Anti-nuclear radiation modified fiber and preparation method thereof
By premodifying the polyacrylonitrile fibers and grafting functional molecules, and mixing them with modified WO3, modified fibers with excellent nuclear radiation resistance, flame retardant and hygroscopic properties are prepared, solving the problem of insufficient performance of existing materials in these aspects.
Patent Information
- Application Number
- CN202510131669.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-02-06
- Publication Date
- 2025-04-11
- Estimated Expiration
- Not applicable · inactive patent
AI Technical Summary
The existing protective clothing materials have shortcomings in their nuclear radiation resistance, hygroscopicity and flame retardancy, and are more prominent when used in high temperature environments.
By premodifying the polyacrylonitrile fibers, functional molecules, including sulfonic acid groups, N-group-containing heterocyclic rings, ether bonds and hydroxyl groups, forming an N-S-P synergistic flame retardant system, and mixing the premodified fibers with the modified WO3 at a mass ratio of 2:5, and modifying the modified fibers by melt spinning.
The modified fibers prepared not only have good flame retardant and hygroscopic properties, but also have good nuclear radiation-resistant shielding properties, and are suitable for national defense, industry and other fields.
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Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of nuclear radiation modified fibers, and in particular, relates to a nuclear radiation resistant modified fiber and a preparation method thereof. Background Art
[0002] As an important green energy, nuclear energy is widely used in defense, industry, medicine and other fields. As a result, the number of radioactive workers has increased dramatically. Nuclear radiation is very harmful to the human body. With the increase of radiation dose, symptoms such as dizziness, insomnia, hair loss, ulcers, diarrhea, vomiting, etc. will appear. Severe cases may even cause chromosome aberration and death. Therefore, the development of protective equipment with excellent anti-nuclear radiation shielding effect is of great significance to the safety of radioactive workers.
[0003] Traditional protective clothing materials are made of rubber or plastic substrates, which are pressed as a whole. The fabrics used to make nuclear radiation protective clothing have the disadvantages of poor nuclear radiation resistance and discomfort. Especially when workers work in high temperature environments, the demand for protective clothing with hygroscopicity and flame retardancy is even stronger. In addition, the development of new radiation protection materials with flame retardant and heat insulation properties can also be widely used in the peripheral radiation protection of nuclear instruments and nuclear equipment with complex shapes. Summary of the invention
[0004] The object of the present invention is to provide a nuclear radiation resistant modified fiber and a preparation method thereof.
[0005] The purpose of the present invention can be achieved through the following technical solutions:
[0006] A method for preparing a modified fiber for nuclear radiation protection is as follows:
[0007] S1. Add hydrazine hydrate solution and polyacrylonitrile fiber into a three-necked flask and react at 95°C for 1 hour. After the reaction, take out the fiber and wash it with deionized water until the aqueous solution is neutral, and place it in an oven at 70°C to dry it to obtain the aminated fiber, i.e., the primary modified polyacrylonitrile fiber. The ratio of hydrazine hydrate to polyacrylonitrile fiber is 20.64g:21.35g, and the mass concentration of hydrazine hydrate solution is 0.4M.
[0008] Polyacrylonitrile fiber contains carbon-nitrogen triple bonds, and hydrazine hydrate contains amino groups. When the two react, the carbon-nitrogen triple bonds in the polyacrylonitrile fiber will not react completely, but the π bond on the -C≡N group will open to generate -NH2, -C=NH and amide groups.
[0009] S2. Add hexachlorotrimer and DMSO to a three-necked flask equipped with a magnet, a thermometer and a spherical condenser, respectively, and obtain a hexachlorotrimer solution after complete dissolution. Dissolve p-aminobenzenesulfonic acid in deionized water, slowly drop it into the above three-necked flask, heat it in an oil bath and stir continuously. After the addition is completed, heat it to 80°C and react for 24 hours. After the reaction is completed, cool it to room temperature, extract, separate the liquids, and rotary evaporate to obtain intermediate 1. The ratio of hexachlorotrimer to p-aminobenzenesulfonic acid is 13.38g:25.98g. The specific reaction steps are as follows:
[0010]
[0011] S3, the intermediate 1 was dissolved in DMSO and placed in a three-necked flask, and the chlorphenesin solution dissolved in propylene glycol was slowly dripped into the three-necked flask, and the temperature was raised to 78 ° C for reaction for 3 hours. After the reaction was completed, it was cooled to room temperature, and then washed with water and distilled to obtain intermediate 2. The ratio of the amount of intermediate 1 to chlorphenesin was 12.41g:2.02g. The specific reaction steps were as follows:
[0012]
[0013] S4. Dissolve the intermediate 2 in DMSO, and add the initially modified polyacrylonitrile fiber prepared in step S1 to the above prepared solution. The prepared initially modified polyacrylonitrile fiber contains amino groups that can react with the sulfonic acid groups in the intermediate 2. The reaction is carried out at 120°C for 2 hours. After cooling to room temperature, the pre-modified polyacrylonitrile fiber is obtained by atmospheric distillation. The ratio of the intermediate 2 to the initially modified polyacrylonitrile fiber is 14.07g:5.98g.
[0014] S5. Mix silane coupling agent KH-570 and xylene to obtain a modified solution, then add WO3 into the modified solution and stir evenly, heat at 120°C for 2 hours under the protection of nitrogen, and after cooling to room temperature, repeat ultrasonic cleaning three times with deionized water to obtain modified WO3. The ratio of silane coupling agent KH-570, xylene and WO3 is 5g:10g:50g.
[0015] S6. Mix the modified WO3 prepared in step S5 and the pre-modified polyacrylonitrile fiber prepared in step S4 in a mass ratio of 2:5, and obtain the modified fiber by melt spinning.
[0016] The present invention pre-modifies the polyacrylonitrile fiber and grafts functional molecules on the ends of its molecular chains by chemical bonding. The functional molecules, from a structural point of view, include sulfonic acid groups, N-containing groups, nitrogen-phosphorus heterocycles, ether bonds and hydroxyl groups, wherein the sulfonic acid groups, N-containing groups and nitrogen-phosphorus heterocycles belong to S-series, N-series and NP-series flame retardant components respectively, forming an NSP synergistic flame retardant system, giving the polyacrylonitrile fiber safe and efficient flame retardant properties; ether bonds and hydroxyl groups are hydrophilic, and the two work together to improve the hygroscopicity of the polyacrylonitrile fiber, making the prepared fabric more comfortable and skin-friendly. It should be particularly noted that the functional molecules are connected to the ends of the molecular chains of the polyacrylonitrile fiber by chemical grafting, so they have a higher interaction force with the polyacrylonitrile molecular chain, making it difficult to migrate and seep out, making various properties more durable and stable.
[0017] In addition, the modified fiber obtained by the present invention by mixing the pre-modified polyacrylonitrile fiber and the modified WO3 in a mass ratio of 2:5 through melt spinning has good anti-nuclear radiation shielding performance.
[0018] Another object of the present invention is to provide a modified fiber prepared by the above preparation method.
[0019] Beneficial effects of the present invention:
[0020] 1. The flame retardant property and hygroscopic property of the modified fiber prepared by the present invention are improved due to the introduction of sulfonic acid group, N-containing group, nitrogen-phosphorus heterocycle, ether bond and hydroxyl group.
[0021] 2. Nano tungsten oxide has shielding properties. After pre-modified polyacrylonitrile fiber and modified WO3 are mixed in a mass ratio of 2:5, the modified fiber obtained by melt spinning has good anti-nuclear radiation shielding properties.
[0022] Therefore, the prepared modified fiber has good flame retardant properties, hygroscopic properties and anti-nuclear radiation shielding properties, and has important application value in the fields of national defense and industry. DETAILED DESCRIPTION
[0023] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
[0024] Embodiment 1
[0025] S1. Add 20.64g of hydrazine hydrate solution (0.4M) and 21.35g of polyacrylonitrile fiber into a three-necked flask and react at 95°C for 1h. After the reaction, take out the fiber and wash it with deionized water until the aqueous solution is neutral, and dry it in an oven at 70°C to obtain the aminated fiber, i.e., the primary modified polyacrylonitrile fiber.
[0026] S2. Add 13.38g of hexachlorotrimer phosphazene and 50mL of DMSO to a three-necked flask equipped with a magnet, a thermometer, and a spherical condenser, respectively, and obtain a hexachlorotrimer phosphazene solution after complete dissolution. Dissolve 25.98g of p-aminobenzenesulfonic acid in 100mL of deionized water, and slowly drop it into the above three-necked flask, heat it in an oil bath and stir it continuously. After the addition is completed, heat it to 80°C and react for 24h. After the reaction is completed, cool it to room temperature, add the product to 130mL of ether solution for extraction, separation, and rotary evaporation to obtain intermediate 1.
[0027] S3. Dissolve 12.41 g of intermediate 1 in 40 mL of DMSO and place in a three-necked flask. Slowly drop 2.02 g of chlorphenesin solution dissolved in 15 mL of propylene glycol into the three-necked flask. Heat to 78 °C and react for 3 h. After the reaction is completed, cool to room temperature, then wash with water and distill to obtain intermediate 2.
[0028] S4, dissolving 14.07g of intermediate 2 in 60mL of DMSO, adding 5.98g of the initially modified polyacrylonitrile fiber prepared in step S1 to the above prepared solution, the prepared initially modified polyacrylonitrile fiber contains amino groups that can react with the sulfonic acid groups in intermediate 2, reacting at 120°C for 2h, and after cooling to room temperature, obtaining pre-modified polyacrylonitrile fiber by atmospheric distillation.
[0029] S5. Mix 5g of silane coupling agent KH-570 and 10g of xylene to obtain a modified solution, then add 50g of WO3 into the modified solution and stir evenly. Heat at 120°C for 2h under the protection of nitrogen. After cooling to room temperature, repeat ultrasonic cleaning three times with deionized water to obtain modified WO3.
[0030] S6. Mix the modified WO3 prepared in step S5 and the pre-modified polyacrylonitrile fiber prepared in step S4 in a mass ratio of 2:5, and obtain the modified fiber by melt spinning.
[0031] Embodiment 2
[0032] S1. Add 41.28g of hydrazine hydrate solution (0.4M) and 42.70g of polyacrylonitrile fiber into a three-necked flask and react at 95°C for 1h. After the reaction, take out the fiber and wash it with deionized water until the aqueous solution is neutral, and dry it in an oven at 70°C to obtain the aminated fiber, i.e., the primary modified polyacrylonitrile fiber.
[0033] S2. Add 26.76g of hexachlorotrimer phosphazene and 100mL of DMSO to a three-necked flask equipped with a magnet, a thermometer, and a spherical condenser, respectively, and obtain a hexachlorotrimer phosphazene solution after complete dissolution. Dissolve 51.96g of p-aminobenzenesulfonic acid in 200mL of deionized water, and slowly drop it into the above three-necked flask, heat it in an oil bath and stir it continuously. After the addition is completed, heat it to 80°C and react for 24h. After the reaction is completed, cool it to room temperature, add the product to 260mL of ether solution for extraction, separation, and rotary evaporation to obtain intermediate 1.
[0034] S3. Dissolve 24.82 g of intermediate 1 in 80 mL of DMSO and place in a three-necked flask. Slowly drop 4.04 g of chlorphenesin solution dissolved in 30 mL of propylene glycol into the three-necked flask. Heat to 78 °C and react for 3 h. After the reaction is completed, cool to room temperature, then wash with water and distill to obtain intermediate 2.
[0035] S4, dissolving 28.14g of intermediate 2 in 120mL of DMSO, adding 11.96g of the initially modified polyacrylonitrile fiber prepared in step S1 to the above prepared solution, the prepared initially modified polyacrylonitrile fiber contains amino groups that can react with the sulfonic acid groups in intermediate 2, reacting at 120°C for 2h, and after cooling to room temperature, obtaining pre-modified polyacrylonitrile fiber by atmospheric distillation.
[0036] S5. Mix 10g of silane coupling agent KH-570 and 20g of xylene to obtain a modified solution, then add 100g of WO3 into the modified solution and stir evenly, heat at 120°C for 2h under the protection of nitrogen, and after cooling to room temperature, repeat ultrasonic cleaning three times with deionized water to obtain modified WO3.
[0037] S6. Mix the modified WO3 prepared in step S5 and the pre-modified polyacrylonitrile fiber prepared in step S4 in a mass ratio of 2:5, and obtain the modified fiber by melt spinning.
[0038] Comparative Example 1
[0039] Ordinary polyacrylonitrile fiber.
[0040] Comparative Example 2
[0041] The pre-modified polyacrylonitrile fiber prepared in Example 1.
[0042] The fibers obtained from the above-mentioned Examples 1 to 2 and Comparative Examples 1 to 2 were processed into standard test samples and subjected to performance tests. The specific test standards and test results are shown in Table 1 below:
[0043]
[0044] It can be seen from the data in the above table that the prepared modified fiber has good flame retardant properties, anti-nuclear radiation shielding properties and certain moisture absorption properties, and has important application value in the fields of national defense and industry.
[0045] In the description of the specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.
[0046] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the invention or exceed the scope defined by the claims, they shall all fall within the protection scope of the present invention.
Claims
1. A method for preparing a modified fiber for nuclear radiation protection, characterized in that: The specific preparation process is as follows: S1. Add hydrazine hydrate solution and polyacrylonitrile fiber into a three-necked flask, react at 95°C for 1 hour, take out the fiber after the reaction, wash it with deionized water until the aqueous solution is neutral, and dry it in an oven at 70°C to obtain the aminated fiber, i.e., the primary modified polyacrylonitrile fiber; S2, dissolving hexachlorotripolyphosphazene in DMSO, placing in a three-necked flask, slowly dropping a solution of p-aminobenzenesulfonic acid dissolved in deionized water into the three-necked flask, heating in an oil bath with continuous stirring, after the dropping is completed, heating to 80° C. to react for 24 h, after the reaction is completed, cooling to room temperature, extracting, separating, and rotary evaporating to obtain intermediate 1; S3, dissolving intermediate 1 in DMSO, placing in a three-necked flask, slowly dripping a solution of chlorphenesin dissolved in propylene glycol into the three-necked flask, heating to 78° C. for 3 h, cooling to room temperature after the reaction, and then washing and distilling to obtain intermediate 2; S4, dissolving the intermediate 2 in DMSO, adding the initially modified polyacrylonitrile fiber prepared in step S1 to the above prepared solution, reacting at 120° C. for 2 h, and after cooling to room temperature, obtaining the pre-modified polyacrylonitrile fiber by atmospheric distillation; S5, mixing silane coupling agent KH-570 and xylene to obtain a modification solution, then adding WO3 to the modification solution and stirring evenly, heating at 120°C for 2h under the protection of nitrogen, and after cooling to room temperature, repeatedly ultrasonically cleaning with deionized water three times to obtain modified WO3; S6. Mix the modified WO3 prepared in step S5 and the pre-modified polyacrylonitrile fiber prepared in step S4 in a certain mass ratio, and obtain the modified fiber by melt spinning.
2. The method for preparing a nuclear radiation-proof modified fiber according to claim 1, characterized in that: In step S1, the ratio of hydrazine hydrate to polyacrylonitrile fiber is 20.64 g:21.35 g, and the mass concentration of hydrazine hydrate solution is 0.4M.
3. The method for preparing a nuclear radiation-proof modified fiber according to claim 1, characterized in that: In step S2, the ratio of hexachlorotripolyphosphazene, DMSO, p-aminobenzenesulfonic acid and deionized water is 13.38 g:50 mL:25.98 g:100 mL.
4. The method for preparing a nuclear radiation resistant modified fiber according to claim 1, characterized in that: In step S3, the ratio of the amount of intermediate 1, DMSO, chlorphenesin and propylene glycol is 12.41 g:40 mL:2.02 g:15 mL.
5. The method for preparing a nuclear radiation resistant modified fiber according to claim 1, characterized in that: In step S4, the ratio of the amount of intermediate 2, DMSO and primary modified polyacrylonitrile fiber is 14.07 g:60 mL:5.98 g.
6. The method for preparing a nuclear radiation resistant modified fiber according to claim 1, characterized in that: In step S5, the ratio of the amount of silane coupling agent KH-570, xylene and WO3 is 5g:10g:50g.
7. The method for preparing a nuclear radiation-proof modified fiber according to claim 1, characterized in that: In step S6, the modified WO3 and the pre-modified polyacrylonitrile fiber are mixed in a mass ratio of 2:
5.
8. A modified fiber for nuclear radiation protection, characterized in that: Prepared according to the method described in any one of claims 1-7.