CN112853741A - Method for producing X-ray shielding material and X-ray shielding material - Google Patents

Method for producing X-ray shielding material and X-ray shielding material Download PDF

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CN112853741A
CN112853741A CN202110122358.1A CN202110122358A CN112853741A CN 112853741 A CN112853741 A CN 112853741A CN 202110122358 A CN202110122358 A CN 202110122358A CN 112853741 A CN112853741 A CN 112853741A
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fiber material
ray shielding
mass ratio
shielding material
barium
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CN112853741B (en
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刘丽影
吴洋
覃文军
其他发明人请求不公开姓名
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Northeastern University China
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Northeastern University China
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/51—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof
    • D06M11/55—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof with sulfur trioxide; with sulfuric acid or thiosulfuric acid or their salts
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/44—Oxides or hydroxides of elements of Groups 2 or 12 of the Periodic System; Zincates; Cadmates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/248—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing sulfur
    • D06M13/256—Sulfonated compounds esters thereof, e.g. sultones
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/325—Amines
    • D06M13/342—Amino-carboxylic acids; Betaines; Aminosulfonic acids; Sulfo-betaines

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

The invention relates to the field of radiation protection, in particular to a manufacturing method of an X-ray shielding material and the X-ray shielding material. The manufacturing method of the X-ray shielding material comprises the following steps: and carrying out sulfonation reaction on the fiber material and 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 X-ray shielding material. The X-ray shielding material has more barium element and has the function of shielding X-rays; the weight is light, the thickness is small, and the wearing is convenient; meanwhile, the method has the advantages of simple steps, short production period, large-scale industrial application and low cost.

Description

Method for producing X-ray shielding material and X-ray shielding material
Technical Field
The invention relates to the field of radiation protection, in particular to a manufacturing method of an X-ray shielding material and the X-ray shielding material.
Background
The X-ray is an electromagnetic wave with shorter wavelength, has strong penetrating power and is widely applied to the fields of medical treatment and the like. However, the long-term exposure to X-rays can cause great harm to human bodies, and diseases such as leukemia, tumors and the like can be caused by the exposure to X-rays in excess of a certain dosage, thereby bringing serious threat to life.
For X-ray protection, elements with higher atomic number and higher density are generally used as materials of the protective barrier. Lead, the earliest of which was utilized. The lead-containing protective material mainly comprises the following components: lead plate, lead glass, lead apron, etc. The protective material plays a good role in protection, but has some disadvantages, for example, lead is a toxic element, and the manufactured protective material is relatively heavy, and generally, the mass of a lead garment exceeds 15kg, and the lead garment is tight and windproof, so that a doctor who intervenes in an operation for hours is challenged, and the agility and the effect of the operation of the doctor are easily affected. In addition, the existing lead protective clothing cannot be applied to arm protection of doctors due to the fact that the existing lead protective clothing is heavy. Therefore, it is important to develop an X-ray shielding material having a small quality and excellent shielding performance.
In the prior art, researches on lead-free X-ray shielding materials mainly use a shielding agent to fill materials such as rubber, polypropylene and the like by means of blending and the like. For example: in the prior art, the rare earth element oxide particles and the polypropylene particles are fully blended, and then the non-woven fabric is prepared by the steps of melt spinning and the like. Or the barium sulfate emulsion slurry and the yellowed and dissolved viscose solution are mixed uniformly, and then the cellulose fiber for preventing X-ray radiation is prepared through the steps of spinning, forming and the like.
Although the flexible X-ray shielding material prepared by the prior art has certain X-ray protection capability, the flexible X-ray shielding material still has certain limitations, for example, the flexible X-ray shielding material is prepared by blending shielding agents such as rare earth elements and the like with a base material and then carrying out melt spinning and other steps, and has complex preparation process and high cost. The shielding agent is filled into the matrix material by the traditional blending mode and the like, the shielding agent is easy to agglomerate and disperse unevenly, and the prepared fiber is easy to generate a plurality of structural defects such as gaps, cavities and the like, so that the X-ray shielding performance of the material is influenced. In addition, the addition fraction of the shielding agent must exceed a certain fraction to have better X-ray protection capability. As the amount of shielding agent increases, the lead equivalent increases accordingly, and the density gradually increases. In order to achieve the shielding effect, a large amount of shielding agent is often added, and the prepared material is heavier. And with the increase of the addition fraction of the shielding agent, the spinning is difficult, the yarn breakage rate is increased, and the industrial application of the shielding material is severely restricted.
Disclosure of Invention
Technical problem to be solved
The technical problem to be solved by the invention is how to manufacture the X-ray shielding material with light weight, simple manufacture and shielding performance.
(II) technical scheme
In order to achieve the purpose, the invention adopts the main technical scheme that:
the invention provides a method for manufacturing an X-ray shielding material, which comprises the following steps: step 1, carrying out sulfonation reaction on a fiber material and a sulfonating agent to form a sulfonated fiber material; and 2, reacting the sulfonated fiber material with a barium ion-containing solution to obtain the X-ray shielding material.
According to the invention, the fibrous material is in the form of a cloth; the fiber material is a fiber with a benzene ring, a fiber with a hydroxyl group or a fiber with an amido bond, and the sulfonating agent is a sulfonating agent capable of performing sulfonation reaction with the benzene ring, the hydroxyl group or the amido bond.
According to the invention, the fiber material is aramid fiber or terylene, and the sulfonating agent is concentrated sulfuric acid or chlorosulfonic acid; or the fiber material is cotton, aramid fiber, chinlon or spandex, and the sulfonating agent is sulfamic acid.
According to the invention, the barium ion-containing solution is a barium hydroxide solution, a barium chloride solution or a barium nitrate solution.
According to the invention, in step 1: mixing a sulfonating agent and an organic solvent according to a preset mass ratio to form a mixed solution, and then immersing the fiber material into the mixed solution according to a preset solid-liquid mass ratio to perform sulfonation reaction; the method comprises the following two combination modes: the first combination mode is as follows: the sulfonating agent is sulfamic acid, the organic solvent is dimethylformamide, the fiber material is cotton, and the preset mass ratio is 1: (12-38), presetting the solid-liquid mass ratio to be 1: (35-42), wherein the sulfonation reaction temperature is 90-130 ℃, and the sulfonation reaction time is more than or equal to 10 min; the second combination mode: the sulfonating agent is chlorosulfonic acid, the organic solvent is dichloroethane, the fiber material is aramid fiber, and the preset mass ratio is 1: (22-29), presetting the solid-liquid mass ratio to be 1: (73-84), the sulfonation reaction temperature is 35-60 ℃, and the sulfonation reaction time is more than or equal to 100 min.
According to the present invention, in the first combination: the sulfonation reaction time is 30-70 min; in the second combination mode: the sulfonation reaction time is 110-130 min.
According to the invention, in step 1: the fiber material and the organic solvent are mixed according to a solid-liquid mass ratio of 1: (45-65), and then taking out the fiber material according to the solid-liquid mass ratio of 1: (58-78) immersing in a sulfonating agent for sulfonation reaction to form a sulfonated fiber material, wherein the sulfonation reaction temperature is 15-35 ℃, and the sulfonation reaction time is more than or equal to 10 min; the fiber material, the organic solvent and the sulfonating agent are selected according to the following combination mode: the combination mode is three: the sulfonating agent is concentrated sulfuric acid, the organic solvent is tetrahydrofuran, and the fiber material is aramid fiber or terylene.
According to the invention, in step 2: immersing the sulfonated fiber material into 0.01-0.15 mol/L barium ion-containing solution; the method comprises the following three combination modes: the first combination mode is as follows: the sulfonating agent is sulfamic acid, the organic solvent is dimethylformamide, the fiber material is cotton, the barium ion-containing solution is a barium hydroxide solution, the reaction temperature in the step 2 is 60-80 ℃, the reaction time is more than or equal to 15min, and the mass ratio of the solute of the barium ion-containing solution to the sulfonated fiber material is (0.5-5): 1; the second combination mode: the sulfonating agent is chlorosulfonic acid, the organic solvent is dichloroethane, the fiber material is aramid fiber, the barium-ion-containing solution is barium hydroxide solution, the reaction temperature in the step 2 is 15-35 ℃, the reaction time is more than or equal to 45min, and the mass ratio of the solute of the barium-ion-containing solution to the sulfonated fiber material is (2.5-4.5): 1; the combination mode is three: the sulfonating agent is concentrated sulfuric acid, the organic solvent is tetrahydrofuran, the fiber material is aramid fiber or terylene, the barium ion-containing solution is barium chloride solution, the reaction temperature in the step 2 is 15-35 ℃, the reaction time is more than or equal to 15min, and the mass ratio of the solute of the barium ion-containing solution to the sulfonated fiber material is (2-4): 1.
According to the invention, in step 2: in the first combination mode: the reaction time is 15-180 min; in the second combination mode: the reaction temperature is room temperature, and the reaction time is 45-75 min; in the third combination mode: the reaction temperature is room temperature, and the reaction time is 15-45 min.
According to the invention, the organic solvent is any one or a mixture of more than two of acetone, tetrahydrofuran, 1, 2-dichloroethane and dimethylformamide.
Another aspect of the present invention provides an X-ray shielding material prepared by any one of the above methods for producing an X-ray shielding material.
(III) advantageous effects
The invention has the beneficial effects that:
the manufacturing method of the X-ray shielding material can enable the fiber material to obtain higher barium content, and the effect of shielding X-rays is achieved; the weight is light, the thickness is small, and the wearing is convenient; the method has the advantages of simple steps, short production period, large-scale industrial application and low cost.
The X-ray shielding material has higher barium element content and forms the effect of shielding X-rays; the weight is light, the thickness is small, and the wearing is convenient; the cost is low.
Drawings
FIG. 1 is an XPS spectrum of raw cotton cloth in example 7 below; fig. 2 is an XPS spectrum of a finished X-ray shielding material in example 7 below. Wherein, the intensity (a.u.) means that the ordinate is intensity; o in O1s represents oxygen atom, 1s represents its 1s orbital, this expression represents O atom, and the rest labels are expressed similarly.
Detailed Description
For the purpose of better explaining the present invention and to facilitate understanding, the present invention will be described in detail by way of specific embodiments with reference to the accompanying drawings.
The embodiment provides a method for manufacturing an X-ray shielding material, which comprises the following steps:
step 1, carrying out sulfonation reaction on the fiber material and a sulfonating agent to form a sulfonated fiber material.
And 2, reacting the sulfonated fiber material with the barium-containing ion solution, so that the barium element is uniformly connected to the fiber material, and obtaining the barium-based X-ray shielding material based on the fiber material.
The X-ray shielding material prepared by the method can obtain higher barium content and has the effect of shielding X-rays. And the X-ray shielding material has light weight and small thickness and is convenient to wear. Meanwhile, the method has the advantages of simple steps, short production period, large-scale industrial application and low cost. In addition, the form of the fiber material is preferably in a cloth shape, and the fiber material can be directly manufactured into common radiation protection equipment such as shielding clothes, shielding caps, shielding gloves and the like, and the shielding effect and the X-ray attenuation rate of the fiber can be further improved by increasing the number of layers of the X-ray shielding fiber.
Specifically, the step 1 includes the following substeps:
step 1.1, mixing a sulfonating agent and an organic solvent according to a preset mass ratio to form a mixed solution.
And step 1.2, soaking the fiber material into the mixed solution according to a preset solid-liquid mass ratio (mass ratio of the fiber material to the mixed solution) to carry out sulfonation reaction to form the sulfonated fiber material.
Step 1.3, the sulfonated fiber material is removed from the mixed solution and washed to neutrality.
Wherein, fiber material and sulfonating agent are preferably selected according to the following matching, and the effect is better:
the fiber material is a fiber with a benzene ring, for example, the fiber material is aramid fiber or polyester fiber; the sulfonating agent is a sulfonating agent capable of undergoing sulfonation with a benzene ring, such as concentrated sulfuric acid or chlorosulfonic acid.
Alternatively, the fibrous material is hydroxyl-bearing fibers, for example, the fibrous material is cotton; the sulfonating agent is a sulfonating agent capable of undergoing a sulfonation reaction with a hydroxyl group, such as sulfamic acid. The combination of cotton and sulfamic acid is better, the obtained X-ray shielding material has better radiation protection effect, softer texture, lower cost and more beautiful surface.
Alternatively, the fiber material is a fiber with amide bonds, for example, the fiber material is aramid fiber, chinlon or spandex, and the sulfonating agent is a sulfonating agent capable of undergoing a sulfonation reaction with the amide bonds, for example, sulfamic acid.
The organic solvent is any one or mixture of more than two of acetone, tetrahydrofuran, 1, 2-dichloroethane and dimethylformamide.
More specifically, it is preferably performed in one of three combinations:
the first combination mode is as follows: the sulfonating agent is sulfamic acid, the organic solvent is dimethylformamide, the fiber material is cotton, and the preset mass ratio is 1: (10-45) [ preferably 1: (12-38) ], presetting a solid-liquid mass ratio of 1: (30-50) [ preferably 1: (35-42) ], wherein the sulfonation reaction temperature is 70-150 ℃ (preferably 90-130 ℃), and the sulfonation reaction time is more than or equal to 10min (preferably 10-135min, more preferably 30-70 min).
The second combination mode: the sulfonating agent is chlorosulfonic acid, the organic solvent is dichloroethane, the fiber material is aramid fiber, and the preset mass ratio is 1: (20-35) [ preferably 1: (22-29) ], presetting a solid-liquid mass ratio of 1: (70-90) [ preferably 1: (73-84) ], the sulfonation reaction temperature is 30-70 ℃ (preferably 35-60 ℃), and the sulfonation reaction time is more than or equal to 100min (preferably 110-.
The combination mode is three: the sulfonating agent is concentrated sulfuric acid, the organic solvent is tetrahydrofuran, the fiber material is aramid fiber or terylene, the sulfonation reaction temperature is 15-35 ℃ (preferably room temperature), and the sulfonation reaction time is more than or equal to 10min (preferably 10-30 min).
Of course, the above combinations are only a few preferred alternatives, the present invention is not limited to the above combinations, and any fiber material and sulfonating agent that can undergo a sulfonation reaction can be used as an embodiment of the present invention, for example, the sulfonating agent can also be changed into sulfur trioxide and sulfite. The sulfur trioxide is matched with a fiber material with a benzene ring, such as aramid or terylene; the sulphite is matched with fibrous materials containing halogenated hydrocarbons, such as polyvinyl chloride fibers, acrylonitrile copolymer fibers.
Of course, step 1 may also be performed as: firstly, mixing a fiber material and an organic solvent according to a solid-liquid mass ratio of 1: (45-65) [ preferably 1:55] and then taking out the fiber material in a solid-liquid mass ratio of 1: (58-78) [ preferably 1:68] immersing in a sulfonating agent to perform sulfonation reaction to form a sulfonated fiber material, wherein the sulfonation reaction temperature is 15-35 ℃ (preferably room temperature), and the sulfonation reaction time is 10min or more (preferably 10-30 min). And the fiber material, the organic solvent and the sulfonating agent are selected according to a combination mode III: namely, the sulfonating agent is concentrated sulfuric acid, the organic solvent is tetrahydrofuran, and the fiber material is aramid fiber or terylene. Of course, the first combination, the second combination, or other combinations may also be utilized.
Specifically, step 2 includes the following substeps:
and 2.1, soaking the sulfonated fiber material obtained in the step 1 and washed to be neutral in a barium ion-containing solution for reaction to form the X-ray shielding material, wherein the concentration of the barium ion-containing solution is 0.01-0.15 mol/L. The barium ion-containing solution is preferably a barium hydroxide solution, a barium chloride solution or a barium nitrate solution. Corresponding to the above three combinations, the following combinations can be further formed:
in the first combination mode: the barium ion-containing solution is a barium hydroxide solution, the reaction temperature in step 2.1 is 50-95 ℃ (preferably 60-80 ℃), the reaction time is more than or equal to 15min (preferably 15-180min), and the mass ratio of the solute of the barium ion-containing solution to the sulfonated fiber material (0.5-5): 1 immersing into a barium ion-containing solution;
in the second combination mode: the barium ion-containing solution is a barium hydroxide solution, the reaction temperature in the step 2.1 is 15-35 ℃ (preferably room temperature), the reaction time is more than or equal to 45min (preferably 45-75min, more preferably 60min), and the sulfonated fiber material is immersed into the barium ion-containing solution according to the mass ratio of the solute of the barium ion-containing solution to the sulfonated fiber material (2.5-4.5):1[ preferably 3.6:1 ];
in the third combination mode: the barium ion-containing solution is a barium chloride solution, the reaction temperature in step 2.1 is 15 to 35 ℃ (preferably room temperature), the reaction time is 15min or more (preferably 15 to 45min, more preferably 30min), and the sulfonated fiber material is immersed in the barium ion-containing solution according to the mass ratio of the solute of the barium ion-containing solution to the sulfonated fiber material (2.5 to 4.5):1[ preferably 3:1 ].
And 2.2, washing and drying the X-ray shielding material reacted in the step 2.1 to obtain a final X-ray shielding material finished product.
According to the ICP-OES test, the content of barium in the obtained X-ray shielding material is more than or equal to 2%, and the X-ray can be better shielded.
Based on the above description of the overall scheme, specific examples are provided below as references:
the amount of pure cotton cloth was the same in the following examples 1 to 15, and the amount of dimethylformamide was the same.
Example 1
Mixing sulfamic acid and dimethylformamide according to the mass ratio of 1:12 to form a mixed solution, soaking pure cotton cloth into the mixed solution according to the solid-liquid mass ratio of 1:42, and reacting at 120 ℃ for 60min to form the sulfonated fiber material. The sulfonated fiber material is then removed and washed to neutrality. Then, the washed sulfonated fiber material is immersed into a barium hydroxide solution with the concentration of 0.06mol/L according to the mass ratio of 2:1 of the solute of the barium ion-containing solution to the sulfonated fiber material, and reacts for 90min at 70 ℃ to form an X-ray shielding material, and then the X-ray shielding material is washed and dried to finally obtain the finished product of the X-ray shielding material.
Example 2
Mixing sulfamic acid and dimethylformamide according to the mass ratio of 1:19 to form a mixed solution, soaking pure cotton cloth into the mixed solution according to the solid-liquid mass ratio of 1:35, and reacting at 120 ℃ for 120min to form the sulfonated fiber material. The sulfonated fiber material is then removed and washed to neutrality. Then, the washed sulfonated fiber material is immersed into a barium hydroxide solution of 0.06mol/L according to the mass ratio of the solute of the barium ion-containing solution to the sulfonated fiber material of 1:1.5, and reacts for 90min at 70 ℃ to form an X-ray shielding material, and then the X-ray shielding material is washed and dried to finally obtain the X-ray shielding material finished product.
Example 3
Mixing sulfamic acid and dimethylformamide according to the mass ratio of 1:38 to form a mixed solution, soaking pure cotton cloth into the mixed solution according to the solid-liquid mass ratio of 1:39, and reacting at 120 ℃ for 60min to form the sulfonated fiber material. The sulfonated fiber material is then removed and washed to neutrality. Then, the washed sulfonated fiber material is immersed into a barium hydroxide solution with the concentration of 0.06mol/L according to the mass ratio of 2:1 of the solute of the barium ion-containing solution to the sulfonated fiber material, and reacts for 90min at 70 ℃ to form an X-ray shielding material, and then the X-ray shielding material is washed and dried to finally obtain the finished product of the X-ray shielding material.
Example 4
Mixing sulfamic acid and dimethylformamide according to the mass ratio of 1:19 to form a mixed solution, soaking pure cotton cloth into the mixed solution according to the solid-liquid mass ratio of 1:40, and reacting at 90 ℃ for 70min to form the sulfonated fiber material. The sulfonated fiber material is then removed and washed to neutrality. Then, the washed sulfonated fiber material is immersed into a barium hydroxide solution with the concentration of 0.06mol/L according to the mass ratio of 2:1 of the solute of the barium ion-containing solution to the sulfonated fiber material, and reacts for 90min at 70 ℃ to form an X-ray shielding material, and then the X-ray shielding material is washed and dried to finally obtain the finished product of the X-ray shielding material.
Example 5
Mixing sulfamic acid and dimethylformamide according to the mass ratio of 1:19 to form a mixed solution, soaking pure cotton cloth into the mixed solution according to the solid-liquid mass ratio of 1:40, and reacting at 100 ℃ for 70min to form the sulfonated fiber material. The sulfonated fiber material is then removed and washed to neutrality. Then, the washed sulfonated fiber material is immersed into a barium hydroxide solution with the concentration of 0.06mol/L according to the mass ratio of 2:1 of the solute of the barium ion-containing solution to the sulfonated fiber material, and reacts for 90min at 70 ℃ to form an X-ray shielding material, and then the X-ray shielding material is washed and dried to finally obtain the finished product of the X-ray shielding material.
Example 6
Mixing sulfamic acid and dimethylformamide according to the mass ratio of 1:19 to form a mixed solution, soaking pure cotton cloth into the mixed solution according to the solid-liquid mass ratio of 1:40, and reacting at 130 ℃ for 70min to form the sulfonated fiber material. The sulfonated fiber material is then removed and washed to neutrality. Then, the washed sulfonated fiber material is immersed into a barium hydroxide solution with the concentration of 0.06mol/L according to the mass ratio of 2:1 of the solute of the barium ion-containing solution to the sulfonated fiber material, and reacts for 90min at 70 ℃ to form an X-ray shielding material, and then the X-ray shielding material is washed and dried to finally obtain the finished product of the X-ray shielding material.
Example 7
Mixing sulfamic acid and dimethylformamide according to the mass ratio of 1:19 to form a mixed solution, soaking pure cotton cloth into the mixed solution according to the solid-liquid mass ratio of 1:40, and reacting at 120 ℃ for 10min to form the sulfonated fiber material. The sulfonated fiber material is then removed and washed to neutrality. Then, the washed sulfonated fiber material is immersed into a barium hydroxide solution with the concentration of 0.06mol/L according to the mass ratio of 2:1 of the solute of the barium ion-containing solution to the sulfonated fiber material, and reacts for 90min at 70 ℃ to form an X-ray shielding material, and then the X-ray shielding material is washed and dried to finally obtain the finished product of the X-ray shielding material.
Referring to fig. 1 and 2, the finished product of the X-ray shielding material is subjected to X-ray photoelectron spectroscopy (XPS) by using a semmer fly esca lab 250Xi instrument, and S, Ba elements are added to the finished product of the X-ray shielding material compared with the original pure cotton cloth.
Example 8
Mixing sulfamic acid and dimethylformamide according to the mass ratio of 1:19 to form a mixed solution, soaking pure cotton cloth into the mixed solution according to the solid-liquid mass ratio of 1:40, and reacting at 120 ℃ for 30min to form the sulfonated fiber material. The sulfonated fiber material is then removed and washed to neutrality. Then, the washed sulfonated fiber material is immersed into a barium hydroxide solution with the concentration of 0.06mol/L according to the mass ratio of 2:1 of the solute of the barium ion-containing solution to the sulfonated fiber material, and reacts for 90min at 70 ℃ to form an X-ray shielding material, and then the X-ray shielding material is washed and dried to finally obtain the finished product of the X-ray shielding material.
Example 9
Mixing sulfamic acid and dimethylformamide according to the mass ratio of 1:19 to form a mixed solution, soaking pure cotton cloth into the mixed solution according to the solid-liquid mass ratio of 1:40, and reacting at 120 ℃ for 60min to form the sulfonated fiber material. The sulfonated fiber material is then removed and washed to neutrality. Then, the washed sulfonated fiber material is immersed into a barium hydroxide solution of 0.01mol/L according to the mass ratio of the solute of the barium ion-containing solution to the sulfonated fiber material of 0.5:1, and reacts for 90min at 70 ℃ to form an X-ray shielding material, and then the X-ray shielding material is washed and dried to finally prepare a finished product of the X-ray shielding material.
Example 10
Mixing sulfamic acid and dimethylformamide according to the mass ratio of 1:19 to form a mixed solution, soaking pure cotton cloth into the mixed solution according to the solid-liquid mass ratio of 1:40, and reacting at 120 ℃ for 60min to form the sulfonated fiber material. The sulfonated fiber material is then removed and washed to neutrality. Then, the washed sulfonated fiber material is immersed into a barium hydroxide solution with the concentration of 0.15mol/L according to the mass ratio of 5:1 of the solute of the barium ion-containing solution to the sulfonated fiber material, the mixture reacts for 90min at 70 ℃ to form an X-ray shielding material, and then the X-ray shielding material is washed and dried to finally obtain the finished product of the X-ray shielding material.
Example 11
Mixing sulfamic acid and dimethylformamide according to the mass ratio of 1:19 to form a mixed solution, soaking pure cotton cloth into the mixed solution according to the solid-liquid mass ratio of 1:40, and reacting at 120 ℃ for 60min to form the sulfonated fiber material. The sulfonated fiber material is then removed and washed to neutrality. Then, the washed sulfonated fiber material is immersed into a barium hydroxide solution of 0.06mol/L according to the mass ratio of the solute of the barium ion-containing solution to the sulfonated fiber material of 2:1, and reacts for 15min at 70 ℃ to form an X-ray shielding material, and then the X-ray shielding material is washed and dried to finally obtain the X-ray shielding material finished product.
Example 12
Mixing sulfamic acid and dimethylformamide according to the mass ratio of 1:19 to form a mixed solution, soaking pure cotton cloth into the mixed solution according to the solid-liquid mass ratio of 1:40, and reacting at 120 ℃ for 60min to form the sulfonated fiber material. The sulfonated fiber material is then removed and washed to neutrality. Then, the washed sulfonated fiber material is immersed into a barium hydroxide solution of 0.06mol/L according to the mass ratio of the solute of the barium ion-containing solution to the sulfonated fiber material of 2:1, and reacts for 150min at 70 ℃ to form an X-ray shielding material, and then the X-ray shielding material is washed and dried to finally obtain the X-ray shielding material finished product.
Example 13
Mixing sulfamic acid and dimethylformamide according to the mass ratio of 1:19 to form a mixed solution, soaking pure cotton cloth into the mixed solution according to the solid-liquid mass ratio of 1:40, and reacting at 120 ℃ for 60min to form the sulfonated fiber material. The sulfonated fiber material is then removed and washed to neutrality. Then, the washed sulfonated fiber material is immersed into a barium hydroxide solution with the concentration of 0.06mol/L according to the mass ratio of 2:1 of the solute of the barium ion-containing solution to the sulfonated fiber material, the mixture reacts for 180min at 70 ℃ to form an X-ray shielding material, and then the X-ray shielding material is washed and dried to finally obtain the X-ray shielding material finished product.
Example 14
Mixing sulfamic acid and dimethylformamide according to the mass ratio of 1:19 to form a mixed solution, soaking pure cotton cloth into the mixed solution according to the solid-liquid mass ratio of 1:40, and reacting at 120 ℃ for 60min to form the sulfonated fiber material. The sulfonated fiber material is then removed and washed to neutrality. Then, the washed sulfonated fiber material is immersed into a barium hydroxide solution with the concentration of 0.06mol/L according to the mass ratio of 2:1 of the solute of the barium ion-containing solution to the sulfonated fiber material, and reacts for 90min at the temperature of 60 ℃ to form an X-ray shielding material, and then the X-ray shielding material is washed and dried to finally obtain a finished product of the X-ray shielding material.
Example 15
Mixing sulfamic acid and dimethylformamide according to the mass ratio of 1:19 to form a mixed solution, soaking pure cotton cloth into the mixed solution according to the solid-liquid mass ratio of 1:40, and reacting at 120 ℃ for 60min to form the sulfonated fiber material. The sulfonated fiber material is then removed and washed to neutrality. Then, the washed sulfonated fiber material is immersed into a barium hydroxide solution with the concentration of 0.06mol/L according to the mass ratio of 2:1 of the solute of the barium ion-containing solution to the sulfonated fiber material, and reacts for 90min at 80 ℃ to form an X-ray shielding material, and then the X-ray shielding material is washed and dried to finally obtain the finished product of the X-ray shielding material.
Example 16
Mixing sulfamic acid and dimethylformamide according to the mass ratio of 1:22 to form a mixed solution, soaking aramid fiber 1313 into the mixed solution according to the solid-liquid mass ratio of 1:42, and reacting at 120 ℃ for 135min to form the sulfonated fiber material. The sulfonated fiber material is then removed and washed to neutrality. Then, the washed sulfonated fiber material is immersed into a barium hydroxide solution with the concentration of barium ion-containing solution being 0.06mol/L according to the mass ratio of the solute to the sulfonated fiber material being 2.5:1, and reacts for 60min at 70 ℃ to form an X-ray shielding material, and then the X-ray shielding material is washed and dried to finally obtain the X-ray shielding material finished product.
Example 17
Chlorosulfonic acid and 1, 2-dichloroethane are mixed according to the mass ratio of 1:22 to form a mixed solution. And soaking aramid fiber 1414 into the mixed solution according to the solid-liquid mass ratio of 1:84, and reacting at 50 ℃ for 120min to form the sulfonated fiber material. The sulfonated fiber material is taken out and washed to be neutral. And (3) immersing the washed sulfonated fiber material into a barium hydroxide solution of 0.06mol/L according to the mass ratio of the solute of the barium ion-containing solution to the sulfonated fiber material of 3.6:1, stirring and reacting at room temperature for 75min to form an X-ray shielding material, and washing and drying to finally obtain a finished product of the X-ray shielding material.
Example 18
Chlorosulfonic acid and 1, 2-dichloroethane are mixed according to the mass ratio of 1:29 to form a mixed solution. And soaking the aramid fiber 1313 into the mixed solution according to the solid-liquid mass ratio of 1:73, and reacting at 50 ℃ for 120min to form the sulfonated fiber material. The sulfonated fiber material is taken out and washed to be neutral. And (3) immersing the washed sulfonated fiber material into a barium hydroxide solution of 0.06mol/L according to the mass ratio of the solute of the barium ion-containing solution to the sulfonated fiber material of 3.6:1, stirring and reacting for 60min at room temperature to form an X-ray shielding material, and washing and drying to finally obtain a finished product of the X-ray shielding material.
Example 19
And stirring the terylene and the tetrahydrofuran for 30min according to the solid-liquid mass ratio of 1:55, and taking out the terylene for later use. And then mixing the terylene with concentrated sulfuric acid according to the solid-liquid mass ratio of 1:68, and reacting at room temperature for 20min to form the sulfonated fiber material. The sulfonated fiber material is taken out and washed to be neutral. And (3) immersing the washed sulfonated fiber material into a 0.05mol/L barium chloride solution according to the mass ratio of the solute of the barium ion-containing solution to the sulfonated fiber material of 3:1, and stirring and reacting for 30min at room temperature to form the X-ray shielding material. The X-ray shielding material is washed and dried to finally obtain the finished product of the X-ray shielding material.
Example 20
Stirring aramid fiber 1414 and tetrahydrofuran for 30min according to the solid-liquid mass ratio of 1:55, and taking out the terylene for later use. Then mixing the aramid fiber 1414 and concentrated sulfuric acid according to the solid-liquid mass ratio of 1:68, and reacting for 20min at room temperature to form the sulfonated fiber material. The sulfonated fiber material is taken out and washed to be neutral. And (3) immersing the washed sulfonated fiber material into a 0.05mol/L barium chloride solution according to the mass ratio of the solute of the barium ion-containing solution to the sulfonated fiber material of 3:1, and stirring and reacting for 30min at room temperature to form the X-ray shielding material. And finally, washing and drying to obtain the finished product of the X-ray shielding material.
The X-ray shielding material finished products of the above examples 1 to 20 were subjected to ICP-OES test using a warian 710-es apparatus in the united states, and the content of barium element in the X-ray shielding material finished products was measured as shown in the following table under the conditions of a constant volume of 25ml and a dilution factor of 50. The occurrence of a large amount of barium element shows that the barium element has good shielding performance on X-rays.
Table one: percentage of barium content corresponding to different examples
Figure BDA0002920025760000131
Figure BDA0002920025760000141
The above examples 1-20 are relatively preferred examples, and it can be seen that the content of barium element is greater than or equal to 2.05%, and of course, any value in the above table can be defined as the performance index of the desired product according to different examples.
The above description is only a preferred embodiment of the present invention, and for those skilled in the art, the present invention should not be limited by the description of the present invention, which should be interpreted as a limitation.

Claims (10)

1. A method for manufacturing an X-ray shielding material is characterized by comprising the following steps:
step 1, carrying out sulfonation reaction on a fiber material and a sulfonating agent to form a sulfonated fiber material;
and 2, reacting the sulfonated fiber material with a barium ion-containing solution to obtain the X-ray shielding material.
2. The method of manufacturing an X-ray shielding material according to claim 1,
the fiber material is in a cloth shape;
the fiber material is a fiber with a benzene ring, a fiber with a hydroxyl group or a fiber with an amido bond, and the sulfonating agent is a sulfonating agent capable of performing sulfonation reaction with the benzene ring, the hydroxyl group or the amido bond in a matching way.
3. The method of manufacturing an X-ray shielding material according to claim 2,
the fiber material is aramid fiber or terylene, and the sulfonating agent is concentrated sulfuric acid or chlorosulfonic acid; or the fiber material is cotton, aramid fiber, chinlon or spandex, and the sulfonating agent is sulfamic acid;
the organic solvent is any one or a mixture of more than two of acetone, tetrahydrofuran, 1, 2-dichloroethane and dimethylformamide.
4. The method of manufacturing an X-ray shielding material according to claim 1,
the barium ion-containing solution is a barium hydroxide solution, a barium chloride solution or a barium nitrate solution.
5. The method of producing an X-ray shielding material according to any one of claims 1 to 4,
in the step 1: mixing the sulfonating agent and an organic solvent according to a preset mass ratio to form a mixed solution, and then immersing the fiber material into the mixed solution according to a preset solid-liquid mass ratio to perform sulfonation reaction;
the method comprises the following two combination modes:
the first combination mode is as follows: the sulfonating agent is sulfamic acid, the organic solvent is dimethylformamide, the fiber material is cotton, and the preset mass ratio is 1: (12-38), wherein the preset solid-liquid mass ratio is 1: (35-42), wherein the sulfonation reaction temperature is 90-130 ℃, and the sulfonation reaction time is more than or equal to 10 min;
the second combination mode: the sulfonating agent is chlorosulfonic acid, the organic solvent is dichloroethane, the fiber material is aramid fiber, and the preset mass ratio is 1: (22-29), wherein the preset solid-liquid mass ratio is 1: (73-84), the sulfonation reaction temperature is 35-60 ℃, and the sulfonation reaction time is more than or equal to 100 min.
6. The method of manufacturing an X-ray shielding material according to claim 5,
in the first combination mode: the sulfonation reaction time is 30-70 min;
in the second combination mode: the sulfonation reaction time is 110-130 min.
7. The method of producing an X-ray shielding material according to any one of claims 1 to 4,
in the step 1: the fiber material and the organic solvent are mixed according to a solid-liquid mass ratio of 1: (45-65), and then taking out the fiber material according to the solid-liquid mass ratio of 1: (58-78) immersing the sulfonated fiber material in the sulfonating agent to carry out sulfonation reaction to form a sulfonated fiber material, wherein the sulfonation reaction temperature is 15-35 ℃, and the sulfonation reaction time is more than or equal to 10 min;
the fiber material, the organic solvent and the sulfonating agent are selected according to the following combination mode:
the combination mode is three: the sulfonating agent is concentrated sulfuric acid, the organic solvent is tetrahydrofuran, and the fiber material is aramid fiber or polyester fiber.
8. The method of producing an X-ray shielding material according to any one of claims 1 to 4,
in the step 2:
immersing the sulfonated fiber material into 0.01-0.15 mol/L of the barium-ion-containing solution;
the method comprises the following three combination modes:
the first combination mode is as follows: the sulfonating agent is sulfamic acid, the organic solvent is dimethylformamide, the fiber material is cotton, the barium ion-containing solution is a barium hydroxide solution, the reaction temperature in the step 2 is 60-80 ℃, the reaction time is more than or equal to 15min, and the mass ratio of the solute of the barium ion-containing solution to the sulfonated fiber material is (0.5-5): 1;
the second combination mode: the sulfonating agent is chlorosulfonic acid, the organic solvent is dichloroethane, the fiber material is aramid fiber, the barium ion-containing solution is a barium hydroxide solution, the reaction temperature in the step 2 is 15-35 ℃, the reaction time is more than or equal to 45min, and the mass ratio of the solute of the barium ion-containing solution to the sulfonated fiber material is (2.5-4.5): 1;
the combination mode is three: the sulfonating agent is concentrated sulfuric acid, the organic solvent is tetrahydrofuran, the fiber material is aramid fiber or polyester fiber, the barium ion-containing solution is a barium chloride solution, the reaction temperature in the step 2 is 15-35 ℃, the reaction time is more than or equal to 15min, and the mass ratio of the solute of the barium ion-containing solution to the sulfonated fiber material is (2-4): 1.
9. the method of manufacturing an X-ray shielding material according to claim 8,
in the step 2:
the first combination mode comprises the following steps: the reaction time is 15-180 min;
in the second combination mode: the reaction temperature is room temperature, and the reaction time is 45-75 min;
in the third combination mode: the reaction temperature is room temperature, and the reaction time is 15-45 min.
10. An X-ray shielding material produced by the method for producing an X-ray shielding material according to any one of claims 1 to 9.
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Citations (4)

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Publication number Priority date Publication date Assignee Title
US3961123A (en) * 1972-12-29 1976-06-01 Kanebo, Ltd. Radiation shielding phenolic fibers and method of producing same
CN104292868A (en) * 2014-09-09 2015-01-21 安徽宏博木业有限公司 X-ray radiation resistant wood fiber and preparation method thereof
CN109898322A (en) * 2019-03-15 2019-06-18 天津工业大学 A kind of sulfonation non-woven cloth and preparation method
CN111535044A (en) * 2020-06-01 2020-08-14 中国科学院合肥物质科学研究院 Electromagnetic shielding and hydrophobic functional fabric with high absorption characteristic and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3961123A (en) * 1972-12-29 1976-06-01 Kanebo, Ltd. Radiation shielding phenolic fibers and method of producing same
GB1446487A (en) * 1972-12-29 1976-08-18 Kanebo Ltd Radiation-shielding textile articles and their preparation
CN104292868A (en) * 2014-09-09 2015-01-21 安徽宏博木业有限公司 X-ray radiation resistant wood fiber and preparation method thereof
CN109898322A (en) * 2019-03-15 2019-06-18 天津工业大学 A kind of sulfonation non-woven cloth and preparation method
CN111535044A (en) * 2020-06-01 2020-08-14 中国科学院合肥物质科学研究院 Electromagnetic shielding and hydrophobic functional fabric with high absorption characteristic and preparation method thereof

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