Fabric with nuclear radiation shielding function

Abstract

The invention discloses a fabric with a nuclear radiation shielding function, and belongs to the technical field of nuclear radiation protection. The preparation method comprises the following steps: preparing modified polyester fibers from the following raw materials in parts by weight: 80-90 parts of polyester resin, 12-24 parts of modified nano tungsten oxide, 8-12 parts of a functional shielding material and 2-4 parts of a processing aid, and blending the modified polyester fibers with wool fibers to prepare the fabric. According to the prepared fabric, the polyester fibers are used as the main raw material of the fabric, so that the fabric is not prone to deformation and good in comfort level; the wool fibers are added, so that the comfort level of the fabric can be improved, and the moisture absorption performance of the fabric can be improved; the added functional shielding material can improve the shielding performance of the fabric; nano tungsten oxide is modified, so that compared with common nano tungsten oxide, the compatibility with polyester is better, the antibacterial property and flame retardance of the fabric can be enhanced, and the performance is stable; in conclusion, the prepared fabric has important application value in the technical field of nuclear radiation protection.

Description

Technical Field

[0001] The invention belongs to the technical field of nuclear radiation protection, and in particular relates to a fabric with nuclear radiation shielding function. Background Art

[0002] With the increasing demand for energy and the emphasis on the environment, new energy sources are developing rapidly. Nuclear energy, as a clean and efficient form of energy, has received widespread attention. The development and utilization of nuclear energy has brought great changes to mankind, but nuclear reactors will produce highly radioactive rays during operation, namely nuclear radiation. Nuclear radiation refers to the particles or electromagnetic waves released by atomic nuclei during decay, fission, fusion, etc., mainly including alpha particles, beta particles, gamma rays and neutrons. These rays have high energy and can affect surrounding substances, posing a serious threat to people's lives, health and property safety.

[0003] In nuclear power plant maintenance, nuclear waste treatment, nuclear fuel production and other nuclear-related places, radiation protective clothing is a must-have protective equipment for workers. Due to its special application scenarios, there are also high requirements for the quality of radiation protective clothing fabrics. Traditional nuclear radiation shielding fabrics are made of polymers as the matrix. Although they can have a certain shielding effect, they are not breathable, have a hard texture, and are not soft. They will affect the wearing comfort of the staff. If the renovation time is too long, it will even affect the mood and work skills of the staff, which is not conducive to improving work efficiency and work quality. Not only that, the anti-ionizing radiation composite materials currently used in China have been limited to using lead or lead compounds as the main additives to prevent the harm of ionizing radiation to the human body, but this type of product has a large specific gravity and a narrow shielding range, and lead itself is toxic, which can easily cause physical harm to the relevant users and also pollute the environment. Therefore, it is urgent to solve the above problems to meet the higher demands in the field of nuclear radiation protection technology. Summary of the invention

[0004] The purpose of the present invention is to overcome the defects of the prior art and provide a fabric with nuclear radiation shielding function.

[0005] The purpose of the present invention can be achieved through the following technical solutions:

[0006] A fabric with nuclear radiation shielding function is prepared by the following steps:

[0007] A1. Place the polyester resin in a vacuum drying oven and dry for 12 hours. Take it out and put it into a mixer with modified nano tungsten oxide, functional shielding material and processing aid for 30 minutes. Add it into a twin-screw extruder and melt-blend and spin to obtain primary fibers. After stretching, obtain modified polyester fibers.

[0008] A2. The modified polyester fiber and wool fiber are combined on a drawing frame to make slivers, which are then drawn and twisted on a roving frame, and further drawn and twisted on a spinning frame to make blended yarn. The fabric with nuclear radiation shielding function is made by a large circular machine weft knitting method.

[0009] Furthermore, the raw materials in step A1 are calculated in parts by weight as follows: 80-90 parts of polyester resin, 12-24 parts of modified nano tungsten oxide, 8-12 parts of functional shielding material, and 2-4 parts of processing aid.

[0010] Furthermore, in step A1, the functional shielding material is one or more of boron nitride, boron carbide, and tantalum powder.

[0011] Furthermore, in step A1, the processing aid is one of paraffin and zinc stearate.

[0012] Furthermore, the raw materials in step A2 are calculated in parts by weight as follows: 55-65 parts of modified polyester fiber and 16-24 parts of wool fiber.

[0013] Polyester fiber is used as the main raw material of the fabric. Polyester fiber has high strength, wear resistance, good elasticity, non-deformation, good chemical resistance and good comfort. Using wool fiber as one of the raw materials can not only improve the wearing comfort, but also greatly improve the moisture absorption performance of the fabric. The added functional shielding material has good shielding ability for thermal neutrons, fast neutrons and high-energy neutrons, which can improve the shielding performance of the fabric.

[0014] Furthermore, the modified nano tungsten oxide is prepared by the following steps:

[0015] S1. Add nano tungsten oxide, ethanol aqueous solution and hydrochloric acid solution to a three-necked round-bottom flask equipped with a thermometer and a stirrer, stir and mix, then ultrasonically treat for 75 minutes, add silane coupling agent KH-580, stir and heat to 60°C, keep warm for 2 hours, then stir and heat to 70°C, keep warm for 5 hours, the reaction is completed, cool, filter, wash with acetone, and vacuum dry to obtain pre-modified nano tungsten oxide; the ratio of nano tungsten oxide, ethanol aqueous solution, hydrochloric acid solution, and silane coupling agent KH-580 is 1g:80mL:15mL:5.6g;

[0016] The surface of nano-tungsten oxide contains a large number of hydroxyl groups, which can react with the silane coupling agent KH-580 to introduce mercapto groups on the nano-tungsten oxide to obtain pre-modified nano-tungsten oxide.

[0017] S2. Place a three-necked round-bottom flask equipped with a thermometer, a stirrer and a reflux condenser in a water bath, add allyl bromide and N,N-dimethylformamide (DMF), mix and stir evenly, and add 5-chloro-2-methylisothiazoline-3-one (CMIT) while stirring. After stirring evenly, raise the temperature of the device to 80° C., condense and reflux to react for 6 hours. After the reaction is completed, remove the solvent by vacuum distillation, wash with acetone 2-3 times, and vacuum dry to obtain intermediate 1; the ratio of allyl bromide, N,N-dimethylformamide, and 5-chloro-2-methylisothiazoline-3-one is 15.3 g:100 mL:19.9 g;

[0018] Allyl bromide reacts with 5-chloro-2-methylisothiazoline-3-one to undergo quaternization to obtain intermediate 1; the specific reaction is shown below:

[0019]

[0020] S3. In a three-necked round-bottom flask equipped with a thermometer and a stirrer, the intermediate 1 and N,N-dimethylformamide were mixed, the stirrer was turned on, potassium carbonate and melamine were added in sequence, and the temperature of the device was slowly raised to 60°C, and the reaction was kept warm for 12 hours. After the reaction was completed, it was filtered, and part of the solvent was first removed by rotary evaporation, and then purified by column chromatography (the eluent was a mixed solvent of benzene / ethyl acetate, and the volume ratio of the two was 1:2), and the eluent was removed by rotary evaporation to obtain intermediate 2; the ratio of the amount of intermediate 1, N,N-dimethylformamide, potassium carbonate, and melamine was 58.7 g: 200 mL: 41.2 g: 12.6 g;

[0021] Under the catalysis of potassium carbonate, intermediate 1 and melamine undergo a nucleophilic substitution reaction, and intermediate 2 is obtained by controlling the molar ratio of the two to be close to 3:1 and a slight excess of intermediate 1. The specific reaction is as follows:

[0022]

[0023] S4. Mix the pre-modified nano tungsten oxide with N,N-dimethylformamide in a three-necked round-bottom flask equipped with a thermometer and a stirrer, turn on the stirrer, stir for 15 minutes to make the pre-modified nano tungsten oxide evenly dispersed, add AIBN (azobisisobutyronitrile) and intermediate 2, maintain the temperature of the system at 65°C, and keep the reaction for 8 hours. After the reaction is completed, wash with anhydrous ethanol 3-4 times, freeze-dry, and grind to obtain modified nano tungsten oxide; the ratio of the amount of pre-modified nano tungsten oxide, N,N-dimethylformamide, azobisisobutyronitrile, and intermediate 2 is 1.0g:100mL:0.2g:8.1g;

[0024] Under the action of AIBN, the thiol group on the pre-modified nano-tungsten oxide and the unsaturated carbon-carbon double bond on the intermediate 2 undergo a thiol-ene click reaction to obtain modified nano-tungsten oxide;

[0025] Nano tungsten oxide has excellent shielding properties. By modifying it, the compatibility of nano tungsten oxide with polyester matrix can be greatly improved, so that nano tungsten oxide can be fully dispersed in the polyester matrix, and the performance of nano tungsten oxide can be fully exerted, which greatly enhances the shielding performance of polyester. Compared with lead, nano tungsten oxide is non-toxic and environmentally friendly. In addition, the modified nano tungsten oxide also contains triazine, isothiazolinone and quaternary ammonium salt structures. Among them, the introduced triazine structure is a nitrogen-based flame retardant, which will produce nitrogen-containing gas during combustion, dilute and reduce the smoke density, and at high temperatures. The self-condensation to form melem makes the carbon layer tight and improves the flame retardant properties of the matrix; the introduced isothiazolinone has excellent properties such as strong antibacterial ability, environmental safety and a broad antibacterial spectrum. It forms a disulfide bond with the sulfhydryl group on the cysteine ​​in the pathogen protein through the bond active site on the heterocyclic ring, thereby inactivating the protein to achieve the purpose of sterilization; finally, the introduction of quaternary ammonium ions will produce a strong electrostatic interaction between the positively charged and negatively charged bacteria, and will have a strong adsorption effect on the bacteria, which can synergize with isothiazolinone to further enhance the flame retardant properties of the matrix.

[0026] It should be further explained that, by modifying nano-tungsten oxide with organic molecular chains, the migration resistance of organic molecules can be improved, and the stability of modified nano-tungsten oxide can be improved.

[0027] Beneficial effects of the present invention:

[0028] 1. The fabric prepared by the present invention uses polyester fiber as the main raw material of the fabric, which makes the fabric not easy to deform and has good comfort;

[0029] 2. Adding wool fiber not only improves the comfort of the fabric, but also improves the moisture absorption performance of the fabric;

[0030] 3. The added functional shielding materials can improve the shielding performance of the fabric;

[0031] 4. By modifying nano tungsten oxide, compared with ordinary nano tungsten oxide, it has better compatibility with polyester, can also enhance the antibacterial and flame retardant properties of the fabric, and has stable performance;

[0032] In summary, the fabric prepared by the present invention has important application value in the field of nuclear radiation protection technology. DETAILED DESCRIPTION

[0033] 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.

[0034] Embodiment 1

[0035] Preparation of modified nano tungsten oxide:

[0036] S1. Add 1g of nano-tungsten oxide, 80mL of ethanol aqueous solution and 15mL of hydrochloric acid solution to a three-necked round-bottom flask equipped with a thermometer and a stirrer, stir and mix, then ultrasonically treat for 75min, add 5.6g of silane coupling agent KH-580, stir and heat to 60℃, keep warm for 2h, then stir and heat to 70℃, keep warm for 5h, the reaction is completed, cool, filter, wash with acetone, and vacuum dry to obtain pre-modified nano-tungsten oxide;

[0037] S2. Place a three-necked round-bottom flask equipped with a thermometer, a stirrer and a reflux condenser in a water bath, add 15.3 g of allyl bromide and 100 mL of N,N-dimethylformamide, mix and stir evenly, and add 19.9 g of 5-chloro-2-methylisothiazoline-3-one while stirring. After stirring evenly, raise the temperature of the device to 80°C, condense and reflux for 6 hours. After the reaction is completed, remove the solvent by distillation under reduced pressure, wash with acetone 3 times, and vacuum dry to obtain intermediate 1;

[0038] S3, in a three-necked round-bottom flask equipped with a thermometer and a stirrer, 58.7 g of intermediate 1 and 200 mL of N,N-dimethylformamide were mixed, the stirrer was turned on, 41.2 g of potassium carbonate and 12.6 g of melamine were added in sequence, and the temperature of the device was slowly raised to 60° C., and the reaction was kept warm for 12 h. After the reaction was completed, it was filtered, part of the solvent was first removed by rotary evaporation, and then purified by column chromatography (the eluent was a mixed solvent of benzene / ethyl acetate, and the volume ratio of the two was 1:2), and the eluent was removed by rotary evaporation to obtain intermediate 2;

[0039] S4. Mix 1.0 g of pre-modified nano-tungsten oxide with 100 mL of N,N-dimethylformamide in a three-necked round-bottom flask equipped with a thermometer and a stirrer, turn on the stirrer, and stir for 15 min to evenly disperse the pre-modified nano-tungsten oxide. Add 0.2 g of azobisisobutyronitrile and 8.1 g of intermediate 2, maintain the temperature of the system at 65 ° C, and keep the reaction for 8 h. After the reaction is completed, wash with anhydrous ethanol 3-4 times, freeze-dry, and grind to obtain modified nano-tungsten oxide.

[0040] Embodiment 2

[0041] Preparation of modified nano tungsten oxide:

[0042] S1. Add 2g of nano-tungsten oxide, 160mL of ethanol aqueous solution and 30mL of hydrochloric acid solution to a three-necked round-bottom flask equipped with a thermometer and a stirrer, stir and mix, then ultrasonically treat for 75min, add 11.2g of silane coupling agent KH-580, stir and heat to 60℃, keep warm for 2h, then stir and heat to 70℃, keep warm for 5h, the reaction is completed, cool, filter, wash with acetone, and vacuum dry to obtain pre-modified nano-tungsten oxide;

[0043] S2. Place a three-necked round-bottom flask equipped with a thermometer, a stirrer and a reflux condenser in a water bath, add 30.6 g of allyl bromide and 200 mL of N,N-dimethylformamide, mix and stir evenly, and add 39.8 g of 5-chloro-2-methylisothiazoline-3-one while stirring. After stirring evenly, raise the temperature of the device to 80°C, condense and reflux for 6 hours. After the reaction is completed, remove the solvent by distillation under reduced pressure, wash twice with acetone, and vacuum dry to obtain intermediate 1;

[0044] S3, in a three-necked round-bottom flask equipped with a thermometer and a stirrer, 117.4 g of intermediate 1 and 400 mL of N,N-dimethylformamide were mixed, the stirrer was turned on, 82.4 g of potassium carbonate and 25.2 g of melamine were added in sequence, and the temperature of the device was slowly raised to 60° C., and the reaction was kept warm for 12 hours. After the reaction was completed, it was filtered, part of the solvent was first removed by rotary evaporation, and then purified by column chromatography (the eluent was a mixed solvent of benzene / ethyl acetate, and the volume ratio of the two was 1:2), and the eluent was removed by rotary evaporation to obtain intermediate 2;

[0045] S4. Mix 2.0 g of pre-modified nano-tungsten oxide with 200 mL of N,N-dimethylformamide in a three-necked round-bottom flask equipped with a thermometer and a stirrer, turn on the stirrer, and stir for 15 min to evenly disperse the pre-modified nano-tungsten oxide. Add 0.4 g of azobisisobutyronitrile and 16.2 g of intermediate 2, maintain the temperature of the system at 65 ° C, and keep the reaction for 8 h. After the reaction is completed, wash with anhydrous ethanol 4 times, freeze-dry, and grind to obtain modified nano-tungsten oxide.

[0046] Embodiment 3

[0047] A1. 80 g of polyester resin was placed in a vacuum drying oven and dried for 12 h. After being taken out, the resin was mixed with 12 g of the modified nano-tungsten oxide prepared in Example 1, 8 g of boron nitride and 2 g of paraffin in a mixer for 30 min. The mixture was added to a twin-screw extruder and melt-blended to obtain primary fibers, which were then stretched to obtain modified polyester fibers.

[0048] A2. 55 g of the modified polyester fiber obtained in step A1 and 16 g of the wool fiber are combined on a drawing frame to make slivers, which are then drawn and twisted on a roving frame, and finally further drawn and twisted on a spinning frame to make blended yarns, which are then made into fabrics with nuclear radiation shielding function by a circular knitting method.

[0049] Embodiment 4

[0050] A1. 85 g of polyester resin was placed in a vacuum drying oven and dried for 12 h. After being taken out, the resin was mixed with 18 g of the modified nano-tungsten oxide prepared in Example 2, 10 g of boron carbide and 3 g of zinc stearate in a mixer for 30 min. The mixture was added to a twin-screw extruder and melt-blended to obtain primary fibers, which were then stretched to obtain modified polyester fibers.

[0051] A2. 60 g of the modified polyester fiber obtained in step A1 and 20 g of the wool fiber are combined on a drawing frame to make slivers, which are then drawn and twisted on a roving frame, and finally further drawn and twisted on a spinning frame to make blended yarns, which are then made into fabrics with nuclear radiation shielding function by a circular knitting method.

[0052] Embodiment 5

[0053] A1. Place 90g of polyester resin in a vacuum drying oven and dry for 12h. Take it out and put it into a mixer with 24g of modified nano tungsten oxide prepared in Example 2, 12g of boron carbide and 4g of zinc stearate for 30min. Add it into a twin-screw extruder, melt blend and spin to obtain primary fibers, and then stretch to obtain modified polyester fibers.

[0054] A2. 65 g of the modified polyester fiber obtained in step A1 and 24 g of the wool fiber are combined on a drawing frame to make slivers, which are then drawn and twisted on a roving frame, and finally further drawn and twisted on a spinning frame to make blended yarns, which are then made into fabrics with nuclear radiation shielding function by a circular knitting method.

[0055] Comparative Example 1

[0056] Ordinary nano tungsten oxide of the same mass is used to replace the modified nano tungsten oxide in Example 5, and the remaining steps are the same as those in Example 5 to obtain a fabric.

[0057] Comparative Example 2

[0058] Use commercially available polyester radiation shielding fabric.

[0059] Embodiments 3, 4, 5, and comparative examples 1 and 2 were made into corresponding shapes according to different test standards, and the following performance tests were performed:

[0060] The oxygen index is determined using the national standard GB / T 2406.2 "Determination of combustion behavior of plastics by oxygen index method";

[0061] The Cf-252 neutron radiation source was used and the 3He counter was used to measure the fast neutron attenuation coefficient.

[0062] Using 60CoY radiation source and NaI crystal detector, the γ radiation attenuation coefficient of the sample was measured;

[0063] The national standard GB / T 20944.2-2007 "Evaluation of antibacterial properties of textiles - Part 2: Absorption method" was used to test the antibacterial rates of Escherichia coli and Staphylococcus aureus, and then the antibacterial rates of Examples 3, 4, and 5 were measured after washing 30 times;

[0064] The measured results are shown in the following table:

[0065]

[0066] It can be seen from the above table that the fabric prepared in the embodiment of the present invention has excellent flame retardant, antibacterial and shielding properties, stable performance, and water-resistant, and has important application value in the field of nuclear radiation protection technology.

[0067] 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.

[0068] 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 fabric with nuclear radiation shielding function, characterized in that: Prepared by the following steps: A1. Dry the polyester resin, put it into a mixer with modified nano tungsten oxide, functional shielding material and processing aid, add it into a twin-screw extruder, melt blend and spin to obtain primary fiber, and then stretch it to obtain modified polyester fiber; A2. The modified polyester fiber and wool fiber are combined on a drawing frame to make slivers, which are then drawn and twisted on a roving frame, and further drawn and twisted on a spinning frame to make blended yarn. The fabric with nuclear radiation shielding function is made by a large circular machine weft knitting method.

2. The fabric with nuclear radiation shielding function according to claim 1, characterized in that: The modified nano tungsten oxide is prepared by the following steps: S1. After mixing nano-tungsten oxide, ethanol aqueous solution and hydrochloric acid solution, ultrasonic treatment is performed for 75 minutes, silane coupling agent KH-580 is added, stirred and heated to 60°C, and the mixture is kept warm for 2 hours, then stirred and heated to 70°C, and kept warm for 5 hours. After the reaction is completed, the mixture is cooled, filtered, washed and dried to obtain pre-modified nano-tungsten oxide; S2, allyl bromide and N,N-dimethylformamide were mixed and stirred evenly, and 5-chloro-2-methylisothiazoline-3-one was added while stirring, and after stirring evenly, the mixture was condensed and refluxed at 80° C. for 6 h. After the reaction was completed, the mixture was distilled under reduced pressure, washed, and dried to obtain intermediate 1; S3, mixing the intermediate 1 and N,N-dimethylformamide, adding potassium carbonate and melamine in sequence, and reacting at 60°C for 12 hours. After the reaction is complete, filtering, rotary evaporation, column chromatography purification, and rotary evaporation are performed to obtain the intermediate 2; S4. Mix the pre-modified nano tungsten oxide with N,N-dimethylformamide, stir for 15 minutes to make the pre-modified nano tungsten oxide evenly dispersed, add AIBN and intermediate 2, and react at 65°C for 8 hours. After the reaction is completed, wash, dry and grind to obtain modified nano tungsten oxide.

3. The fabric with nuclear radiation shielding function according to claim 2, characterized in that: In step S1, the ratio of the amount of nano-tungsten oxide, ethanol aqueous solution, hydrochloric acid solution, and silane coupling agent KH-580 is 1 g: 80 mL: 15 mL: 5.6 g.

4. The fabric with nuclear radiation shielding function according to claim 2, characterized in that: In step S2, the ratio of allyl bromide, N,N-dimethylformamide, and 5-chloro-2-methylisothiazoline-3-one is 15.3 g:100 mL:19.9 g.

5. The fabric with nuclear radiation shielding function according to claim 2, characterized in that: In step S3, the ratio of the amount of intermediate 1, N,N-dimethylformamide, potassium carbonate and melamine is 58.7 g: 200 mL: 41.2 g: 12.6 g.

6. The fabric with nuclear radiation shielding function according to claim 2, characterized in that: In step S4, the ratio of the amount of pre-modified nano-tungsten oxide, N,N-dimethylformamide, azobisisobutyronitrile, and intermediate 2 is 1.0 g: 100 mL: 0.2 g: 8.1 g.

7. The fabric with nuclear radiation shielding function according to claim 1, characterized in that: The raw materials in step A1 are calculated in parts by weight as follows: 80-90 parts of polyester resin, 12-24 parts of modified nano tungsten oxide, 8-12 parts of functional shielding material, and 2-4 parts of processing aid.

8. The fabric with nuclear radiation shielding function according to claim 1, characterized in that: In step A1, the functional shielding material is one or more of boron nitride, boron carbide, and tantalum powder.

9. The fabric with nuclear radiation shielding function according to claim 1, characterized in that: In step A1, the processing aid is one of paraffin and zinc stearate.

10. The fabric with nuclear radiation shielding function according to claim 1, characterized in that: The raw materials in step A2 are calculated in parts by weight as follows: 55-65 parts of modified polyester fiber and 16-24 parts of wool fiber.

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