CN106928701A - A kind of high temperature resistant nylon base X-ray shield composite and preparation method thereof - Google Patents

A kind of high temperature resistant nylon base X-ray shield composite and preparation method thereof Download PDF

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CN106928701A
CN106928701A CN201511008830.XA CN201511008830A CN106928701A CN 106928701 A CN106928701 A CN 106928701A CN 201511008830 A CN201511008830 A CN 201511008830A CN 106928701 A CN106928701 A CN 106928701A
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high temperature
temperature resistant
resistant nylon
dry
coupling agent
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杨桂生
李庆丰
赵冬云
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Shanghai Genius Advanced Materials Group Co Ltd
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Shanghai Genius Advanced Materials Group Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06Polyamides derived from polyamines and polycarboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/002Physical properties
    • C08K2201/003Additives being defined by their diameter
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/014Additives containing two or more different additives of the same subgroup in C08K
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/016Additives defined by their aspect ratio
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/08Stabilised against heat, light or radiation or oxydation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

A kind of high temperature resistant nylon base X-ray shield composite, is made up of the component of following weight portion:60-100 parts of high temperature resistant nylon resin;Maleic anhydride is grafted 15-25 parts of high temperature resistant nylon;Tungsten powder 500-700 parts;Tungsten fiber 60-100 parts;Organic rare-earth ligand 240-400 parts;Antioxidant 1-3 parts.The preparation method of the high temperature resistant nylon base X-ray shield composite:To be crossed through coupling agent surface treatment tungsten powder 500-700 parts, tungsten fiber 60-100 parts crossed through coupling agent surface treatment, 60-100 parts of dry high temperature resistant nylon resin, 15-25 part of high temperature resistant nylon of dry maleic anhydride grafting, dry organic rare-earth ligand 240-400 parts and antioxidant 1-3 parts be well mixed, heat temperature raising, pressure, again heat-insulation pressure keeping, intensification, again heat-insulation pressure keeping, cooling pressure release, obtain the excellent high temperature resistant nylon base X-ray shield composite of nontoxic, processing and forming.

Description

A kind of high temperature resistant nylon base X-ray shield composite and preparation method thereof
Technical field
The invention belongs to radiation protection field of material technology, be related to a kind of high temperature resistant nylon base X-ray shield composite and its Preparation method.
Background technology
At present, most widely used radiation proof material be containing high atomic number lead (such as lead, refined lead, organic lead glass) and barium (if any Machine barium glass) material.Lead and its compound are poisonous, and can produce serious environmental pollution when preparing, using and abandon, organic Barium glass has the shortcomings that case hardness is low, shielding property is poor.As various countries progressively to lead and lead-containing materials production and use The raising of limitation and people to radiation protection performance requirement, finding a kind of environment-friendly and strong material of radiation protection ability turns into The problem demanding prompt solution of radiation protection field one.
Tungsten is a kind of metal of stable chemical nature, and density is up to 19.4g/cm3, it is preferable radiation proof material;Additionally, tungsten is not Produce secondary electron radiation;But, tungsten metal has that hardness is high, fusing point is high, the property such as crisp limits its and applies.As ray Shielding material, the shielding properties of polymer matrix composite tungsten material is extremely important, and significantly polymer/composite tungsten material is adopted With conventional melting extrusion, molding and injection molding method, the complexity zero that tungsten is difficult to be molded can be easily prepared Part.
The K layers of ABSORPTION EDGE (from the 38.9keV of lanthanum to the 63.3keV of lutetium) of rare earth element, in excellent diagnostics X-ray absorption area, Their compound has the advantages that chemical stability is good, nontoxic, degradation is low, cheap, is shielding diagnosis ray Ideal material.Using rare earth/polymer composites obtained in lanthanide series, with good shield effectiveness, have with leadwork There is same protective capacities lower density lower.
Matrix resin semi-aromatic and aromatic series high temperature resistant nylon compare aliphatic due to having imported aromatic rings, temperature capacity in main chain Nylon is greatly improved, and water absorption rate declines, good stability of the dimension, it is adaptable to the working environment of HTHP.
The A of patent CN 101074315 provide a kind of production method of high-specific weight resin, although used polyamide, but, gather The fineness of acid amides is powder more than 80 mesh, and high temperature resistant nylon and organic rare-earth ligand is not used.
The content of the invention
For the defect of prior art, it is an object of the invention to provide a kind of nontoxic, molding processibility is excellent, high temperature resistant, impact The high temperature resistant nylon base X-ray shield composite that better performances and X-ray shield work well.
It is a further object to provide a kind of preparation method of the high temperature resistant nylon base X-ray shield composite.
In order to achieve the above object, the present invention is adopted the following technical scheme that:
A kind of high temperature resistant nylon base X-ray shield composite, is made up of the component of following weight portion:
The high temperature resistant nylon resin is selected from least in the semi-aromatic nylon or all aromatic nylon that fusing point is 290~320 DEG C Kind;Wherein:The semi-aromatic nylon is poly- paraphenylene terephthalamide's decamethylene diamine, poly- phthalyl nonamethylene diamine, poly- paraphenylene terephthalamide Hexamethylene diamine-co- hexamethylene adipamides copolymer, poly-paraphenylene terephthalamide's nonamethylene diamine, the carbon diamines of poly- paraphenylene terephthalamide 12, poly- neighbour's benzene two At least one in formyl decamethylene diamine;The all aromatic nylon is in polyphthalamide or poly- terephthalate p-phenylenediamine It is at least one.
High temperature resistant nylon in maleic anhydride grafting high temperature resistant nylon in semi-aromatic nylon or all aromatic nylon at least It is a kind of;Wherein:The semi-aromatic nylon is poly- paraphenylene terephthalamide's decamethylene diamine, poly- phthalyl nonamethylene diamine, poly- terephthaldehyde Acyl hexamethylene diamine-co- hexamethylene adipamides copolymer, poly-paraphenylene terephthalamide's nonamethylene diamine, the carbon diamines of poly- paraphenylene terephthalamide 12, poly- neighbour's benzene At least one thing in two formyl decamethylene diamines;The all aromatic nylon is polyphthalamide or poly- terephthalate p-phenylenediamine In at least one.
The organic rare-earth ligand is lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium unit At least one in the methacrylate of element.
The antioxidant is the mixture of antioxidant 1098 and antioxidant 1790.
The tungsten powder is the tungsten powder crossed through coupling agent surface treatment, and average grain diameter is 0.4-40 μm.
The tungsten fiber is the tungsten fiber crossed through coupling agent surface treatment, and a diameter of 10-50 μm, draw ratio is 100-500.
The tungsten powder crossed through coupling agent surface treatment, processing method is comprised the following steps:
Dry tungsten powder mixes with hydrolysis coupling agent, and heating is reacted, suction filtration, again washing, suction filtration, heating after reaction completely Dry, obtain the tungsten powder crossed through coupling agent surface treatment.
The dry tungsten powder is under conditions of temperature is for 100-120 DEG C, to dry 1-5h.
The tungsten powder is (0.1-5) with the mass ratio of hydrolysis coupling agent:1.
The temperature reacted that heats is 50-70 DEG C, while it is 3-5 to keep pH value, the time of reaction is 1-5h.
The temperature of the heat drying is 100-120 DEG C, and the time is 3-8h.
The tungsten fiber crossed through coupling agent surface treatment, processing method is comprised the following steps:
Dry tungsten fiber mixes with hydrolysis coupling agent, and heat drying obtains the tungsten fiber crossed through coupling agent surface treatment.
The tungsten fiber is (0.1-5) with the mass ratio of hydrolysis coupling agent:1.
The dry tungsten fiber is under conditions of temperature is for 100-120 DEG C, to dry 1-5h.
The time that the dry tungsten fiber mixes with hydrolysis coupling agent is 1-10h.
The temperature of the heat drying is 100-120 DEG C, and the time is 3-8h.
The preparation method of the hydrolysis coupling agent is comprised the following steps:Silane coupler is dissolved into the solution of ethanol and distilled water, The silane coupler, ethanol, the proportion of distilled water are (10-30):(10-30):(40-80), adds grass after heating Acid is reacted, and the temperature of heating is 50-70 DEG C;Oxalic acid is (0.33-3) with the mass ratio of silane coupler:1;Reaction when Between be 1-3h, regulation pH value be 3-5, obtain the hydrolysis coupling agent.
A kind of preparation method of the high temperature resistant nylon base X-ray shield composite, comprises the following steps:
To be crossed through coupling agent surface treatment tungsten powder 500-700 parts, it is tungsten fiber 60-100 parts crossed through coupling agent surface treatment, dry Dry 60-100 parts of high temperature resistant nylon resin, 15-25 parts of high temperature resistant nylon of dry maleic anhydride grafting, dry organic RE Complex 240-400 parts and antioxidant 1-3 part are well mixed, heat temperature raising, pressure, again heat-insulation pressure keeping, intensification, again Heat-insulation pressure keeping, cooling pressure release, obtain the high temperature resistant nylon base X-ray shield composite.
The temperature of the heat temperature raising is 260-300 DEG C.
The pressure of the pressure is 11-13MPa.
The time of the heat-insulation pressure keeping is 1-5h.
The temperature for heating up again is 310-340 DEG C.
The time of the heat-insulation pressure keeping again is 1-5h.
The temperature of the cooling pressure release is to be down to less than 100 DEG C.
The dry high temperature resistant nylon resin, dry maleic anhydride grafting high temperature resistant nylon and dry organic rare-earth ligand It is under conditions of temperature is for 100-120 DEG C, to dry 4-8h.
There is advantages below and beneficial effect due to using above-mentioned technical proposal, the present invention:
The present invention prepare high temperature resistant nylon base X-ray shield composite, add tungsten powder while, using tungsten fiber with it is resistance to High-temperature nylon resin compounded, so that the mechanical performance of composite is ensured;The organic rare-earth ligand for being used with it is poly- Compound matrix has more preferable compatibility, so as to maintain the mechanical performance of composite;Matrix resin semi-aromatic and aromatic series High temperature resistant nylon is greatly improved due to having imported aromatic rings, temperature capacity in main chain than amorphous nylon, and water absorption rate declines, chi Very little good stability, it is adaptable to the working environment of HTHP.
High temperature resistant nylon base X-ray shield composite prepared by the present invention has excellent nontoxic, processing and forming, high temperature resistant, punching Hit better performances and the features such as X-ray shield works well;The material has in fields such as nuclear facilities, medicine equipment, rays safety detection apparatus Wide application prospect.
Specific embodiment
With reference to embodiment, the present invention is further detailed explanation.
The preparation method of the high temperature resistant nylon base X-ray shield composite of embodiment 1 to 7, comprises the following steps:
The preparation method for hydrolyzing coupling agent is comprised the following steps:Silane coupling agent KH550 is dissolved into the solution of ethanol and distilled water In, the Silane coupling agent KH550, ethanol, the proportion of distilled water are 15:15:50, add oxalic acid to carry out instead after heating Should, the temperature of heating is 60 DEG C;Oxalic acid is 1.5 with the mass ratio of silane coupler:1;The time of reaction is 2h, adjusts pH value It is 4, obtains the hydrolysis coupling agent..
The processing method of the tungsten powder crossed through coupling agent surface treatment is comprised the following steps:
Dry tungsten powder mixes with hydrolysis coupling agent, and dry tungsten powder is under conditions of temperature is for 110 DEG C, to dry 3h, tungsten powder Ratio with hydrolysis coupling agent is 2.5:1, heating is reacted, and bath temperature is 60 DEG C, while with electric mixer with constant Speed is stirred, while it is 4 to keep pH value, the time of reaction is 3h;Silane coupler is set fully to be wrapped in tungsten powder particles surface; Suction filtration is carried out to the modified tungsten powder reaction solution in surface, and the tungsten powder after suction filtration is repeatedly placed in electric heating with distillation water washing, again suction filtration Heat drying in constant temperature blast drying oven, temperature is 110 DEG C, and the time is 6h, moisture is volatilized completely, obtains described through coupling The surface-treated tungsten powder of agent.
The tungsten fiber crossed through coupling agent surface treatment, processing method is comprised the following steps:
Dry tungsten fiber and hydrolysis coupling agent mixing 5h, be sufficiently impregnated tungsten fiber, dry tungsten fiber be temperature be 110 DEG C Under conditions of, 3h is dried, dry tungsten fiber is 2.5 with the ratio of hydrolysis coupling agent:1;, impregnated tungsten fiber is placed in electricity In hot constant temperature blast drying oven, heat drying makes moisture volatilize completely, obtains the tungsten fiber crossed through coupling agent surface treatment, The temperature of heat drying is 110 DEG C, and the time is 6h.
The tungsten fiber crossed by the tungsten powder crossed through coupling agent surface treatment, through coupling agent surface treatment, dry high temperature resistant nylon resin, Dry maleic anhydride grafting high temperature resistant nylon, dry organic rare-earth ligand and antioxidant are well mixed, are then added to mould In tool, mould is placed in compression molding instrument, dry high temperature resistant nylon resin, dry maleic anhydride grafting high temperature resistant nylon It is under conditions of temperature is for 110 DEG C, to dry 6h with dry organic rare-earth ligand;Heating mould is warming up to 280 DEG C, applies Pressure 12MPa, heat-insulation pressure keeping 1.5h, are warming up to 325 DEG C, again heat-insulation pressure keeping 1.5h again, are cooled to less than 100 DEG C pressure releases, The high temperature resistant nylon base X-ray shield composite is obtained, the demoulding obtains composite material moulded part, molding is processed into survey Sample needed for examination.
The formula of each component of embodiment 1 to 4 is as shown in table 1.
Table 1
The formula of each component of embodiment 5 to 7 and comparative example is as shown in table 2.
Table 2
The performance such as table of the high temperature resistant nylon base X-ray shield composite that embodiment 1 to 7 is obtained and the material that comparative example is obtained Shown in 3.
Table 3
Cantilever beam impact strength is tested according to ASTM D256 in table 3;After sample being penetrated using CT machines measure X-ray CT values and attenuation rate, by CT values and attenuation rate, COMPOSITE MATERIALS is to the shield effectiveness of X-ray, CT values and decay Rate is bigger, and composite is better to the shielding properties of X-ray.
The cantilever beam impact strength highest of embodiment 1 is can be seen that by the properties of table 3, CT values and attenuation rate are maximum, are Most preferred embodiment, has used the heat distortion temperature of the embodiment of high temperature resistant nylon to be above using common polyamide nylon comparative example Heat distortion temperature.By table 3 it can also be seen that attenuation rate is all more than 95% after X-ray penetrates sample.Show present invention preparation High temperature resistant nylon base X-ray shield composite possesses high temperature resistant, impact property preferably and X-ray shield works well etc. spy Point;The material has broad application prospects in fields such as nuclear facilities, medicine equipment, rays safety detection apparatus.
The above-mentioned description to embodiment is to be understood that and apply the present invention for ease of those skilled in the art.It is familiar with The personnel of art technology obviously can easily make various modifications to these embodiments, and should General Principle described herein Use in other embodiment without by performing creative labour.Therefore, the invention is not restricted to embodiment here, this area skill Art personnel announcement of the invention, does not depart from improvement that scope made and modification all should be in protection model of the invention Within enclosing.

Claims (10)

1. a kind of high temperature resistant nylon base X-ray shield composite, it is characterised in that:It is made up of the component of following weight portion:
2. high temperature resistant nylon base X-ray shield composite according to claim 1, it is characterised in that:The resistance to height Warm nylon resin is selected from least one in the semi-aromatic nylon or all aromatic nylon that fusing point is 290~320 DEG C;Preferably, The semi-aromatic nylon is poly- paraphenylene terephthalamide's decamethylene diamine, poly- phthalyl nonamethylene diamine, poly- hexamethylene terephthalamide-co- Hexamethylene adipamide copolymer, poly-paraphenylene terephthalamide's nonamethylene diamine, the carbon diamines of poly- paraphenylene terephthalamide 12, the poly- phthalyl last of the ten Heavenly stems two At least one in amine;Preferably, all aromatic nylon is in polyphthalamide or poly- terephthalate p-phenylenediamine It is at least one;
Preferably, the high temperature resistant nylon in the maleic anhydride grafting high temperature resistant nylon is semi-aromatic nylon or all aromatic nylon In at least one;Preferably, the semi-aromatic nylon be poly- paraphenylene terephthalamide's decamethylene diamine, poly- phthalyl nonamethylene diamine, Poly- hexamethylene terephthalamide-co- hexamethylene adipamides copolymer, poly-paraphenylene terephthalamide's nonamethylene diamine, the carbon two of poly- paraphenylene terephthalamide 12 At least one in amine, poly- phthalyl decamethylene diamine;Preferably, all aromatic nylon is polyphthalamide or poly- At least one in terephthalate p-phenylenediamine;
Preferably, the organic rare-earth ligand be lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, At least one in ytterbium, the methacrylate of lutetium element;
Preferably, the antioxidant is the mixture of antioxidant 1098 and antioxidant 1790.
3. high temperature resistant nylon base X-ray shield composite according to claim 1, it is characterised in that:The tungsten powder It is the tungsten powder crossed through coupling agent surface treatment, average grain diameter is 0.4-40 μm;
Preferably, the tungsten fiber is the tungsten fiber crossed through coupling agent surface treatment, a diameter of 10-50 μm, and draw ratio is 100-500。
4. high temperature resistant nylon base X-ray shield composite according to claim 3, it is characterised in that:It is described through idol The surface-treated tungsten powder of connection agent, processing method is comprised the following steps:
Dry tungsten powder mixes with hydrolysis coupling agent, and heating is reacted, suction filtration, again washing, suction filtration, heating after reaction completely Dry, obtain the tungsten powder crossed through coupling agent surface treatment.
5. high temperature resistant nylon base X-ray shield composite according to claim 4, it is characterised in that:The drying Tungsten powder be temperature be 100-120 DEG C under conditions of, dry 1-5h;
Preferably, the tungsten powder and the mass ratio of hydrolysis coupling agent are (0.1-5):1;
Preferably, the temperature reacted that heats is 50-70 DEG C, while it is 3-5 to keep pH value, the time of reaction is 1-5h;
Preferably, the temperature of the heat drying is 100-120 DEG C, and the time is 3-8h.
6. high temperature resistant nylon base X-ray shield composite according to claim 4, it is characterised in that:It is described through idol The surface-treated tungsten fiber of connection agent, processing method is comprised the following steps:
Dry tungsten fiber mixes with hydrolysis coupling agent, and heat drying obtains the tungsten fiber crossed through coupling agent surface treatment.
7. high temperature resistant nylon base X-ray shield composite according to claim 6, it is characterised in that:The tungsten is fine Dimension is (0.1-5) with the mass ratio of hydrolysis coupling agent:1;
Preferably, the dry tungsten fiber is under conditions of temperature is for 100-120 DEG C, to dry 1-5h;
Preferably, the time that the tungsten fiber mixes with hydrolysis coupling agent is 1-10h;
Preferably, the temperature of the heat drying is 100-120 DEG C, and the time is 3-8h.
8. the high temperature resistant nylon base X-ray shield composite according to claim 4 or 6, it is characterised in that:It is described The preparation method for hydrolyzing coupling agent is comprised the following steps:Silane coupler is dissolved into the solution of ethanol and distilled water, the silane Coupling agent, ethanol, the proportion of distilled water are (10-30):(10-30):(40-80), adds oxalic acid to carry out instead after heating Should, the temperature of heating is 50-70 DEG C;Oxalic acid is (0.33-3) with the mass ratio of silane coupler:1;The time of reaction is 1-3h, Regulation pH value is 3-5, obtains the hydrolysis coupling agent.
9. the preparation method of any described high temperature resistant nylon base X-ray shield composite of a kind of claim 1 to 8, its It is characterised by:Comprise the following steps:
To be crossed through coupling agent surface treatment tungsten powder 500-700 parts, it is tungsten fiber 60-100 parts crossed through coupling agent surface treatment, dry Dry 60-100 parts of high temperature resistant nylon resin, 15-25 parts of high temperature resistant nylon of dry maleic anhydride grafting, dry organic RE Complex 240-400 parts and antioxidant 1-3 part are well mixed, heat temperature raising, pressure, again heat-insulation pressure keeping, intensification, again Heat-insulation pressure keeping, cooling pressure release, obtain the high temperature resistant nylon base X-ray shield composite.
10. the preparation method of high temperature resistant nylon base X-ray shield composite according to claim 9, it is characterised in that: The temperature of the heat temperature raising is 260-300 DEG C;
Preferably, the pressure of the pressure is 11-13MPa;
Preferably, the time of the heat-insulation pressure keeping is 1-5h;
Preferably, the temperature for heating up again is 310-340 DEG C;
Preferably, the time of the heat-insulation pressure keeping again is 1-5h;
Preferably, the temperature of the cooling pressure release is to be down to less than 100 DEG C;
Preferably, the dry high temperature resistant nylon resin, dry maleic anhydride grafting high temperature resistant nylon and dry organic dilute Native complex is under conditions of temperature is for 100-120 DEG C, to dry 4-8h.
CN201511008830.XA 2015-12-29 2015-12-29 A kind of high temperature resistant nylon base X-ray shield composite and preparation method thereof Pending CN106928701A (en)

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CN112011180A (en) * 2020-08-28 2020-12-01 武汉市莎卡娜尔科技有限公司 Wave-absorbing radiation-proof plastic and preparation method thereof
CN113861414A (en) * 2021-10-29 2021-12-31 山东东辰瑞森新材料科技有限公司 Self-cleaning transparent nylon material for shielding radioactive rays and preparation method thereof

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