CN113321877A - Recyclable flexible radiation-proof sheet and preparation method thereof - Google Patents

Recyclable flexible radiation-proof sheet and preparation method thereof Download PDF

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CN113321877A
CN113321877A CN202110660199.0A CN202110660199A CN113321877A CN 113321877 A CN113321877 A CN 113321877A CN 202110660199 A CN202110660199 A CN 202110660199A CN 113321877 A CN113321877 A CN 113321877A
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radiation
powder
chlorinated polyethylene
proof
sheet
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CN113321877B (en
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李永明
马全亮
张立顺
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Tianjin Tianyi Keyuan Technology Co ltd
Institute of Radiation Medicine of CAMMS
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Tianjin Tianyi Keyuan Technology Co ltd
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
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    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
    • C08J2323/28—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment by reaction with halogens or halogen-containing compounds
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    • C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08J2409/02—Copolymers with acrylonitrile
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    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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    • C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2425/02—Homopolymers or copolymers of hydrocarbons
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    • C08J2425/14—Homopolymers or copolymers of styrene with unsaturated esters
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    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2433/08—Homopolymers or copolymers of acrylic acid esters
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
    • C08J2433/12—Homopolymers or copolymers of methyl methacrylate
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    • C08K5/00—Use of organic ingredients
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    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/45—Heterocyclic compounds having sulfur in the ring
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients

Abstract

The invention provides a recyclable flexible radiation-proof sheet and a preparation method thereof, wherein the recyclable flexible radiation-proof sheet is prepared from the following raw materials in percentage by mass: 5-14% of base material, 60-89% of radiation-proof filler, 0.5-3% of acrylate, 0.01-2% of nitrile rubber, 0.01-2% of thermoplastic elastomer, 3-8% of plasticizer, 1-4% of cold-resistant agent, 0.2-1% of calcium-zinc composite stabilizer, 0.02-0.07% of ultraviolet absorbent, 0.02-0.07% of antioxidant and 0-2.8% of the rest; the radiation-proof filler is metal micro-nano powder with the surface coated with metal oxide. The product of the invention is light and soft, can replace lead rubber products and can be recycled.

Description

Recyclable flexible radiation-proof sheet and preparation method thereof
Technical Field
The invention relates to the technical field of ray shielding materials, in particular to a recyclable flexible radiation-proof sheet and a preparation method thereof.
Background
With the continuous development and wide application of nuclear technology in the fields of radiology, nuclear industry, scientific research and the like, high-energy rays (particularly X rays and gamma rays) can cause irreversible damage to people in an irradiation range and can also cause serious damage to the environment, so that economic loss is brought, and the research on high-efficiency and flexible ray shielding materials becomes a hotspot. However, the commercially available material is basically a rubber material, an internal mixing production process is adopted for feeding in the early stage of processing, the filler is difficult to be uniformly distributed, vulcanization treatment is required in the later stage of processing, the strength of the material is improved through the vulcanization process, the whole processing process is complicated, the ozone resistance of the material is poor, and the aged sheet cannot be subjected to calendering molding and use through adding additives; the adoption of the desulfurization treatment has high cost, complex operation and heavy pollution. In addition, the commercially available shielding material has a heavy weight, a thick material and a high hardness, which directly affect the wearing comfort and flexibility, so that it is necessary to research and develop a new shielding material, to realize a thin material and a light weight, and to recycle the material.
Disclosure of Invention
In order to overcome the defects of the existing radiation-proof material, the invention provides a recyclable flexible radiation-proof sheet which is light and soft, can replace lead rubber products and can be recycled.
The recyclable flexible radiation-proof sheet is prepared from the following raw materials in percentage by mass: 5-14% of base material, 60-89% of radiation-proof filler, 0.5-3% of acrylate, 0.01-2% of nitrile rubber, 0.01-2% of thermoplastic elastomer, 3-8% of plasticizer, 1-4% of cold-resistant agent, 0.2-1% of calcium-zinc composite stabilizer, 0.02-0.07% of ultraviolet absorbent, 0.02-0.07% of antioxidant and 0-2.8% of other components; the radiation-proof filler is metal micro-nano powder with the surface coated with metal oxide.
Wherein, the chlorine content of the base material chlorinated polyethylene is 5-7%, and the molecular weight is 3200 +/-200.
Wherein, the coating of the radiation-proof filler is one or more of tungsten, bismuth, lead, cerium, chromium, rhenium, gadolinium, nickel, tantalum, europium and erbium metal spherical micro-nano powder, and the coating is tungsten oxide, bismuth oxide and rare earth metal oxide.
Wherein the acrylic ester is a copolymer of two or more monomers selected from four monomers of methyl methacrylate, ethyl acrylate, butyl acrylate and styrene, and the viscosity is 4-13 Pa.s; the nitrile rubber is powder with the purity of more than or equal to 90 percent and the granularity of 300 meshes; the thermoplastic elastomer is selected from one or more of the trade names G130D, G140D, G155D, G163D and G172D; the plasticizer is selected from one or more of dioctyl phthalate, dioctyl terephthalate, diisodecyl phthalate, tricresyl phosphate, cresyldiphenyl phosphate, epoxidized soybean oil, epoxy butyl oleate and triisooctyl 1,2, 4-trimellitate; the cold-resistant agent is selected from one or more of dioctyl adipate, diisodecyl adipate, dioctyl azelate, dibutyl sebacate, dioctyl sebacate and diisooctyl sebacate; the purity of the calcium-zinc composite stabilizer is more than or equal to 90 percent, and the metal content is more than or equal to 7 percent; the ultraviolet absorbent is any one of salicylic acid esters, benzophenones, benzotriazoles, substituted acrylonitrile and triazines; the antioxidant is selected from any one of phosphite esters and phenol powder or liquid antioxidant.
Among them, the other components may preferably include stearic acid, PE wax, an anti-mold agent and an antistatic agent; the stearic acid is powder with the granularity of 300 meshes; the PE wax is powder with the granularity of 300 meshes; the mildew inhibitor is any one of polyhexamethylene guanidine hydrochloride and 4, 5-dichloro-2-octyl-4-isothiazoline-3-ketone; the antistatic agent is octadecyl diethanol amine.
The preparation method of the recyclable flexible radiation-proof sheet comprises the following steps: the raw materials for preparing the radiation-proof sheet are mixed and stirred highly, plasticized at the temperature of 160-200 ℃ after complete oil absorption, and then rolled into the sheet at the temperature of 180-230 ℃.
The radiation-proof sheet is prepared from the following raw materials, namely chlorinated polyethylene as a base material by the following method: adding 5-10 wt% of chlorinated polyethylene suspension into a reaction kettle to be used as seed crystal; then adding a dispersing agent, stirring at a high speed, and dispersing the seed crystal; then adding an initiator; stirring at low speed, introducing chloroethylene and ethylene gas into the reaction kettle at the same time, and controlling the speed ratio of the chloroethylene to the ethylene gas to be 1: 15-25; controlling the pressure of the reaction kettle at 0.09-0.35Mpa, and obtaining the chlorinated polyethylene base material after centrifugation, liquid removal and drying.
Further, in the preparation process of the base material chlorinated polyethylene, the chlorine content of the seed crystal chlorinated polyethylene is 7-12%; the solvent is any one or more of acetone, ethanol, benzene, distilled water and diethyl ether; the dispersant is polyvinyl alcohol, and the addition amount is 0.05-3 wt%; the initiator is dibenzoyl peroxide and TiCl4-AlR30.01-1.2 wt% of one or more of di-tert-butyl peroxide, isopropyl peroxydicarbonate and acetyl peroxycyclo-sulfonate; the introducing speed of the chloroethylene is 0.3-0.6 Kg/min; the feeding speed of the ethylene is 2 to 4 Kg/min.
The radiation-proof sheet is prepared from the following raw materials in a radiation-proof filling manner: heating tungsten, bismuth or rare earth metal salt, dissolving in solvent (such as distilled water), adding the micro-nano metal powder and dispersant polyvinyl alcohol, stirring, pumping into precipitant, boiling for a period of time, cooling to room temperature, filtering, and washing. Acidifying: adding filter residues into water for size mixing, pumping liquid acid, stirring, heating, boiling, cooling, filtering, washing, drying, and finally calcining in a muffle furnace at 800 ℃ at 500 ℃ to obtain the metal micro-nano powder with the surface coated with metal oxides.
Compared with the prior art, the invention has the following beneficial effects:
the recyclable flexible radiation-proof sheet provided by the invention has the advantages of good radiation-proof performance, low possibility of aging, light weight, good rebound resilience, softness, ozone resistance, no odor, good filler dispersion, corrosion resistance, wear resistance, flame retardance and the like; in addition, the finished product is close-fitting and more comfortable to wear, can be completely recycled after being scrapped, is calendered and molded again, does not need a vulcanization process, has a constant protection effect, does not cause the problems of storage pressure, environmental pollution and the like, and has a wide market prospect in the field of ray protection instead of rubber products.
In particular, the sheet of the invention is thin and light: (1) the base material and the acrylic ester are compounded for use, so that the filler particles can be tightly combined, the gap is small, and the shielding effect is good. (2) The metal oxide coats another metal particle to form a core-shell structure, so that the shielding efficiency is high, the required sheet is thin under the same radiation protection capability, and the total weight is small. Equivalent effects can be achieved without adding a larger proportion of filler. (0.11-0.15 mmPb, the thickness of the material is less than or equal to 0.35 mm).
In particular, the sheet of the invention has good environmental protection: (1) can be recycled: the commercially available radiation-proof sheet is basically made of rubber, and due to vulcanization treatment, the cost of the radiation-proof sheet which cannot be reused or is reused after aging is high and far exceeds the production cost of new materials, and the radiation-proof sheet causes environmental pollution. (2) The sheet material can be recycled and reused, and after corresponding additives (plasticizer, cold-proof agent, ultraviolet absorbent, antioxidant, calcium-zinc composite stabilizer and mildew-resistant agent) are added, the sheet material is simply and repeatedly calendered and formed for continuous use.
Detailed Description
For a better understanding of the present invention, the following detailed description is given in conjunction with specific examples. Technical terms used in the following description have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs.
The preparation method of the recyclable flexible radiation-proof sheet provided by the invention comprises the steps of synthesis of a base material, treatment of a filler and preparation of the sheet.
(1) Synthesis of base materials: prepared by reacting raw materials of chloroethylene, ethylene, a solvent, an initiator, a seed crystal and a dispersing agent in a reaction kettle.
At present, the synthesis of chlorinated polyethylene basically adopts a chlorination mode, and uses raw materials of polyethylene and chlorine gas, but the method has the problems of many byproducts, easy caking, equipment corrosion and the like, so that the invention preferably adopts a new synthesis method: adding 5-10 wt% of chlorinated polyethylene suspension into a reaction kettle to be used as seed crystal; then adding a dispersing agent, stirring at a high speed, and dispersing the seed crystal; then adding an initiator; stirring at low speed, introducing chloroethylene and ethylene gas into the reaction kettle at the same time, and controlling the speed ratio of the chloroethylene to the ethylene gas to be 1: 15-25; controlling the pressure of the reaction kettle at 0.09-0.35Mpa, and obtaining the chlorinated polyethylene base material after centrifugation, liquid removal and drying. The method can control the chlorine-containing range with accuracy, has simple steps, zero unsaturation degree of a target product and high stability, and a finished product has both flexibility and hot melt strength and is deficient in the existing single product.
The chlorine content of the seed crystal chlorinated polyethylene is 7-12%.
The solvent is any one or more of acetone, ethanol, benzene, distilled water and diethyl ether.
The dispersant is polyvinyl alcohol, and the addition amount is 0.05-3 wt%.
The initiator is dibenzoyl peroxide and TiCl4-AlR30.01-1.2 wt% of one or more of di-tert-butyl peroxide, isopropyl peroxydicarbonate and acetyl peroxycyclo-sulfonate.
The introducing speed of the chloroethylene is 0.3-0.6 Kg/min; the feeding speed of the ethylene is 2 to 4 Kg/min.
The chlorinated polyethylene base material has a chlorine content of 5-7%, and the vinyl chloride monomer can be uniformly dispersed and grafted with the vinyl monomer to form a high molecular weight polymer base material with a molecular weight of 3200 +/-200.
The novel synthesis method of the chlorinated polyethylene adopted by the invention changes the chlorine content, polymerization degree and rebound resilience of the material by adjusting the proportion of vinyl chloride and ethylene. Since chloroethylene and ethylene are gaseous and have difficulty in the aspects of dissolution speed and dispersion degree in the solvent, a proper amount of solvent and proper seed crystal are added into the reaction kettle, and the collision between the gas and the chlorinated polyethylene seed crystal increases the dissolution speed and dispersion degree of the gas and is beneficial to accurately controlling the chlorine content.
(2) And (3) treatment of the filler: and (3) immersing metal powder into the liquid (metal salt solution), coating, filtering, acidifying, drying and sintering to form a metal oxide coating layer different from the core metal particles.
The coating is one or more of spherical micro-nano powder of tungsten, bismuth, lead, cerium, chromium, rhenium, gadolinium, nickel, tantalum, europium and erbium.
The wrappage is tungsten oxide, bismuth oxide and rare earth metal oxide.
Heating tungsten, bismuth or rare earth metal salt to dissolve in distilled water or other solvent capable of dissolving the metal salt, adding the micro-nano metal powder and dispersant polyvinyl alcohol, stirring, pumping into precipitant, boiling for a period of time, cooling to room temperature, filtering, and washing. Acidifying: adding the filter residue into water for size mixing, pumping acid (liquid), stirring, heating, boiling, cooling, filtering, washing, drying, and calcining in a muffle furnace at 800 ℃ at 500 ℃ to obtain the metal micro-nano powder with the surface coated with metal oxide.
When the filler receives radiation, rays firstly irradiate on the surface of the oxide, atomic nuclei of the oxide reflect, refract and absorb part of the rays, electrons outside the nuclei absorb part of the energy of the rays, and the energy is converted into heat and released back to the ground state. Most rays pass through the outer layer oxide and contact with the inner layer metal particles, because the metal density is high, the atoms are tightly combined, so that the rays are blocked and absorbed, the capability of a small amount of reflected, refracted and scattered rays is low, and the rays are more easily absorbed by the outer layer oxide.
(3) Preparation of a sheet:
the weight percentages are as follows: 5-14% of base material, 0.5-3% of acrylate, 0.01-2% of nitrile rubber, 0.01-2% of thermoplastic elastomer, 60-89% of radiation-proof filler, 3-8% of plasticizer, 1-4% of cold-resistant agent, 0.2-1% of calcium-zinc composite stabilizer, 0.02-0.07% of ultraviolet absorbent, 0.02-0.07% of antioxidant, 0-1% of stearic acid, 0-1% of PE wax, 0-0.5% of mildew inhibitor and 0-0.3% of antistatic agent, adding the mixture into a mixing tank for high stirring, transferring the mixture to an open mill 160 for plasticizing at 200 ℃ after completely absorbing oil, and rolling the mixture on a four-roll forming machine for flaking at 180 ℃ and 230 ℃.
The acrylate is a base material and a processing aid, so that the bonding strength of the base material and the metal powder can be enhanced, and the plasticizing rate can be increased; two or more monomers selected from methyl methacrylate, ethyl acrylate, butyl acrylate and styrene are copolymerized, and the viscosity is 4-13 Pa.s.
The nitrile rubber is a toughening agent, the purity is more than or equal to 90%, and the granularity is powder of-300 meshes.
The thermoplastic elastomer is a toughening agent and is compounded with the nitrile rubber for use, so that the hardness of the material is prevented from being changed by single addition; one or more selected from the group consisting of designations G130D, G140D, G155D, G163D, and G172D.
The plasticizer is selected from one or more of dioctyl phthalate, dioctyl terephthalate, diisodecyl phthalate, tricresyl phosphate, cresyldiphenyl phosphate, epoxidized soybean oil, epoxy butyl oleate and triisooctyl 1,2, 4-trimellitate.
The cold-resistant agent is selected from one or more of dioctyl adipate, diisodecyl adipate, dioctyl azelate, dibutyl sebacate, dioctyl sebacate and diisooctyl sebacate, and is compounded with a plasticizer for use, so that the processing temperature can be reduced, the plasticizing time can be shortened, and the original performance of the material can be maintained under the freezing condition.
The addition proportion of the calcium-zinc composite stabilizer is related to acrylate and a plasticizer, and excessive addition can increase the plasticizing difficulty; the purity is more than or equal to 90 percent; the metal content is more than or equal to 7 percent.
The ultraviolet absorbent is any one of salicylic acid esters, benzophenones, benzotriazoles, substituted acrylonitrile and triazines.
The antioxidant is selected from any one of phosphite esters and phenol powder (or liquid) antioxidants.
The stearic acid is an internal lubricant and is powder with the granularity of-300 meshes.
The PE wax is an external lubricant, is compounded with stearic acid for use, has internal and external lubrication, improves the fluidity and the dispersity of the metal powder, and is powder with the granularity of-300 meshes.
The mildew inhibitor is any one of polyhexamethylene guanidine hydrochloride and 4, 5-dichloro-2-octyl-4-isothiazoline-3-ketone.
The antistatic agent is octadecyl diethanol amine.
The base material which does not need to be vulcanized in the general technology can not bear excessive filler and can not be rolled into a sheet and loose due to low bonding strength between polymer molecules. According to the sheet material, through optimizing the reasonable proportioning in the base material synthesis process and the coating treatment and compounding of the filler, the input amount of the radiation-proof filler can be increased, the actual highest filling weight ratio of the filler can reach more than 90%, the thickness can be reduced, the weight is reduced, the surface of the sheet material is smooth and flat, and the flexibility is good. Meanwhile, the filler and the base material are good in mixing uniformity, both adopt powder raw materials, the powder raw materials are easy to mix uniformly by using high-stirring equipment, banburying (rubber sheets are required to be used and the raw materials are rubber sheets and need to be vulcanized) is not required, and the production process is simple.
The invention is further illustrated by the following specific examples.
Example 1:
the recyclable flexible radiation-proof sheet comprises the following components in percentage by mass: 12% of chlorinated polyethylene, 2.2% of acrylic ester, 0.8% of nitrile rubber, 0.23% of G130D 0.23, 72% of radiation-proof filler, 8% of dioctyl phthalate, 2% of dioctyl adipate, 0.4% of calcium-zinc composite stabilizer, 0.02% of benzotriazole ultraviolet absorbent, 0.02% of phosphite antioxidant, 0.2% of stearic acid, 0.2% of PE wax, 0.03% of 4, 5-dichloro-2-octyl-4-isothiazoline-3-ketone and 0.1% of octadecyl diethanol amine.
Preparation of the sheet: the weight percentages are as follows: 12% of chlorinated polyethylene, 2.2% of acrylate, 0.8% of nitrile rubber, 0.23% of G130D 0.23, 72% of radiation-proof filler, 8% of dioctyl phthalate, 2% of dioctyl adipate, 0.4% of calcium-zinc composite stabilizer, 0.02% of benzotriazole ultraviolet absorbent, 0.02% of phosphite antioxidant, 0.2% of stearic acid, 0.2% of PE wax, 0.03% of 4, 5-dichloro-2-octyl-4-isothiazoline-3-ketone and 0.1% of octadecyl diethanol amine, adding the mixture into a mixing tank, stirring the mixture in a high speed, completely absorbing oil, transferring the mixture to an open mill for plasticizing at 180 ℃, and rolling the mixture on a four-roll forming machine for tabletting at 210 ℃.
And (3) synthesis of the base material: adding 10 wt% of chlorinated polyethylene suspension into a reaction kettle to be used as seed crystals; then adding 0.1 wt% of polyvinyl alcohol, stirring at high speed, and dispersing seed crystals; then 0.1 wt% of dibenzoyl peroxide is added; stirring at a low speed, introducing chloroethylene and ethylene gas into the reaction kettle at the same time, and controlling the speed ratio of the chloroethylene to the ethylene gas to be 1: 17; controlling the pressure of the reaction kettle at 0.09-0.35Mpa, and obtaining the chlorinated polyethylene base material after centrifugation, liquid removal and drying.
And (3) treating the filler: heating ammonium tungstate to dissolve in solvent, preparing 2L ammonium tungstate solution, adding 2kg nanometer bismuth powder and 5g dispersant polyvinyl alcohol, stirring, pumping precipitator saturated calcium chloride, boiling for a period of time, cooling to room temperature, filtering, and washing. Adding the filter residue into water for size mixing, pumping 0.1mol/L dilute hydrochloric acid, stirring, heating, boiling, cooling, filtering, washing, drying, and calcining in a muffle furnace at 600 ℃ for 3h to obtain the bismuth nano powder with the surface coated with tungsten oxide. (can be expanded in equal proportion according to equipment conditions)
Example 2:
the recyclable flexible radiation-proof sheet comprises the following components in percentage by mass: 14% of chlorinated polyethylene, 3% of acrylic ester, 1.9% of nitrile rubber, 0.2% of G130D 0.2, 70% of radiation-proof filler, 7% of dioctyl phthalate, 3% of dioctyl adipate, 0.4% of calcium-zinc composite stabilizer, 0.02% of benzotriazole ultraviolet absorbent, 0.02% of phosphite antioxidant, 0.15% of stearic acid, 0.15% of PE wax, 0.03% of 4, 5-dichloro-2-octyl-4-isothiazoline-3-ketone and 0.13% of octadecyl diethanol amine.
Preparation of the sheet: the weight percentages are as follows: 14% of chlorinated polyethylene, 3% of acrylate, 1.9% of nitrile rubber, 0.2% of G130D 0.2, 70% of radiation-proof filler, 7% of dioctyl phthalate, 3% of dioctyl adipate, 0.4% of calcium-zinc composite stabilizer, 0.02% of benzotriazole ultraviolet absorbent, 0.02% of phosphite antioxidant, 0.15% of stearic acid, 0.15% of PE wax, 0.03% of 4, 5-dichloro-2-octyl-4-isothiazoline-3-ketone and 0.13% of octadecyl diethanol amine, adding the mixture into a mixing tank, stirring the mixture in a high speed, completely absorbing oil, transferring the mixture to a mill for plasticizing at 190 ℃, and rolling the mixture on a four-roll forming machine for sheeting at 200 ℃.
And (3) synthesis of the base material: adding 7 wt% of chlorinated polyethylene suspension into a reaction kettle to be used as seed crystal; then adding 0.1 wt% of polyvinyl alcohol, stirring at high speed, and dispersing seed crystals; then 0.1 wt% of dibenzoyl peroxide is added; stirring at low speed, introducing chloroethylene and ethylene gas into the reaction kettle at the same time, and controlling the speed ratio of the chloroethylene to the ethylene gas to be 1: 20; controlling the pressure of the reaction kettle at 0.09-0.35Mpa, and obtaining the chlorinated polyethylene base material after centrifugation, liquid removal and drying.
And (3) treating the filler: heating gadolinium chloride to dissolve in a solvent to prepare 2L gadolinium chloride solution, adding 2kg of nano tungsten powder and 5g of dispersant polyvinyl alcohol into the gadolinium chloride solution, stirring, pumping in oxalic acid serving as a precipitant, boiling for a period of time, cooling to room temperature, filtering, washing, drying, and finally calcining in a muffle furnace at 700 ℃ for 3 hours to obtain the tungsten nano powder with the surface coated with gadolinium oxide. (can be expanded in equal proportion according to equipment conditions)
Example 3:
the recyclable flexible radiation-proof sheet comprises the following components in percentage by mass: 10% of chlorinated polyethylene, 1.3% of acrylic ester, 0.3% of nitrile rubber, 0.2% of G130D 0.2, 80% of radiation-proof filler, 6% of dioctyl phthalate, 1.5% of dioctyl adipate, 0.3% of calcium-zinc composite stabilizer, 0.02% of benzotriazole ultraviolet absorbent, 0.02% of phosphite antioxidant, 0.13% of stearic acid, 0.15% of PE wax, 0.03% of 4, 5-dichloro-2-octyl-4-isothiazoline-3-ketone and 0.05% of octadecyl diethanol amine.
Preparation of the sheet: the weight percentages are as follows: 10% of chlorinated polyethylene, 1.3% of acrylate, 0.3% of nitrile rubber, 0.2% of G130D 0.2, 80% of radiation-proof filler, 6% of dioctyl phthalate, 1.5% of dioctyl adipate, 0.3% of calcium-zinc composite stabilizer, 0.02% of benzotriazole ultraviolet absorbent, 0.02% of phosphite antioxidant, 0.13% of stearic acid, 0.15% of PE wax, 0.03% of 4, 5-dichloro-2-octyl-4-isothiazoline-3-ketone and 0.05% of octadecyl diethanol amine, adding the mixture into a mixing tank, stirring the mixture in high temperature, completely absorbing oil, transferring the mixture to an open mill for plasticizing at 185 ℃, and rolling the mixture on a four-roll forming machine for sheeting at 205 ℃.
And (3) synthesis of the base material: adding 10 wt% of chlorinated polyethylene suspension into a reaction kettle to be used as seed crystals; then adding 0.1 wt% of polyvinyl alcohol, stirring at high speed, and dispersing seed crystals; then 0.1 wt% of dibenzoyl peroxide is added; stirring at a low speed, introducing chloroethylene and ethylene gas into the reaction kettle at the same time, and controlling the speed ratio of the chloroethylene to the ethylene gas to be 1: 17; controlling the pressure of the reaction kettle at 0.09-0.35Mpa, and obtaining the chlorinated polyethylene base material after centrifugation, liquid removal and drying.
And (3) treating the filler: heating ammonium tungstate to dissolve in solvent, preparing 2L ammonium tungstate solution, adding 2kg of nano tantalum powder and 5g of dispersant polyvinyl alcohol, stirring, pumping precipitator saturated calcium chloride, boiling for a period of time, cooling to room temperature, filtering, and washing. Adding the filter residue into water for size mixing, pumping 0.1mol/L dilute hydrochloric acid, stirring, heating, boiling, cooling, filtering, washing, drying, and calcining in a muffle furnace at 600 ℃ for 3h to obtain the tantalum nano powder with the surface coated with tungsten oxide. (can be expanded in equal proportion according to equipment conditions)
Example 4:
in the open milling process, the formed sheet materials recovered after 3-5 months of use in examples 1-3 are directly mixed and milled with the respective highly stirred powder new materials in the same formula according to the weight ratio of 1:1, and the mixture is rolled into sheets on a four-roll forming machine.
Example 5:
according to the process of the embodiment 4, the sheet materials of the embodiments 1 to 3 are recycled after each 3 to 5 months of use, the recycled sheet materials are directly mixed and milled with respective high-stirring powder new materials under the same formula according to the weight ratio of 1:1, and the recycling and the reprocessing are repeated for 5 times.
Performance detection
The performance test method for the sheets obtained in examples 1 to 5 is as follows:
(1) tensile property: (determination of tensile Properties of plastics according to GB/T1040.3-2006 part 3: test conditions for films and sheets)
Sample preparation: a strip sample with the width of 20mm and the length of 200mm is selected, and two parallel marked lines with the interval of 50mm are arranged in the middle of the sample.
The experimental steps are as follows: the width and thickness were measured within 5mm of the middle of the sample from each end of the gauge. The width is accurate to 0.1mm and the thickness is accurate to 0.02 mm. The maximum and minimum values of the specimen width and thickness were recorded. The sample is placed in the clamp and the sample is tightened slightly before tightening the clamp and then the clamp is clamped smoothly and firmly. After the pre-stress was balanced, the calibrated extensometer was mounted on the gauge of the specimen and adjusted. And opening the servo control tension tester at room temperature of 23 ℃ and 51% RH, controlling the speed to be 50mm/min (tolerance +/-10%), testing the numerical value, and calculating the result.
ε＝η1/η
In the formula:
ε -strain, expressed as a ratio or percentage;
η1-sample gauge length, in units (mm);
η -increment of length between sample marks, in units (mm).
(2) Shore hardness: (determination of indentation hardness (Shore hardness) in accordance with GB/T2411-
Sample preparation: the samples 12 were laminated to give sample pieces having a thickness of more than 4mm, and cut to have a length and a width of 100mm each. The surface of the sample is flat, and the area covered by the pressure seat when the pressure seat is contacted with the sample at least has a radius of 6mm away from the top end of the pressure pin.
The experimental steps are as follows:
the sample is placed on a hard, firm and stable horizontal surface and the durometer is held in a vertical position with the tip of the stylus at least 9mm from either edge of the sample. The pressure pad was applied to the sample without impact, parallel to the sample and pressure was applied, the pad was in intimate contact with the sample, and the value was read (15. + -.1) s later. On the same sample, 5 hardness values were measured at least 6mm apart, and the average value was calculated.
(3) Lead equivalent: (carried out according to the determination of the attenuation Performance of the GBZ/T147-
Sample preparation: the sample was cut into a length and a width of 200mm each. The thickness of 4 points 20mm from the edge, and the thickness of 1 center point were measured and recorded, respectively.
The experimental steps are as follows:
adjusting the tube voltage to 120kV, adjusting the diameter of a radiation beam to be 20 +/-1 mm, adjusting the distance between a detector and a sample to be more than 700mm, placing a 2.50mm Al filter at a radiation beam port, performing ray filtration, measuring blank values without the sample, then placing a plurality of pure lead standard sheets of 0.1mm, 0.15mm, 0.2mm and the like on a clamp for measuring and recording the values, finally placing the sample on the clamp for measuring and recording the values, calculating the transmittance, and comparing the transmittance with the pure lead standard sheets to obtain the lead equivalent.
R＝M/M0
In the formula:
m-the measurement reading of the X-ray passing through the sample to be measured;
M0-X-ray measurement readings in the absence of the sample to be measured.
The results of detection of the sheets obtained in examples 1 to 5 above were as follows:
table 1 examples 1-3 test results of properties of formed sheets
Figure BDA0003114891640000081
Table 2 test results of the recycled sheet recycling performance of example 4
Figure BDA0003114891640000082
TABLE 3 result of measurement of recycled sheet recycling performance of example 5
Figure BDA0003114891640000083
Figure BDA0003114891640000091
Table 1 shows the results of measuring the properties of the molded sheets of examples 1 to 3. Has a lead equivalent of 0.125mmPb, a thickness of at least 0.4mm, and a weight of 2kg/m2Examples 1-3 of the present invention have smaller thickness and weight at better lead equivalent.
Table 2 shows the results of the measurement of the recycling properties of the recovered sheet in example 4. The recovery 1 to 3 are the performance test results of examples 1 to 3 in which each raw material was recovered and used 1 time. It can be seen that the sheet recycling performance is substantially equivalent to that of the new material, except that the tensile strength and hardness are slightly increased and the elongation is slightly reduced, and the overall performance is not adversely affected.
Table 3 shows the results of the measurement of the recycling properties of the recovered sheet in example 5. The recovery 1 to 3 are the results of performance tests after repeating 5 times of the recovery reprocessing of each raw material of examples 1 to 3, respectively. Similarly, the sheet recycling performance is basically equivalent to that of the new material except that the tensile strength and hardness are slightly increased and the elongation is slightly reduced.
The results in tables 1-3 show that the recyclable flexible radiation-proof sheet prepared by the invention has light weight, small hardness, small thickness and small transmissivity (large lead equivalent); can be recycled, and the performances of the sheet are basically unchanged after recycling and reprocessing.
Table 4 examples 1-3 test results of the properties of 2 laminated formed sheets
Figure BDA0003114891640000092
Table 5 examples 1-3 test results of performance of formed sheet material stack with 4 layers
Figure BDA0003114891640000093
Table 6 test results of the recycled sheet of example 4 for recycling by stacking 2 layers
Figure BDA0003114891640000094
Table 7 test results of the performance of the recycled sheet of example 4 in which 4 layers were stacked.
Figure BDA0003114891640000095
Figure BDA0003114891640000101
Table 8 test results of the recycled sheet of example 5 for recycling by stacking 2 layers
Figure BDA0003114891640000102
TABLE 9 test results of the recycled sheet of example 5 for reuse with 4 layers stacked
Figure BDA0003114891640000103
Tables 4-9 show the performance test results of the recyclable flexible radiation-proof sheet prepared by the method of the invention after multi-layer superposition tests, the results are consistent with the single-layer test results, and the transmittance is reduced along with the increase of the number of layers.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (9)

1. A recyclable flexible radiation-proof sheet is prepared from the following raw materials in percentage by mass: 5-14% of base material, 60-89% of radiation-proof filler, 0.5-3% of acrylate, 0.01-2% of nitrile rubber, 0.01-2% of thermoplastic elastomer, 3-8% of plasticizer, 1-4% of cold-resistant agent, 0.2-1% of calcium-zinc composite stabilizer, 0.02-0.07% of ultraviolet absorbent, 0.02-0.07% of antioxidant and 0-2.8% of other components; the radiation-proof filler is metal micro-nano powder with the surface coated with metal oxide, and other components are selected from stearic acid, PE wax, an anti-mildew agent and an antistatic agent.
2. The recyclable flexible radiation protective sheet according to claim 1, wherein the base chlorinated polyethylene has a chlorine content of 5-7% and a molecular weight of 3200 ± 200.
3. The recyclable flexible radiation protective sheet according to claim 1, wherein the radiation protective filler is wrapped with one or more of spherical micro-nano powders of tungsten, bismuth, lead, cerium, chromium, rhenium, gadolinium, nickel, tantalum, europium and erbium, and the wrapping is tungsten oxide, bismuth oxide and rare earth metal oxide.
4. The recyclable flexible radiation protective sheet of claim 1 wherein the acrylate is a copolymer of two or more monomers selected from the group consisting of methyl methacrylate, ethyl acrylate, butyl acrylate, styrene, and has a viscosity of 4 to 13 pa.s; the nitrile rubber is powder with the purity of more than or equal to 90 percent and the granularity of 300 meshes; the thermoplastic elastomer is selected from one or more of the trade names G130D, G140D, G155D, G163D and G172D; the plasticizer is selected from one or more of dioctyl phthalate, dioctyl terephthalate, diisodecyl phthalate, tricresyl phosphate, cresyldiphenyl phosphate, epoxidized soybean oil, epoxy butyl oleate and triisooctyl 1,2, 4-trimellitate; the cold-resistant agent is selected from one or more of dioctyl adipate, diisodecyl adipate, dioctyl azelate, dibutyl sebacate, dioctyl sebacate and diisooctyl sebacate; the purity of the calcium-zinc composite stabilizer is more than or equal to 90 percent, and the metal content is more than or equal to 7 percent; the ultraviolet absorbent is any one of salicylic acid esters, benzophenones, benzotriazoles, substituted acrylonitrile and triazines; the antioxidant is selected from any one of phosphite esters and phenol powder or liquid antioxidant.
5. The recyclable flexible radiation protective sheet of claim 1 wherein the stearic acid is a powder having a particle size of 300 mesh; the PE wax is powder with the granularity of 300 meshes; the mildew inhibitor is any one of polyhexamethylene guanidine hydrochloride and 4, 5-dichloro-2-octyl-4-isothiazoline-3-ketone; the antistatic agent is octadecyl diethanol amine.
6. A method of making a recyclable flexible radiation protective sheet according to any of claims 1 to 5 comprising the steps of: mixing and stirring the raw materials for preparing the radiation-proof sheet, plasticizing at the temperature of 160-230 ℃ after completely absorbing oil, and rolling into the sheet at the temperature of 160-230 ℃.
7. The method for preparing flexible radiation protection sheet material capable of being recycled according to claim 6, wherein the radiation protection sheet material is prepared from chlorinated polyethylene as base material by the following method: adding 5-10 wt% of chlorinated polyethylene suspension into a reaction kettle to be used as seed crystal; then adding a dispersing agent, stirring at a high speed, and dispersing the seed crystal; then adding an initiator; stirring at low speed, introducing chloroethylene and ethylene gas into the reaction kettle at the same time, and controlling the speed ratio of the chloroethylene to the ethylene gas to be 1: 15-25; controlling the pressure of the reaction kettle at 0.09-0.35Mpa, and obtaining the chlorinated polyethylene base material after centrifugation, liquid removal and drying.
8. The method for preparing flexible radiation protective sheet material capable of being recycled according to claim 7, wherein in the process of preparing base material chlorinated polyethylene, the chlorine content of the seed crystal chlorinated polyethylene is 7-12%; the solvent is any one or more of acetone, ethanol, benzene, distilled water and diethyl ether; the dispersant is polyvinyl alcohol, and the addition amount is 0.05-3 wt%; the initiator is dibenzoyl peroxide and TiCl4-AlR30.01-1.2 wt% of one or more of di-tert-butyl peroxide, isopropyl peroxydicarbonate and acetyl peroxycyclo-sulfonate; the introducing speed of the chloroethylene is 0.3-0.6 Kg/min; the feeding speed of the ethylene is 2 to 4 Kg/min.
9. The method for preparing the recyclable flexible radiation protective sheet according to claim 6, wherein the radiation protective filler in the raw materials of the radiation protective sheet is prepared by the following method: heating and dissolving tungsten, bismuth or rare earth metal salt in a solvent, adding the micro-nano metal powder and dispersant polyvinyl alcohol, stirring, pumping a precipitator, boiling for a period of time, cooling to room temperature, filtering and washing; acidifying: adding filter residues into water for size mixing, pumping liquid acid, stirring, heating, boiling, cooling, filtering, washing, drying, and finally calcining in a muffle furnace at 800 ℃ at 500 ℃ to obtain the metal micro-nano powder with the surface coated with metal oxides.
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CN103275417A (en) * 2013-05-28 2013-09-04 上海肃盛贸易有限公司 Composite anti-radiation material
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
CN112831078A (en) * 2021-02-08 2021-05-25 南通大学 Preparation method of core-shell structure tungsten/gadolinium oxide PVC (polyvinyl chloride) calendered material for X and gamma ray protection
CN112895621A (en) * 2021-02-23 2021-06-04 武汉市莎卡娜尔科技有限公司 Anti-radiation gradient composite material and preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103275417A (en) * 2013-05-28 2013-09-04 上海肃盛贸易有限公司 Composite anti-radiation material
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
CN112831078A (en) * 2021-02-08 2021-05-25 南通大学 Preparation method of core-shell structure tungsten/gadolinium oxide PVC (polyvinyl chloride) calendered material for X and gamma ray protection
CN112895621A (en) * 2021-02-23 2021-06-04 武汉市莎卡娜尔科技有限公司 Anti-radiation gradient composite material and preparation method and application thereof

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