Environment-friendly flexible anti-radiation composite material and preparation method thereof

Abstract

The invention discloses an environment-friendly flexible wearable anti-radiation composite material and a preparation method thereof. The anti-radiation composite material comprises: a support layer made of a high polymer material; the ionizing radiation shielding layer A is arranged on the supporting layer in a stacked mode, and the ionizing radiation shielding layer A is prepared from, by weight, a polymer base material, anti-radiation composite powder, a binding agent and an auxiliary agent; the flexible ionizing radiation shielding layer B is arranged on the ionizing radiation shielding layer A in a stacked mode, and the flexible ionizing radiation shielding layer B is a fiber material containing barium ions obtained through sulfonation reaction and ion exchange reaction. The anti-radiation composite material provided by the invention is flexible, non-toxic and wearable, has efficient ionizing radiation shielding performance, and can be used for manufacturing protective clothing, protective tents and the like.

Description

Technical Field

[0001] The present invention relates to the technical field of preparation of radiation protection materials, and in particular to a non-toxic, environmentally friendly, flexible, wearable radiation protection composite material and a preparation method thereof. Background Art

[0002] Radiation is now widely used in various fields, and high-energy radiation significantly increases the probability of human exposure. Long-term exposure to radiation can lead to long-term or short-term biological effects in humans, such as gene mutations, cancer, and organ failure. Therefore, effective protective measures must be taken to reduce the harm of radiation to the human body.

[0003] With the advancement of nuclear protection technology, traditional radiation shielding materials containing lead and its oxides no longer meet increasingly stringent environmental and health safety standards. Lead-based radiation shielding materials suffer from drawbacks such as excessive weight, inflexibility, and human toxicity. Furthermore, they have a weak absorption band between 40 and 88 keV. These issues limit their application in medical, industrial testing, and nuclear power facilities. Therefore, the development of a lead-free, flexible, and efficient radiation shielding material is crucial for promoting technological innovation. Summary of the Invention

[0004] The present invention provides a non-toxic, environmentally friendly, flexible, wearable radiation-proof composite material and its preparation method, which provides efficient ionizing radiation protection. The radiation-proof composite material can effectively protect against various radiation forms, including alpha, beta, gamma rays, X-rays, and neutrons, and can be used to manufacture radiation protection products such as protective clothing, protective tents, and protective screens.

[0005] The technical solution adopted in the present invention is as follows:

[0006] An environmentally friendly flexible radiation-proof composite material comprises a support layer, an ionizing radiation shielding layer, and a flexible ionizing radiation shielding layer. The support layer is made of a polymer material; the ionizing radiation shielding layer is laminated on the support layer; the ionizing radiation shielding layer comprises, by weight, 5 to 50 parts of a polymer matrix material, 10 to 80 parts of a radiation-resistant composite powder, 1 to 15 parts of an auxiliary agent, and 1 to 15 parts of a binder; the flexible ionizing radiation shielding layer is laminated on the ionizing radiation shielding layer; the flexible ionizing radiation shielding layer is formed by firstly subjecting a fiber material to a sulfonation reaction with a sulfonating agent to form a sulfonated fiber material; and then reacting the sulfonated fiber material with a barium ion-containing solution to obtain the flexible ionizing radiation shielding layer.

[0007] The support layer adopts at least one of the polymer materials selected from Oxford cloth, rubber, synthetic fiber and engineering plastics, thermoplastics, cotton cloth, stretch cloth, leather, flexible textiles, natural and special materials, and lead-free PEEK resin.

[0008] The synthetic fibers and engineering plastics are polyamide, poly(p-phenylene terephthalamide), polyethylene terephthalate, poly(butylene terephthalate), and polyethylene naphthalate;

[0009] The thermoplastic material is polyethylene or polypropylene;

[0010] The natural and special materials are polyvinyl alcohol, polyacrylonitrile, cellulose, and protein;

[0011] The rubber is silicone rubber, styrene-butadiene rubber, chlorosulfonated polyethylene, chloroprene rubber, organic silicone rubber, and EPDM rubber.

[0012] The polymer matrix material is selected from at least one of polyurethane, polyvinyl alcohol, polyacrylonitrile, polycarbonate, acrylonitrile-butadiene-styrene copolymer, epoxy resin, polyacrylic acid, high-density polyethylene, medium-density polyethylene, low-density polyethylene, silicone resin, alkyd resin, phenolic resin, polypropylene, polyvinyl chloride, polystyrene, polystyrene-ethylene-butadiene-styrene, cellulose and protein.

[0013] The radiation-proof composite powder is selected from at least one of bismuth, tantalum, zirconium, niobium and their metal compounds; or selected from at least one of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium and their rare earth-based compounds.

[0014] The binder is a coupling agent, which is at least one of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, an aluminum-titanium composite coupling agent, and a phosphate coupling agent.

[0015] The method for preparing the above-mentioned radiation-proof composite material comprises the following steps:

[0016] (1) Add the polymer matrix material and the radiation protection composite powder into a high-speed mixer at a preset mass ratio and mix at high speed. When the materials are evenly mixed, reduce the stirring speed to 50% of the original speed and then add the thickener and defoamer. The preset mass ratio is 1: (2-8) and the mixing time is 5 min to 60 min.

[0017] (2) Combine the polymer matrix material with the PVC artificial leather, connect it to the PVC artificial leather coating equipment through human and mechanical transmission, and place it in an oven for drying;

[0018] (3) The mixed coating is scraped onto the pre-adjusted PVC polymer matrix material through a scraper, and the composite material is placed in an oven and kept still for heat preservation, and then scraped twice; the mixed coating is scraped onto the dried coating, and the composite material is placed in an oven and kept still for heat preservation, and then scraped three times; the mixed coating is scraped onto the dried coating, and the composite material is placed in an oven and kept still for heat preservation, and then enters the composite operation link;

[0019] (4) The coated product is evenly compounded with the lining cloth under the double-roll co-extrusion action of the compounding machine and then put into the oven for further drying;

[0020] (5) Replace the polymer matrix material with free paper and repeat the process of 3-4 to produce an intermediate;

[0021] (6) The free composite material and the polymer matrix material composite material are compounded for a second time under the operation of a compounding machine, and the free paper is peeled off during the compounding process to form a uniform composite material.

[0022] The preparation of the ionizing radiation shielding layer comprises the following steps:

[0023] (1) A sulfonating agent and an organic solvent are mixed in a preset mass ratio to prepare a mixed solution, and then a fiber material is immersed in the mixed solution in a preset solid-liquid mass ratio to perform a sulfonation reaction to obtain a sulfonated fiber material, wherein the sulfonating agent is aminosulfonic acid, the organic solvent is N,N-dimethylformamide, the fiber material is pure cotton fiber, the preset mass ratio is 1:(12-38), the preset solid-liquid mass ratio is 1:(35-42), the sulfonation reaction temperature is 60-130°C, and the sulfonation reaction time is greater than or equal to 10 minutes;

[0024] (2) Immersing the sulfonated fiber material in a 0.01-0.15 mol / L barium ion solution for reaction to obtain the X-ray shielding material; the barium ion solution is preferably a barium hydroxide solution, a barium chloride solution or a barium nitrate solution; the reaction temperature in step 2 is 30-80°C, the reaction time is greater than or equal to 15 minutes, and the mass ratio of the solute in the barium ion solution to the sulfonated fiber material is (0.5-5):1.

[0025] The preparation of the shielding slurry includes the following steps: pre-treating the surface of the radiation-proof composite powder with the coupling agent to obtain pre-treated radiation-proof composite powder; and mixing the pre-treated composite powder with a polymer matrix material to obtain the shielding slurry.

[0026] In summary, the present invention has the following beneficial effects:

[0027] This invention utilizes a polymer material as a support layer, upon which an ionizing radiation shielding layer A and a flexible ionizing radiation shielding layer B are placed. By optimizing the composition of these two layers, the composite material achieves highly effective radiation protection while also possessing the advantages of being non-toxic, environmentally friendly, flexible, and wearable. This composite material not only meets the requirements of high strength and lightweight, but also exhibits excellent flexibility and wearability, significantly enhancing its versatility and flexibility in practical applications. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1The scanning electron microscope image of the radiation-proof powder bismuth powder of the present invention is shown.

[0029] Figure 2 The scanning electron microscope image of the radiation-resistant zirconium powder of the present invention is shown. DETAILED DESCRIPTION

[0030] First, a radiation-proof composite material according to a first aspect of an embodiment of the present invention is described. The radiation-proof composite material includes a support layer, an ionizing radiation shielding layer A, and a flexible ionizing radiation shielding layer B.

[0031] Wherein, the supporting layer adopts polymer material.

[0032] The ionizing radiation shielding layer A is arranged on the supporting layer. The ionizing radiation shielding layer A comprises 5-50 parts of a polymer matrix material, 10-80 parts of a radiation-resistant composite powder, 1-15 parts of an auxiliary agent and 1-15 parts of a binder in parts by weight.

[0033] The flexible ionizing radiation shielding layer B is provided on the ionizing radiation shielding layer A. The flexible ionizing radiation shielding layer B includes a sulfonation reaction and an ion exchange reaction.

[0034] The radiation protection composite material of the embodiment of the present invention, as an example, the supporting layer uses a polymer material of at least one of Oxford cloth, rubber, synthetic fiber and engineering plastics, thermoplastics, cotton cloth, stretch fabric, leather, flexible textiles, natural and special materials, and PEEK resin that does not contain lead.

[0035] In the radiation-proof composite material of the embodiment of the present invention, the radiation-proof composite powder in the ionizing radiation shielding layer A is selected from at least one of bismuth, tantalum, zirconium, niobium and their metal compounds; or selected from at least one of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium and their rare earth-based compounds.

[0036] For cost-effectiveness considerations, radiation-proof composite powders with a particle size in the range of 50~100nm are selected.

[0037] In the radiation-proof composite material of the embodiment of the present invention, the polymer matrix material of the ionizing radiation shielding layer A is at least one of polyurethane, polyvinyl alcohol, polyacrylonitrile, polycarbonate, acrylonitrile-butadiene-styrene copolymer, epoxy resin, polyacrylic acid, high-density polyethylene, medium-density polyethylene, low-density polyethylene, silicone resin, alkyd resin, phenolic resin, polypropylene, polyvinyl chloride, polystyrene, polystyrene-ethylene-butadiene-styrene, cellulose and protein.

[0038] The polymer matrix material of the ionizing radiation shielding layer A is not limited to the above materials, as long as the radiation protection composite powder can be uniformly dispersed in the ionizing radiation shielding layer A and stably attached to the surface of the flexible ionizing radiation shielding layer B.

[0039] In the radiation-proof composite material of the embodiment of the present invention, the binder in the ionizing radiation shielding layer A is a coupling agent, and the coupling agent is at least one of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, an aluminum-titanium composite coupling agent, and a phosphate coupling agent.

[0040] The present invention further provides a method for preparing a radiation-proof composite material, which comprises the following steps:

[0041] S100, providing a support layer, wherein the support layer is made of polymer material.

[0042] S200, preparing a shielding slurry, which includes, by weight, 5-50 parts of a polymer matrix material, 10-80 parts of an anti-radiation composite powder, 1-15 parts of an auxiliary agent, and 1-15 parts of a binder.

[0043] Prepare the ionizing radiation shielding layer A, step S300 includes:

[0044] S310, a coupling agent is used as a binder, and the surface of the radiation-proof composite powder is pretreated by the coupling agent to obtain a pretreated radiation-proof powder.

[0045] S320, adding the polymer matrix material and the radiation protection composite powder into a high-speed mixer at a preset mass ratio, mixing at high speed, and adding the additive after the materials are evenly mixed and reducing the stirring speed to 50% of the original speed; the preset mass ratio is 1: (2-8), and the mixing time is 5 minutes to 60 minutes.

[0046] S330 combines the polymer matrix material with PVC artificial leather, connects it to the PVC artificial leather scraping equipment through human and mechanical transmission, and puts it into the oven for drying.

[0047] S340, the mixed coating is applied to the pre-adjusted PVC base material by a scraper, the composite material is placed in an oven and kept still for heat preservation, and a second scraping is performed.

[0048] S350: scrape the mixed coating onto the dried coating, place it in an oven and keep it still for three times.

[0049] S360, apply the mixed coating on the dried coating, put it into the oven and keep it still to keep warm, and then carry out the composite operation.

[0050] S370, the coated product is evenly compounded with the lining cloth under the double-roll co-extrusion action of the compounding machine, and then enters the oven for further drying.

[0051] S380, the polymer matrix material is replaced with free paper, and the process of S340 to S370 is repeated to produce an intermediate.

[0052] S390, the free composite material and the polymer matrix material composite material are compounded for a second time under the operation of a compounding machine, and the free paper is peeled off during the compounding process to form a uniform composite material.

[0053] Additives may include defoamers, which can reduce or eliminate the chemical substances that form foam in the liquid, thereby improving the stability and uniformity of the shielding material, thereby enhancing the shielding effect. Defoamers can be silicone oil defoamers, mineral oil defoamers, polyether defoamers, alcohol defoamers, etc.

[0054] The additives may also include a thickener, which can increase the viscosity of the shielding slurry, thereby improving the radiation shielding effect. The thickener may be sodium alginate, hydroxypropyl methylcellulose, polyacrylate, polyvinyl alcohol, etc.

[0055] S400, coating the shielding slurry on the support layer, and drying the ionizing radiation shielding layer A.

[0056] In step S400 , the drying process is performed at a temperature of 70° C. to 145° C. and for a time of 3 minutes to 30 minutes.

[0057] Prepare the flexible ionizing radiation shielding layer B, step S500 includes:

[0058] S510, mixing the sulfonating agent and the organic solvent in a mass ratio of 1:(12-38) to obtain a mixed solution.

[0059] S520, immersing the fiber material in a mixed solution according to a preset solid-liquid mass ratio to perform a sulfonation reaction.

[0060] In step S520, the sulfonating agent is aminosulfonic acid, the organic solvent is N,N-dimethylformamide, the fiber material is pure cotton fiber, the preset solid-liquid mass ratio is 1:(35~42), the sulfonation reaction temperature is 60℃~130℃, and the sulfonation reaction time is greater than or equal to 15 minutes.

[0061] S530, immersing the sulfonated fiber material in a 0.01-0.15 mol / L barium ion-containing solution to perform an ion exchange reaction.

[0062] In step S530 , the barium ion-containing solution is preferably a barium hydroxide solution, a barium chloride solution, or a barium nitrate solution.

[0063] Example 1

[0064] S100, Oxford cloth is used as the supporting layer.

[0065] S200, preparing an ionizing radiation shielding layer A:

[0066] S210, performing surface pretreatment on the tantalum powder by using a silane coupling agent to obtain a pretreated radiation-proof powder.

[0067] S220, add polyurethane and tantalum powder into a high-speed mixer at a mass ratio of 1:2.5, mix at high speed for 30 minutes, and when the materials are evenly mixed, reduce the stirring speed to 50% of the original speed, then add thickener and defoaming agent, and observe the materials until they are uniform.

[0068] S230 combines Oxford cloth with 130m long PVC artificial leather, connects it to the PVC artificial leather scraping equipment through human and mechanical transmission, turns on the oven and sets the temperature to 95℃, and turns on the equipment after the equipment performance is stable and the temperature is constant.

[0069] S240: The mixed coating is applied to a pre-adjusted PVC Oxford cloth using a doctor blade at a pulling speed of 3 m / min. The initial coating thickness is 0.45 mm. The coating is kept in a static state for 5 minutes in an oven (the oven length is 25 m) while the hot air circulation system of the oven is turned on. After drying, the coating thickness is measured to be 0.22 mm, and a second doctor blade coating is performed.

[0070] S250, the mixed coating is scraped on the dried coating, the pulling speed is controlled at 2.4m / min, the thickness is increased to 0.65mm, and it enters the oven and rests for 5 minutes (the oven length is 20m). At the same time, the hot air circulation system of the oven is turned on. After drying, the coating thickness is 0.48mm, and three more scraping operations are performed.

[0071] S260: Apply the mixed coating on the dried coating with a scraper. The pulling speed is controlled at 4m / min, the oven temperature is set at 95°C, and the hot air circulation system of the oven is turned on. The coating is left to stand for 3 minutes (the oven length is 25m). After drying, the coating thickness is 0.7mm, and then the composite operation phase is entered.

[0072] S270, the coated product is evenly compounded with the lining cloth under the double-roll co-extrusion action of the laminating machine (double-roll temperature 135℃), and then enters the oven for further drying. The oven temperature is 115℃ (oven length is 15m) and the pulling speed is 3m / min.

[0073] S280, replace the Oxford cloth with free paper, repeat the operation process of S230 to S260 to produce the intermediate.

[0074] S290, the free composite material and the Oxford cloth composite material are compounded for the second time under the operation of the compounding machine to produce a product that meets the requirements. The free paper is peeled off during the compounding process to form a uniform composite material.

[0075] S300, preparing a flexible ionizing radiation shielding layer B:

[0076] S310, aminosulfonic acid and N, N-dimethylformamide are mixed in a mass ratio of 1:12, and a weight of 210g / m 2 The pure cotton fiber was added to the mixed solution and reacted in an oil bath at 100°C for 80 minutes.

[0077] S320, taking out the pure cotton fiber, adjusting the pH value of the pure cotton fiber to neutral, immersing it in a 0.15 mol / L, 70°C barium hydroxide solution, reacting for 150 minutes, and then taking it out. After adjusting the pH value of the pure cotton fiber to neutral, it is placed in a 40°C oven to dry.

[0078] S400, placing the flexible ionizing radiation shielding layer B on the ionizing radiation shielding layer A, and adopting a lamination technology to obtain a composite material.

[0079] Example 2

[0080] S100, neoprene is selected as the supporting layer.

[0081] S200, preparing an ionizing radiation shielding layer A:

[0082] S210, performing surface pretreatment on the bismuth powder by using a silane coupling agent to obtain a pretreated radiation-proof powder.

[0083] S220, polyvinyl alcohol and bismuth powder are added into a high-speed mixer in a mass ratio of 1:2.5, and mixed at high speed for 30 minutes. When the materials are evenly mixed, the stirring speed is reduced to 50% of the original speed, and then the thickener and defoaming agent are added. The materials are observed until they are uniform.

[0084] S230 combines neoprene with 130m long PVC artificial leather, connects it to the PVC artificial leather scraping equipment through human and mechanical transmission, turns on the oven and sets the temperature to 100℃, and turns on the equipment after the equipment performance is stable and the temperature is constant.

[0085] S240: The mixed coating is applied to the pre-adjusted PVC neoprene by a scraper at a pulling speed of 3 m / min. The initial scraping thickness is 0.45 mm. The coating enters the oven and is kept at rest for 5 minutes (the oven length is 25 m). The hot air circulation system of the oven is turned on at the same time. After drying, the coating thickness is measured to be 0.22 mm, and a second scraping is performed.

[0086] S250, the mixed coating is scraped on the dried coating, the pulling speed is controlled at 2.4m / min, the thickness is increased to 0.65mm, and it enters the oven and rests for 5 minutes (the oven length is 20m). At the same time, the hot air circulation system of the oven is turned on. After drying, the coating thickness is 0.48mm, and three more scraping operations are performed.

[0087] S260, the mixed coating is scraped onto the dried coating, the pulling speed is controlled at 4m / min, the oven temperature is set at 100℃, and the hot air circulation system of the oven is turned on. It is left to stand for 3 minutes (the oven length is 25m). After drying, the coating thickness is 0.7mm, and then the composite operation phase is entered.

[0088] S270, the coated product is evenly compounded with the lining cloth under the double-roll co-extrusion action of the laminating machine (double-roll temperature 135℃), and then enters the oven for further drying. The oven temperature is 120℃ (oven length is 15m) and the pulling speed is 3m / min.

[0089] S280, replacing the chloroprene rubber with free paper, repeating the operation process of S230 to S260 to produce the intermediate.

[0090] S290, the free compound material and the chloroprene rubber compound material are compounded for the second time under the operation of the compounding machine to produce a product that meets the requirements. The free paper is peeled off during the compounding process to form a uniform composite material.

[0091] S300, preparing a flexible ionizing radiation shielding layer B:

[0092] S310, aminosulfonic acid and N, N-dimethylformamide are mixed in a mass ratio of 1:15, and a weight of 210g / m 2 The pure cotton fiber was added to the mixed solution and reacted in an oil bath at 105°C for 90 minutes.

[0093] S320, taking out the pure cotton fiber, adjusting the pH value of the pure cotton fiber to neutral, immersing it in a 0.15 mol / L, 70°C barium hydroxide solution, reacting for 150 minutes, and then taking it out. After adjusting the pH value of the pure cotton fiber to neutral, it is placed in a 40°C oven to dry.

[0094] S400, placing the flexible ionizing radiation shielding layer B on the ionizing radiation shielding layer A, and adopting a lamination technology to obtain a composite material.

[0095] Example 3

[0096] S100, polyethylene is selected as the support layer.

[0097] S200, preparing an ionizing radiation shielding layer A:

[0098] S210, performing surface pretreatment on the zirconium powder using a silane coupling agent to obtain a pretreated radiation-proof powder.

[0099] S220, add epoxy resin and zirconium powder in a mass ratio of 1:2 into a high-speed mixer and mix at high speed for 30 minutes. When the materials are evenly mixed, reduce the stirring speed to 50% of the original speed, then add thickener and defoaming agent, and observe the materials until they are uniform.

[0100] S230 combines polyethylene with 130m long PVC artificial leather, connects it to the PVC artificial leather scraping equipment through human and mechanical transmission, turns on the oven and sets the temperature to 105℃, and turns on the equipment after the equipment performance is stable and the temperature is constant.

[0101] S240: The mixed coating is applied to the pre-adjusted PVC polyethylene using a scraper at a pulling speed of 3 m / min. The initial scraping thickness is 0.45 mm. The coating is kept stationary and warm in the oven for 5 minutes (the oven length is 25 m). The hot air circulation system of the oven is turned on at the same time. After drying, the coating thickness is measured to be 0.22 mm, and a second scraping is performed.

[0102] S250, the mixed coating is scraped on the dried coating, the pulling speed is controlled at 2.4m / min, the thickness is increased to 0.65mm, and it enters the oven and rests for 5 minutes (the oven length is 20m). At the same time, the hot air circulation system of the oven is turned on. After drying, the coating thickness is 0.48mm, and three more scraping operations are performed.

[0103] S260, apply the mixed coating on the dried coating, control the pulling speed to 4m / min, set the oven temperature to 105℃, and turn on the hot air circulation system of the oven. Let it stand for 3 minutes (the oven length is 25m). After drying, the coating thickness is 0.7mm, and then enter the composite operation link.

[0104] S270, the coated product is evenly compounded with the lining cloth under the double-roll co-extrusion action of the laminating machine (double-roll temperature 135℃), and then enters the oven for further drying. The oven temperature is 125℃ (oven length is 15m) and the pulling speed is 3m / min.

[0105] In S280, polyethylene is replaced with free paper, and the operation process of S230 to S260 is repeated to produce an intermediate.

[0106] S290, the free compound material and the polyethylene compound material are compounded for the second time under the operation of the compounding machine to produce a product that meets the requirements. The free paper is peeled off during the compounding process to form a uniform composite material.

[0107] S300, preparing a flexible ionizing radiation shielding layer B:

[0108] S310, aminosulfonic acid and N, N-dimethylformamide are mixed in a mass ratio of 1:18, and a weight of 210g / m 2 The pure cotton fiber was added to the mixed solution and reacted in an oil bath at 110°C for 90 minutes.

[0109] S320, taking out the pure cotton fiber, adjusting the pH value of the pure cotton fiber to neutral, immersing it in a 0.15 mol / L, 70°C barium hydroxide solution, reacting it for 160 minutes, and then taking it out. After adjusting the pH value of the pure cotton fiber to neutral, it is placed in a 40°C oven to dry.

[0110] S400, placing the flexible ionizing radiation shielding layer B on the ionizing radiation shielding layer A, and adopting a lamination technology to obtain a composite material.

[0111] Example 4

[0112] S100, Oxford cloth is used as the supporting layer.

[0113] S200, preparing an ionizing radiation shielding layer A:

[0114] S210, performing surface pretreatment on bismuth powder and tantalum powder using a silane coupling agent to obtain pretreated radiation-proof powder.

[0115] S220, add epoxy resin, bismuth powder and tantalum powder in a mass ratio of 1:0.5:1.5 into a high-speed blender and mix at high speed for 30 minutes. When the materials are evenly mixed, reduce the stirring speed to 50% of the original speed, then add thickener and defoaming agent, and observe the materials until they are uniform.

[0116] S230 combines Oxford cloth with 130m long PVC artificial leather, connects it to the PVC artificial leather scraping equipment through human and mechanical transmission, turns on the oven and sets the temperature to 110℃, and turns on the equipment after the equipment performance is stable and the temperature is constant.

[0117] S240: The mixed coating is applied to a pre-adjusted PVC Oxford cloth using a doctor blade at a pulling speed of 3 m / min. The initial coating thickness is 0.55 mm. The coating is kept in a static state for 5 minutes in an oven (the oven length is 25 m) while the hot air circulation system of the oven is turned on. After drying, the coating thickness is measured to be 0.32 mm, and a second doctor blade coating is performed.

[0118] S250, the mixed coating is scraped on the dried coating, the pulling speed is controlled at 2.4m / min, the thickness is increased to 0.85mm, and it enters the oven and rests for 5 minutes (the oven length is 20m). At the same time, the hot air circulation system of the oven is turned on. After drying, the coating thickness is 0.58mm, and three more scraping operations are performed.

[0119] S260, apply the mixed coating on the dried coating, control the pulling speed to 4m / min, set the oven temperature to 110℃, and turn on the hot air circulation system of the oven. Let it stand for 3 minutes (the oven length is 25m). After drying, the coating thickness is 0.8mm, and then enter the composite operation link.

[0120] S270, the coated product is evenly compounded with the lining cloth under the double-roll co-extrusion action of the laminating machine (double-roll temperature 135℃), and then enters the oven for further drying. The oven temperature is 125℃ (oven length is 15m) and the pulling speed is 3m / min.

[0121] S280, replace the Oxford cloth with free paper, repeat the operation process of S230 to S260 to produce the intermediate.

[0122] S290, the free composite material and the Oxford cloth composite material are compounded for the second time under the operation of the compounding machine to produce a product that meets the requirements. The free paper is peeled off during the compounding process to form a uniform composite material.

[0123] S300, preparing a flexible ionizing radiation shielding layer B:

[0124] S310, aminosulfonic acid and N, N-dimethylformamide are mixed in a mass ratio of 1:20, and a weight of 210g / m 2 The pure cotton fiber was added to the mixed solution and reacted in an oil bath at 115°C for 90 minutes.

[0125] S320, taking out the pure cotton fiber, adjusting the pH value of the pure cotton fiber to neutral, immersing it in a 0.15 mol / L, 70°C barium hydroxide solution, reacting it for 170 minutes, and then taking it out. After adjusting the pH value of the pure cotton fiber to neutral, it is placed in a 40°C oven to dry.

[0126] S400, placing the flexible ionizing radiation shielding layer B on the ionizing radiation shielding layer A, and adopting a lamination technology to obtain a composite material.

[0127] Example 5

[0128] S100, styrene-butadiene rubber is used as the supporting layer.

[0129] S200, preparing an ionizing radiation shielding layer A:

[0130] S210, performing surface pretreatment on bismuth powder and tantalum powder using a silane coupling agent to obtain pretreated radiation-proof powder.

[0131] S220, add polyurethane, bismuth powder and tantalum powder in a mass ratio of 1:1:3 into a high-speed mixer and mix at high speed for 30 minutes. When the materials are evenly mixed, reduce the stirring speed to 50% of the original speed, then add thickener and defoaming agent, and observe the materials until they are uniform.

[0132] S230 combines styrene-butadiene rubber with 130m long PVC artificial leather, connects it to the PVC artificial leather coating equipment through human and mechanical transmission, turns on the oven and sets the temperature to 115℃, and turns on the equipment after the equipment performance is stable and the temperature is constant.

[0133] S240: The mixed coating is applied to the pre-adjusted PVC styrene-butadiene rubber by a scraper at a pulling speed of 3 m / min. The initial scraping thickness is 0.55 mm. The coating enters the oven and is kept still for 5 minutes (the oven length is 25 m). The hot air circulation system of the oven is turned on at the same time. After drying, the coating thickness is measured to be 0.32 mm, and a second scraping is performed.

[0134] S250, the mixed coating is scraped on the dried coating, the pulling speed is controlled at 2.4m / min, the thickness is increased to 0.85mm, and it enters the oven and rests for 5 minutes (the oven length is 20m). At the same time, the hot air circulation system of the oven is turned on. After drying, the coating thickness is 0.58mm, and three more scraping operations are performed.

[0135] S260, apply the mixed coating on the dried coating, control the pulling speed to 4m / min, set the oven temperature to 115℃, and turn on the hot air circulation system of the oven. Let it stand for 3 minutes (the oven length is 25m). After drying, the coating thickness is 0.8mm, and then enter the composite operation link.

[0136] S270, the coated product is evenly compounded with the lining cloth under the double-roll co-extrusion action of the laminating machine (double-roll temperature 135℃), and then enters the oven for further drying. The oven temperature is 130℃ (oven length is 15m) and the pulling speed is 3m / min.

[0137] S280: Replace the styrene-butadiene rubber with free paper and repeat the operation of S230 to S260 to produce an intermediate.

[0138] S290, the free compound material and the styrene-butadiene rubber compound material are compounded for the second time under the operation of the compounding machine to produce a product that meets the requirements. The free paper is peeled off during the compounding process to form a uniform composite material.

[0139] S300, preparing a flexible ionizing radiation shielding layer B:

[0140] S310, aminosulfonic acid and N, N-dimethylformamide are mixed in a mass ratio of 1:20, and a weight of 210g / m 2 The pure cotton fiber was added into the mixed solution and reacted in an oil bath at 120°C for 90 minutes.

[0141] S320, taking out the pure cotton fiber, adjusting the pH value of the pure cotton fiber to neutral, immersing it in a 0.15 mol / L, 70°C barium hydroxide solution, reacting it for 170 minutes, and then taking it out. After adjusting the pH value of the pure cotton fiber to neutral, it is placed in a 40°C oven to dry.

[0142] S400, placing the flexible ionizing radiation shielding layer B on the ionizing radiation shielding layer A, and adopting a lamination technology to obtain a composite material.

[0143] Example 6

[0144] S100, neoprene is selected as the supporting layer.

[0145] S200, preparing an ionizing radiation shielding layer A:

[0146] S210, performing surface pretreatment on zirconium powder and lanthanum powder using a silane coupling agent to obtain pretreated radiation-proof powder.

[0147] S220, add epoxy resin, zirconium powder and lanthanum powder in a mass ratio of 1:1:3 into a high-speed mixer and mix at high speed for 30 minutes. When the materials are evenly mixed, reduce the stirring speed to 50% of the original speed, then add thickener and defoaming agent, and observe the materials until they are uniform.

[0148] S230 combines neoprene with 130m long PVC artificial leather, connects it to the PVC artificial leather scraping equipment through human and mechanical transmission, turns on the oven and sets the temperature to 95℃, and turns on the equipment after the equipment performance is stable and the temperature is constant.

[0149] S240: The mixed coating is applied to the pre-adjusted PVC neoprene by a scraper at a pulling speed of 3 m / min. The initial scraping thickness is 0.55 mm. The coating enters the oven and is kept still for 5 minutes (the oven length is 25 m). The hot air circulation system of the oven is turned on at the same time. After drying, the coating thickness is measured to be 0.32 mm, and a second scraping is performed.

[0150] S250, the mixed coating is scraped on the dried coating, the pulling speed is controlled at 2.4m / min, the thickness is increased to 0.85mm, and it enters the oven and rests for 5 minutes (the oven length is 20m). At the same time, the hot air circulation system of the oven is turned on. After drying, the coating thickness is 0.58mm, and three more scraping operations are performed.

[0151] S260, apply the mixed coating on the dried coating, control the pulling speed to 4m / min, set the oven temperature to 95℃, and turn on the hot air circulation system of the oven. Let it stand for 3 minutes (the oven length is 25m). After drying, the coating thickness is 0.8mm, and then enter the composite operation link.

[0152] S270, the coated product is evenly compounded with the lining cloth under the double-roll co-extrusion action of the laminating machine (double-roll temperature 135℃), and then enters the oven for further drying. The oven temperature is 115℃ (oven length is 15m) and the pulling speed is 3m / min.

[0153] S280, replacing the chloroprene rubber with free paper, repeating the operation process of S230 to S260 to produce the intermediate.

[0154] S290, the free compound material and the chloroprene rubber compound material are compounded for the second time under the operation of the compounding machine to produce a product that meets the requirements. The free paper is peeled off during the compounding process to form a uniform composite material.

[0155] S300, preparing a flexible ionizing radiation shielding layer B:

[0156] S310, sulfamic acid and N, N-dimethylformamide are mixed in a mass ratio of 1:25, and a weight of 210 g / m 2 The pure cotton fiber was added to the mixed solution and reacted in an oil bath at 100°C for 90 minutes.

[0157] S320, taking out the pure cotton fiber, adjusting the pH value of the pure cotton fiber to neutral, immersing it in a 0.15 mol / L, 70°C barium hydroxide solution, reacting for 150 minutes, and then taking it out. After adjusting the pH value of the pure cotton fiber to neutral, it is placed in a 40°C oven to dry.

[0158] S400, placing the flexible ionizing radiation shielding layer B on the ionizing radiation shielding layer A, and adopting a lamination technology to obtain a composite material.

[0159] Example 7

[0160] S100, uses stretch fabric as the support layer.

[0161] S200, preparing an ionizing radiation shielding layer A:

[0162] S210, performing surface pretreatment on zirconium powder and cerium powder using a silane coupling agent to obtain pretreated radiation-proof powder.

[0163] S220, add polyacrylonitrile, zirconium powder and cerium powder in a mass ratio of 1:2:6 into a high-speed mixer and mix at high speed for 30 minutes. When the materials are evenly mixed, reduce the stirring speed to 50% of the original speed, then add thickener and defoaming agent, and observe the materials until they are uniform.

[0164] S230 combines stretch fabric with 130m long PVC artificial leather, connects it to the PVC artificial leather scraping equipment through human and mechanical transmission, turns on the oven and sets the temperature to 100℃, and turns on the equipment after the equipment performance is stable and the temperature is constant.

[0165] S240: The mixed coating is applied to the pre-adjusted PVC stretch fabric using a scraper at a speed of 3 m / min. The initial scraping thickness is 0.55 mm. The coating is then placed in an oven for 5 minutes (the oven length is 25 m) while the hot air circulation system is turned on. After drying, the coating thickness is measured to be 0.32 mm, and a second scraping is performed.

[0166] S250, the mixed coating is scraped on the dried coating, the pulling speed is controlled at 2.4m / min, the thickness is increased to 0.85mm, and it enters the oven and rests for 5 minutes (the oven length is 20m). At the same time, the hot air circulation system of the oven is turned on. After drying, the coating thickness is 0.58mm, and three more scraping operations are performed.

[0167] S260, apply the mixed coating on the dried coating, control the pulling speed to 4m / min, set the oven temperature to 100℃, and turn on the hot air circulation system of the oven. Let it stand for 3 minutes (the oven length is 25m). After drying, the coating thickness is 0.8mm, and then enter the composite operation link.

[0168] S270, the coated product is evenly compounded with the lining cloth under the double-roll co-extrusion action of the laminating machine (double-roll temperature 135℃), and then enters the oven for further drying. The oven temperature is 120℃ (oven length is 15m) and the pulling speed is 3m / min.

[0169] In S280, the elastic fabric is replaced with free paper, and the operation process of S230 to S260 is repeated to produce the intermediate.

[0170] S290, the free composite material and the stretch fabric composite material are compounded for the second time under the operation of the compounding machine to produce a product that meets the requirements. The free paper is peeled off during the compounding process to form a uniform composite material.

[0171] S300, preparing a flexible ionizing radiation shielding layer B:

[0172] S310, aminosulfonic acid and N, N-dimethylformamide are mixed in a mass ratio of 1:30, and a weight of 210g / m 2 The pure cotton fiber was added to the mixed solution and reacted in an oil bath at 110°C for 90 minutes.

[0173] S320, taking out the pure cotton fiber, adjusting the pH value of the pure cotton fiber to neutral, immersing it in a 0.15 mol / L, 70°C barium hydroxide solution, reacting it for 160 minutes, and then taking it out. After adjusting the pH value of the pure cotton fiber to neutral, it is placed in a 40°C oven to dry.

[0174] S400, placing the flexible ionizing radiation shielding layer B on the ionizing radiation shielding layer A, and adopting a lamination technology to obtain a composite material.

[0175] Example 8

[0176] S100, cotton cloth was selected as the support layer.

[0177] S200, preparing an ionizing radiation shielding layer A:

[0178] S210, performing surface pretreatment on cerium powder, neodymium powder, and samarium powder using a silane coupling agent to obtain pretreated radiation-proof powder.

[0179] S220, add polyvinyl chloride, cerium powder, neodymium powder and samarium powder in a mass ratio of 1:1:1.5:2 into a high-speed blender and mix at high speed for 30 minutes. When the materials are evenly mixed, reduce the stirring speed to 50% of the original speed, then add thickener and defoaming agent, and observe the materials until they are uniform.

[0180] S230, combines cotton cloth with 130m long PVC artificial leather, connects it to the PVC artificial leather scraping equipment through human and mechanical transmission, turns on the oven and sets the temperature to 110℃, and turns on the equipment after the equipment performance is stable and the temperature is constant.

[0181] S240: The mixed coating is applied to a pre-adjusted PVC cotton cloth using a doctor blade at a pulling speed of 3 m / min. The initial coating thickness is 0.55 mm. The coating is kept stationary and warm in an oven for 5 minutes (the oven length is 25 m). The hot air circulation system of the oven is turned on at the same time. After drying, the coating thickness is measured to be 0.32 mm, and a second doctor blade coating is performed.

[0182] S250, the mixed coating is scraped on the dried coating, the pulling speed is controlled at 2.4m / min, the thickness is increased to 0.85mm, and it enters the oven and rests for 5 minutes (the oven length is 20m). At the same time, the hot air circulation system of the oven is turned on. After drying, the coating thickness is 0.58mm, and three more scraping operations are performed.

[0183] S260, apply the mixed coating on the dried coating, control the pulling speed to 4m / min, set the oven temperature to 110℃, and turn on the hot air circulation system of the oven. Let it stand for 3 minutes (the oven length is 25m). After drying, the coating thickness is 0.8mm, and then enter the composite operation link.

[0184] S270, the coated product is evenly compounded with the lining cloth under the double-roll co-extrusion action of the laminating machine (double-roll temperature 135℃), and then enters the oven for further drying. The oven temperature is 130℃ (oven length is 15m) and the pulling speed is 3m / min.

[0185] S280, the cotton cloth is replaced with free paper, and the operation process of S230 to S260 is repeated to produce an intermediate.

[0186] S290, the free composite material and the cotton cloth composite material are compounded for the second time under the operation of the compounding machine to produce a product that meets the requirements. The free paper is peeled off during the compounding process to form a uniform composite material.

[0187] S300, preparing a flexible ionizing radiation shielding layer B:

[0188] S310, aminosulfonic acid and N, N-dimethylformamide are mixed in a mass ratio of 1:35, and a weight of 210g / m 2 The pure cotton fiber was added into the mixed solution and reacted in an oil bath at 130°C for 90 minutes.

[0189] S320, taking out the pure cotton fiber, adjusting the pH value of the pure cotton fiber to neutral, immersing it in a 0.15 mol / L, 70°C barium hydroxide solution, reacting it for 170 minutes, and then taking it out. After adjusting the pH value of the pure cotton fiber to neutral, it is placed in a 40°C oven to dry.

[0190] S400, placing the flexible ionizing radiation shielding layer B on the ionizing radiation shielding layer A, and adopting a lamination technology to obtain a composite material.

[0191] Example 9

[0192] S100, Oxford cloth is used as the supporting layer.

[0193] S200, preparing an ionizing radiation shielding layer A:

[0194] S210, performing surface pretreatment on samarium powder and europium powder using a silane coupling agent to obtain pretreated radiation-proof powder.

[0195] S220, add high-density polyethylene, samarium powder and europium powder in a mass ratio of 1:1:2 into a high-speed mixer and mix at high speed for 30 minutes. When the materials are evenly mixed, reduce the stirring speed to 50% of the original speed, then add thickener and defoaming agent, and observe the materials until they are uniform.

[0196] S230 combines Oxford cloth with 130m long PVC artificial leather, connects it to the PVC artificial leather scraping equipment through human and mechanical transmission, turns on the oven and sets the temperature to 120℃, and turns on the equipment after the equipment performance is stable and the temperature is constant.

[0197] S240: The mixed coating is applied to a pre-adjusted PVC Oxford cloth using a doctor blade at a pulling speed of 3 m / min. The initial coating thickness is 0.55 mm. The coating is kept in a static state for 5 minutes in an oven (the oven length is 25 m) while the hot air circulation system of the oven is turned on. After drying, the coating thickness is measured to be 0.32 mm, and a second doctor blade coating is performed.

[0198] S250, the mixed coating is scraped on the dried coating, the pulling speed is controlled at 2.4m / min, the thickness is increased to 0.85mm, and it enters the oven and rests for 5 minutes (the oven length is 20m). At the same time, the hot air circulation system of the oven is turned on. After drying, the coating thickness is 0.58mm, and three more scraping operations are performed.

[0199] S260, apply the mixed coating on the dried coating, control the pulling speed to 4m / min, set the oven temperature to 120℃, and turn on the hot air circulation system of the oven. Let it stand for 3 minutes (the oven length is 25m). After drying, the coating thickness is 0.8mm, and then enter the composite operation link.

[0200] S270, the coated product is evenly compounded with the lining cloth under the double-roll co-extrusion action of the laminating machine (double-roll temperature 135℃), and then enters the oven for further drying. The oven temperature is 140℃ (oven length is 15m) and the pulling speed is 3m / min.

[0201] S280, replace the Oxford cloth with free paper, repeat the operation process of S230 to S260 to produce the intermediate.

[0202] S290, the free composite material and the Oxford cloth composite material are compounded for the second time under the operation of the compounding machine to produce a product that meets the requirements. The free paper is peeled off during the compounding process to form a uniform composite material.

[0203] S300, preparing a flexible ionizing radiation shielding layer B:

[0204] S310, sulfamic acid and N, N-dimethylformamide are mixed in a mass ratio of 1:25, and a weight of 210 g / m 2 The pure cotton fiber was added into the mixed solution and reacted in an oil bath at 130°C for 90 minutes.

[0205] S320, taking out the pure cotton fiber, adjusting the pH value of the pure cotton fiber to neutral, immersing it in a 0.15 mol / L, 70°C barium hydroxide solution, reacting for 180 minutes, and then taking it out. After adjusting the pH value of the pure cotton fiber to neutral, it is placed in a 40°C oven to dry.

[0206] S400, the flexible ionizing radiation shielding layer B is placed on the ionizing radiation shielding layer A, and a lamination technology is used to obtain a composite material.

[0207] Example 10

[0208] S100, styrene-butadiene rubber is used as the supporting layer.

[0209] S200, preparing an ionizing radiation shielding layer A:

[0210] S210, performing surface pretreatment on europium powder and gadolinium powder using a silane coupling agent to obtain pretreated radiation-proof powder.

[0211] S220, add high-density polyethylene, europium powder, and gadolinium powder in a mass ratio of 1:2:2.5 into a high-speed blender and mix at high speed for 30 minutes. When the materials are evenly mixed, reduce the stirring speed to 50% of the original speed, then add the thickener and defoaming agent and observe the materials until they are uniform.

[0212] S230 combines styrene-butadiene rubber with 130m long PVC artificial leather, connects it to the PVC artificial leather coating equipment through human and mechanical transmission, turns on the oven and sets the temperature to 130℃, and turns on the equipment after the equipment performance is stable and the temperature is constant.

[0213] S240: The mixed coating is applied to the pre-adjusted PVC styrene-butadiene rubber by a scraper at a pulling speed of 3 m / min. The initial scraping thickness is 0.55 mm. The coating enters the oven and is kept still for 5 minutes (the oven length is 25 m). The hot air circulation system of the oven is turned on at the same time. After drying, the coating thickness is measured to be 0.32 mm, and a second scraping is performed.

[0214] S250, the mixed coating is scraped on the dried coating, the pulling speed is controlled at 2.4m / min, the thickness is increased to 0.85mm, and it enters the oven and rests for 5 minutes (the oven length is 20m). At the same time, the hot air circulation system of the oven is turned on. After drying, the coating thickness is 0.58mm, and three more scraping operations are performed.

[0215] S260: Apply the mixed coating on the dried coating with a scraper. The pulling speed is controlled at 4m / min, the oven temperature is set at 130°C, and the hot air circulation system of the oven is turned on. The coating is left to stand for 3 minutes (the oven length is 25m). After drying, the coating thickness is 0.8mm, and then the composite operation phase is entered.

[0216] S270, the coated product is evenly compounded with the lining cloth under the double-roll co-extrusion action of the laminating machine (double-roll temperature 135℃), and then enters the oven for further drying. The oven temperature is 140℃ (oven length is 15m) and the pulling speed is 3m / min.

[0217] S280: Replace the styrene-butadiene rubber with free paper and repeat the operation of S230 to S260 to produce an intermediate.

[0218] S290, the free compound material and the styrene-butadiene rubber compound material are compounded for the second time under the operation of the compounding machine to produce a product that meets the requirements. The free paper is peeled off during the compounding process to form a uniform composite material.

[0219] S300, preparing a flexible ionizing radiation shielding layer B:

[0220] S310, aminosulfonic acid and N, N-dimethylformamide are mixed in a mass ratio of 1:30, and a weight of 210g / m 2 The pure cotton fiber was added into the mixed solution and reacted in an oil bath at 130°C for 90 minutes.

[0221] S320, taking out the pure cotton fiber, adjusting the pH value of the pure cotton fiber to neutral, immersing it in a 0.15 mol / L, 70°C barium hydroxide solution, reacting for 190 minutes, and then taking it out. After adjusting the pH value of the pure cotton fiber to neutral, it is placed in a 40°C oven to dry.

[0222] S400: placing the flexible ionizing radiation shielding layer B on the ionizing radiation shielding layer A using a lamination technique to obtain a composite material.

[0223]

Claims

1. A radiation protection composite material comprising a support layer, an ionizing radiation shielding layer and a flexible ionizing radiation shielding layer, characterized in that: The supporting layer is made of polymer material; An ionizing radiation shielding layer is laminated on the support layer; the ionizing radiation shielding layer comprises, by weight, 5 to 50 parts of a polymer matrix material, 10 to 80 parts of a radiation-resistant composite powder, 1 to 15 parts of an auxiliary agent, and 1 to 15 parts of a binder; a flexible ionizing radiation shielding layer, stacked on the ionizing radiation shielding layer; The flexible ionizing radiation shielding layer is first formed by sulfonating a fiber material with a sulfonating agent to form a sulfonated fiber material; Furthermore, the sulfonated fiber material reacts with a solution containing barium ions to obtain a flexible ionizing radiation shielding layer.

2. The radiation protection composite material according to claim 1, characterized in that: The support layer adopts at least one of the polymer materials selected from Oxford cloth, rubber, synthetic fiber and engineering plastics, thermoplastics, cotton cloth, stretch cloth, leather, flexible textiles, natural and special materials, and lead-free PEEK resin.

3. The radiation protection composite material according to claim 1 or 2, characterized in that: The synthetic fibers and engineering plastics are selected from polyamide, poly(p-phenylene terephthalamide), polyethylene terephthalate, poly(butylene terephthalate), and polyethylene naphthalate; The thermoplastic material is polyethylene or polypropylene; The natural and special materials are selected from polyvinyl alcohol, polyacrylonitrile, cellulose, and protein; The rubber is selected from silicone rubber, styrene-butadiene rubber, chlorosulfonated polyethylene, chloroprene rubber, organic silicone rubber, and EPDM rubber.

4. The radiation protection composite material according to claim 3, characterized in that: The polymer matrix material is selected from at least one of polyurethane, polyvinyl alcohol, polyacrylonitrile, polycarbonate, acrylonitrile-butadiene-styrene copolymer, epoxy resin, polyacrylic acid, high-density polyethylene, medium-density polyethylene, low-density polyethylene, silicone resin, alkyd resin, phenolic resin, polypropylene, polyvinyl chloride, polystyrene, polystyrene-ethylene-butadiene-styrene, cellulose and protein.

5. The radiation-proof composite material and preparation method thereof according to claim 1, characterized in that: The radiation-proof composite powder is selected from at least one of bismuth, tantalum, zirconium, niobium and their metal compounds; or selected from at least one of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium and their rare earth-based compounds.

6. The radiation-proof composite material and preparation method thereof according to claim 1, characterized in that: The binder is a coupling agent, which is at least one of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, an aluminum-titanium composite coupling agent, and a phosphate coupling agent.

7. The radiation-proof composite material and preparation method thereof according to claims 1-6, characterized in that: The preparation of the ionizing radiation shielding layer includes the following steps: (1) Add the polymer matrix material and the radiation protection composite powder into a high-speed mixer at a preset mass ratio and mix at high speed. When the materials are evenly mixed, reduce the stirring speed to 50% of the original speed and then add the thickener and defoamer. The preset mass ratio is 1: (2-8) and the mixing time is 5 min to 60 min. (2) Combine the polymer matrix material with the PVC artificial leather, connect it to the PVC artificial leather coating equipment through human and mechanical transmission, and place it in an oven for drying; (3) The mixed coating is scraped onto the pre-adjusted PVC polymer matrix material through a scraper, and the composite material is placed in an oven and kept still for heat preservation, and then scraped twice; the mixed coating is scraped onto the dried coating, and the composite material is placed in an oven and kept still for heat preservation, and then scraped three times; the mixed coating is scraped onto the dried coating, and the composite material is placed in an oven and kept still for heat preservation, and then enters the composite operation link; (4) The coated product is evenly compounded with the lining cloth under the double-roll co-extrusion action of the compounding machine and then put into the oven for further drying; (5) Replace the polymer matrix material with free paper and repeat the process of 3-4 to produce an intermediate; (6) The free composite material and the polymer matrix material composite material are compounded for a second time under the operation of a compounding machine, and the free paper is peeled off during the compounding process to form a uniform composite material.

8. The radiation-proof composite material and preparation method thereof according to claim 1, characterized in that: The preparation of the ionizing radiation shielding layer includes the following steps: (1) A sulfonating agent and an organic solvent are mixed in a preset mass ratio to prepare a mixed solution, and then a fiber material is immersed in the mixed solution in a preset solid-liquid mass ratio to perform a sulfonation reaction to obtain a sulfonated fiber material, wherein the sulfonating agent is aminosulfonic acid, the organic solvent is N,N-dimethylformamide, the fiber material is pure cotton fiber, the preset mass ratio is 1:(12-38), the preset solid-liquid mass ratio is 1:(35-42), the sulfonation reaction temperature is 60-130°C, and the sulfonation reaction time is greater than or equal to 10 minutes; (2) Immersing the sulfonated fiber material in a 0.01-0.15 mol / L barium ion solution for reaction to obtain the X-ray shielding material; the barium ion solution is preferably a barium hydroxide solution, a barium chloride solution or a barium nitrate solution; the reaction temperature in step 2 is 30-80°C, the reaction time is greater than or equal to 15 minutes, and the mass ratio of the solute in the barium ion solution to the sulfonated fiber material is (0.5-5):

1.

9. The radiation-proof composite material and preparation method thereof according to claim 8, characterized in that: The preparation of the shielding slurry includes the following steps: pre-treating the surface of the radiation-proof composite powder with the coupling agent to obtain pre-treated radiation-proof composite powder; and mixing the pre-treated composite powder with a polymer matrix material to obtain the shielding slurry.

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