediamine) to the emulsion, continuing the stirring reaction for 30 to 60 minutes, so that the prepolymer is further chain extended to form a high molecular weight polymer molecular chain, thereby obtaining a stable modified polymer.

[0016] The present invention first pre-oxidizes a polyurethane prepolymer using an acidic system composed of chromic acid and sulfuric acid, which can significantly increase the surface roughness and specific surface area of ​​the polyurethane prepolymer and form micropores, thereby facilitating bonding with graphene oxide, forming an interlocking structure, and improving interface bonding strength. In addition, the carbon and oxygen functional groups on the surface of the polyurethane prepolymer are increased, and after bonding with graphene oxide, more amino and hydroxyl active groups can be formed, which provide more active sites for subsequent bonding with functional particles. The oxygen-containing functional groups in the porous graphene provide abundant sites for the formation of hydrogen bonds between the polymer and the porous graphene, thereby avoiding agglomeration or accumulation of the polymer system, and can form more stable bonds with the modified functional particles, thereby improving the dispersion stability and interface compatibility between the polymer and the functional particles. More importantly, a uniformly distributed microporous structure can be formed inside the material, which is conducive to enhancing reflection and scattering, thereby forming electromagnetic wave absorption, thereby exerting a better radiation shielding effect. In addition, the modification treatment by adding graphene oxide can enhance the hydrophobicity of the polymer, ensuring its applicability in humid environments.

[0017] A method for preparing a radiation protection material comprises the following steps:

[0018] S1. After the dried modified functional particles, boron and / or its compound are mixed evenly, 5% coupling agent solution is added, mixed for 15 minutes, and dried at 100 to 150 ° C for 30 to 60 minutes to obtain a shield pretreatment material;

[0019] S2. The shield pretreatment material is mixed with a modified polymer and an antioxidant and added to an internal mixer, heated to 150 to 180°C and plasticized for 5 to 15 minutes;

[0020] S3. The mixed material is placed in a mold and hot-pressed to obtain a radiation-proof material. During hot-pressing, the pressure is 10-15 MPa, the temperature is 150-250°C, and the time is 5-20 min.

[0021] The present invention also provides an application of the radiation protection material in protective products in the fields of medicine and chemical industry.

[0022] Specifically, the protective products include protective clothing, protective gloves, protective blankets, surgical gowns, isolation gowns, clean clothes, surgical towels, isolation cloths or interventional surgical protection packs.

[0023] The technical solutions of the embodiments of the present invention have at least the following advantages and beneficial effects:

[0024] The radiation-proof material of the present invention has good absorption performance for X-rays, and is lead-free and has the advantages of being environmentally friendly and non-toxic. Functional particles are used as the main radiation-absorbing components, and after modification, their compatibility with polymers is significantly improved, and the stability during the preparation process is improved. At the same time, the modification of the polymer allows for more stable bonding with the modified functional particles, resulting in better dispersion stability and interface compatibility between the polymer and the functional particles. More importantly, it can form a uniformly distributed microporous structure inside the material, which is conducive to enhancing reflection and scattering, thereby forming electromagnetic wave absorption, thereby exerting a better ray shielding effect. Moreover, by adding graphene oxide for modification, the hydrophobicity of the polymer can be enhanced, ensuring its applicability in humid environments. DETAILED DESCRIPTION

[0025] To make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are described clearly and completely below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer are used. Where the manufacturer of the reagents or instruments is not specified, all are conventional products that can be purchased commercially.

[0026] The following is a detailed description of a radiation protection material provided by an embodiment of the present invention, and its preparation method and application.

[0027] Example 1

[0028] A radiation protection material, comprising the following components, by weight: 30 parts of modified polyurethane, 60 parts of modified bismuth oxide, 7 parts of boron carbide, 2 parts of Irganox 1010 antioxidant, and 1 part of KH-550 silane coupling agent;

[0029] The modified bismuth oxide is prepared as follows: 100 mL of an ethanol aqueous solution (ethanol to ultrapure water volume ratio of 4:1) is placed in a beaker, the pH is adjusted to 3 with a 0.3 mol / L dilute hydrochloric acid solution, 0.5 g of a KH-570 silane coupling agent is added, and the mixture is stirred and hydrolyzed at room temperature for 50 minutes. Then, 4 g of the dried functional particles are added, and the mixture is ultrasonically treated in an ice bath for 40 minutes. Then, the mixture is heated to 80° C. in an oil bath and stirred at a constant temperature for 3 hours. After the reaction is completed, the mixture is centrifuged, washed, and finally dried in an 80° C. oven to constant weight to obtain the modified functional particles.

[0030] The preparation method of the modified polyurethane is as follows:

[0031] (1) 10 mg of porous graphene powder was dispersed in 10 mL of deionized water to prepare a porous graphene suspension with a concentration of 1 mg / mL, which was then added to 100 mL of DMF and ultrasonically dispersed at 300 W for 1 h to obtain a dispersion;

[0032] (2) 150 g of concentrated sulfuric acid, 7 g of sodium chromate, and 15 g of deionized water were mixed evenly, and then 100 g of polyurethane prepolymer was added to the mixed solution, fully immersed, reacted for 20 min, and then washed with deionized water for 10 min to obtain a pre-oxidized polyurethane prepolymer;

[0033] (3) 10 mL of the dispersion obtained in step (1) was slowly added dropwise to 100 g of the pre-oxidized polymer prepolymer obtained in step (2) in three portions. After reacting at 80° C. for 1 h, 0.5 wt % of polyvinylpyrrolidone was added, mixed evenly, and the reaction was continued for 1 h. The mixture was then cooled to room temperature. Under stirring conditions, 1000 mL of deionized water was slowly added for emulsification to obtain an emulsion. Then, 0.5 wt % of ethylenediamine was added to the emulsion, and the reaction was continued with stirring for 30 min to obtain a modified polymer.

[0034] A method for preparing a radiation protection material comprises the following steps:

[0035] S1. After the dried modified bismuth oxide and boron carbide were mixed, 5% coupling agent solution was added, mixed for 15 minutes, and dried at 120 ° C for 30 minutes to obtain a shield pretreatment material;

[0036] S2. The shield pretreatment material is mixed with modified polyurethane and antioxidant and added to an internal mixer, heated to 160°C and plasticized for 10min;

[0037] S3. The mixed material is placed in a mold and hot-pressed to obtain a radiation-proof material. During hot-pressing, the pressure is 10 MPa, the temperature is 200°C, and the time is 10 min.

[0038] The present invention also provides an interventional surgery protective bag, the inner layer of which is made of the above-mentioned protective material.

[0039] Example 2

[0040] The difference between this embodiment and embodiment 1 is that: a radiation protection material comprises the following components, by weight: 40 parts of modified polyurethane, 70 parts of modified tungsten oxide, 8 parts of boron nitride, 3 parts of Irganox 1010 antioxidant and 1 part of KH-550 silane coupling agent.

[0041] Example 3

[0042] The difference between this embodiment and embodiment 1 is that: a radiation protection material comprises the following components, by weight: 40 parts of modified polyurethane, 70 parts of modified samarium oxide, 8 parts of boron nitride, 3 parts of Irganox 1010 antioxidant and 1 part of KH-550 silane coupling agent.

[0043] Example 4

[0044] The difference between this embodiment and embodiment 1 is that: a radiation protection material comprises the following components, by weight: 50 parts of modified polyurethane, 50 parts of modified lanthanum oxide, 8 parts of boron carbide, 1 part of Irganox 1010 antioxidant and 1 part of KH-550 silane coupling agent.

[0045] Comparative Example 1

[0046] The difference between this comparative example and Example 1 is that: a radiation protection material, including the following components, by weight: 10 parts of modified polyurethane, 10 parts of modified lanthanum oxide, 1 part of boron carbide, 0.1 parts of Irganox 1010 antioxidant and 0.1 parts of KH-550 silane coupling agent.

[0047] Comparative Example 2

[0048] The difference between this comparative example and Example 1 is that: the polymer of the radiation protection material is not modified.

[0049] Comparative Example 3

[0050] The difference between this comparative example and Example 1 is that: the functional particles of the radiation protection material are not modified.

[0051] Experimental Example 1

[0052] The performance X-ray shielding test was performed on the interventional surgical kits obtained in each embodiment and comparative example. The test was performed three times respectively, and the average value was taken. The test results are shown in Table 1.

[0053] Test method: In accordance with GBZ / T 147-2002 "Determination of attenuation properties of X-ray protective materials", the operation is as follows: Place the detector 3.0mm away from the X-ray (120kV), with the rays incident perpendicular to the detector surface. Measure the dose rate of the interventional surgical package samples obtained without sample and after exposure to the samples in each embodiment and comparative example. Calculate the lead equivalent of the sample based on the shielding rate of the standard lead sheet.

[0054] Table 1 - X-ray shielding test results

[0055] Lead equivalent / mmPb Example 1 0.16 Example 2 0.15 Example 3 0.16 Example 4 0.16 Comparative Example 1 0.10 Comparative Example 2 0.03 Comparative Example 3 0.08

[0056] As shown in Table 1, the radiation-proof material produced by the present invention, when used in protective products, exhibits excellent radiation protection, enhancing radiation protection during surgery and ensuring the safety of medical personnel and patients. In embodiments of the present invention, by adding radiation-proof material to the inner surface of an interventional surgical kit, the radiation-proof material can be used to alter the scattering direction and path of X-rays, reducing the generation and propagation of scattered radiation and thereby suppressing scattering.

[0057] However, in the radiation protection material of Comparative Example 1, since the ratios of the raw material components are not within the scope of the technical solution of the present invention, the overall synergistic effect between the components is poor, and a good radiation protection effect cannot be exerted;

[0058] In Comparative Example 2, since the polymer was not modified, the polymer system agglomerated, and the binding force between the polymer and the functional particles was poor and the dispersion was unstable. This made it difficult for the functional particles to stably exert their radiation protection effect and form good reflection and scattering inside the material, making it difficult to exert a good X-ray shielding effect.

[0059] In Comparative Example 3, since the functional particles were not modified, the compatibility between the functional particles and the polymer was poor, which greatly affected the shielding performance of the functional particles.

[0060] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Those skilled in the art will readily appreciate that various modifications and variations of the present invention are possible. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present invention shall be included within the scope of protection of the present invention.

Claims

1. A radiation protection material, characterized in that: The invention comprises the following components in parts by weight: 15 to 60 parts of modified polymer, 40 to 80 parts of modified functional particles, and 6.5 to 15 parts of additives; the additives comprise: 5 to 10 parts of boron and / or its compounds, 1 to 3 parts of antioxidant, and 0.5 to 2 parts of coupling agent.

2. The radiation protection material according to claim 1, characterized in that: The polymer is polyurethane.

3. The radiation protection material according to claim 1, characterized in that: The functional particles include one or more of bismuth, samarium, barium, lanthanum, gadolinium, tantalum, tungsten and compounds thereof.

4. The radiation protection material according to claim 1, characterized in that The modified functional particles are prepared by adding a pH regulator to an ethanol aqueous solution to adjust the solution pH to 3-4, adding a silane coupling agent, stirring and hydrolyzing at room temperature, then adding the dried functional particles and mixing them evenly, heating the mixture, centrifuging, washing, and drying to obtain the modified functional particles.

5. The radiation protection material according to claim 1, characterized in that: The preparation method of the modified polymer is as follows: (1) adding the porous graphene suspension into DMF and ultrasonically dispersing the mixture for a period of time to obtain a dispersion; (2) pre-oxidizing the surface of the polyurethane prepolymer: adding concentrated sulfuric acid, sodium chromate and deionized water to the polyurethane prepolymer, fully impregnating, reacting for 10-30 minutes, and then washing with deionized water for 5-10 minutes to obtain a pre-oxidized polyurethane prepolymer; (3) slowly adding the dispersion obtained in step (1) dropwise to the pre-oxidized polyurethane prepolymer obtained in step (2) in multiple portions, reacting for a period of time, adding polyvinyl pyrrolidone, mixing evenly, continuing to react for a period of time, cooling, and slowly adding deionized water under stirring conditions to obtain an emulsion after a period of time; then, adding a chain extender to the emulsion, continuing to stir and react for a period of time to obtain a stable modified polymer.

6. The radiation protection material according to claim 5, characterized in that: The concentration of the porous graphene suspension is 1-3 mg / mL; the liquid-to-solid ratio of the dispersion to the polymer prepolymer is 1:10-20 mL / g.

7. A method for preparing the radiation protection material according to any one of claims 1 to 6, characterized in that: The following steps are involved: S1. After the dried modified functional particles, boron and / or its compound are mixed uniformly, a coupling agent solution is added, mixed, and dried to obtain a shield pretreatment material; S2. The shield pretreatment material is mixed with a modified polymer and an antioxidant and added to an internal mixer, and the temperature is raised for a period of time; S3. Place the mixed material in a mold and perform hot pressing to obtain a radiation shielding material.

8. The method for preparing the radiation protection material according to claim 7, characterized in that: During drying treatment: drying at 100-150°C for 30-60 minutes; during heating treatment: plasticizing at 150-180°C for 5-15 minutes; during hot pressing molding: pressure is 10-15MPa, temperature is 150-250°C, and time is 5-20 minutes.

9. Use of the radiation protection material according to any one of claims 1 to 6 in protective products in the fields of medicine and chemical industry.