Nuclear radiation protective clothing fabric

Abstract

The invention discloses a nuclear radiation protective clothing fabric, and belongs to the technical field of nuclear radiation protection, the nuclear radiation protective clothing fabric is prepared by blending polyester fibers, Gd / PET fibers and wool fibers, the mass ratio of the polyester fibers to the Gd / PET fibers to the wool fibers is 80: (30-35): (15-20), and the polyester fibers are prepared by melt blending and spinning PBT and modified carbon nanotubes; the mass ratio of the PBT to the modified carbon nanotubes is 60: (6-8). Due to the introduction of the modified carbon nanotubes into the polyester fibers in the fabric, the fibers not only have uniform, lasting and efficient shielding performance, but also have lasting flame-retardant performance and antibacterial performance; gd is added into the Gd / PET fiber, so that the fiber has lasting and efficient nuclear radiation resistance, tensile property and thermal stability; the wool fiber is added, so that the fiber has better air permeability and has important application significance.

Description

Technical Field

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

[0002] As the world's energy problems become increasingly severe, nuclear energy has developed into an indispensable energy source as a green energy source. However, with several major nuclear leakage incidents, people are "terrified of nuclear power". The widespread application of nuclear technology has brought huge benefits to mankind, but it has also increased people's chances of being exposed to various radiations and the impact of their radiation hazards. The development of nuclear technology is closely related to people's lives. Industrial flaw detection, sterilization and disinfection, irradiation processing, medical diagnosis and treatment, space exploration, imaging technology, etc. have greatly promoted the progress of human society. However, people are gradually aware of the irreversible damage caused by high-energy rays to the human body and the damage to the environment and facilities. Protection work is the guarantee of safe operation. In particular, protection for some complex environments requires the study of a new type of efficient flexible radiation shielding material to minimize the harm of radiation. In addition, the protective materials of traditional protective clothing are pressed as a whole with rubber or plastic substrates, and the clothing does not consider the problem of breathability. Nuclear workers work under hot and humid conditions for a long time, and the moisture generated by the body cannot be released, which is easy to breed bacteria. Especially when workers work in high temperature environments, the demand for breathability and flame retardancy of protective clothing is also stronger. Summary of the invention

[0003] The purpose of the present invention is to overcome the defects of the prior art and provide a nuclear radiation protective clothing fabric.

[0004] The purpose of the present invention can be achieved through the following technical solutions:

[0005] A nuclear radiation protective clothing fabric is obtained by blending polyester fiber, Gd / PET fiber and wool fiber, wherein the mass ratio of the polyester fiber, the Gd / PET fiber and the wool fiber is 80:30-35:15-20.

[0006] The chemical composition of wool fiber is mainly protein, which has good moisture absorption and air permeability, and can give the fabric better comfort, breathability, moisture permeability and warmth retention.

[0007] Furthermore, the polyester fiber is prepared by melt blending and spinning PBT and modified carbon nanotubes; the mass ratio of PBT to modified carbon nanotubes is 60:6-8.

[0008] Furthermore, the modified carbon nanotubes are prepared by the following steps:

[0009] S1. Place cyanuric chloride, deionized water and ethanol in a three-necked flask, stir and cool to 0-5°C, then add tetramethylguanidine dropwise to the three-necked flask, and after dripping, stir the mixed solution at 0-5°C for 2h. Then dry to constant weight to obtain intermediate 1, the ratio of cyanuric chloride, tetramethylguanidine and ethanol is 9.23g:7.11g:50mL. The specific reaction steps are as follows:

[0010]

[0011] S2, intermediate 1 and DMF are placed in a three-necked flask, and stirred and cooled to 0°C. Then monomethylphenyl phosphate is added dropwise to the above three-necked flask. After the dripping is complete, the system temperature is raised to 10-20°C and continued to stir for 6-8h, and then concentrated and dried to constant weight to obtain intermediate 2. The ratio of intermediate 1, monomethylphenyl phosphate, and DMF is 13.20g:9.40g:60mL. The specific reaction steps are as follows:

[0012]

[0013] S3, add intermediate 2 and DMF to a three-necked flask, heat and stir to 10-15°C, then add 2'2-diamino-4'4-(9-fluorenyl)biphenol solution dropwise to the above three-necked flask, after dripping, continue stirring the mixed solution at 15-20°C for 2h, then concentrate and dry to constant weight to obtain intermediate 3, intermediate 2, 2'2-diamino-4'4-(9-fluorenyl)biphenol, DMF usage ratio is 20.80g:19.02g:60mL. The specific reaction steps are as follows:

[0014]

[0015] S4, add the prepared intermediate 3 and the carboxylated carbon nanotubes dispersed by ultrasound for 3h to the DMF solution, mix and place in a three-necked flask, add DCC (dicyclohexylcarbodiimide) dropwise as a dehydrating agent, heat to 65°C, and stir and react for 24h under the protection of nitrogen. After the reaction is completed, filter and collect the product, wash with NMP and DMF for 5-10 times respectively, and then vacuum dry at 60°C for one week to obtain modified carbon nanotubes; the ratio of the amount of intermediate 3, carboxylated carbon nanotubes and DCC is 31.00g:8.60g:10.32g.

[0016] Carbon nanotubes are highly efficient inorganic conductive substances and are difficult to disperse evenly in a polyester matrix. The present invention modifies carbon nanotubes and introduces organic molecular chains on their surface by chemical bonding. On the one hand, an organic layer can be coated on the surface of the carbon nanotubes to enhance the compatibility between the two and promote the uniform dispersion of the carbon nanotubes in the polyester matrix. On the other hand, from the perspective of the introduced molecular chain structure, the carbon nanotubes contain nitrogen-containing benzene rings, guanidine groups (tetramethylguanidine), and phosphate groups. The introduction of nitrogen-containing benzene rings and phosphate groups can constitute a composite flame retardant material that integrates nitrogen-phosphorus flame retardant elements, exerts a synergistic flame retardant effect at the same site, and provides long-lasting flame retardant properties to a certain extent. The guanidine groups (tetramethylguanidine) give the modified carbon nanotubes long-lasting antibacterial properties.

[0017] Further, the carboxylated carbon nanotubes are prepared by the following steps:

[0018] The carbon nanotubes were soaked in HNO3 (mass fraction of 20%) for 14 hours, filtered, washed with water until neutral, and dried to constant weight to obtain purified carbon nanotubes; the purified carbon nanotubes were ultrasonically treated in HNO3-H2SO4 mixed acid for 5 hours, washed with water until neutral, filtered, and dried at 120°C to obtain carboxylated carbon nanotubes, the ratio of nitric acid to sulfuric acid was 1:3; the ratio of purified carbon nanotubes to HNO3-H2SO4 was 9.65g:120mL.

[0019] By subjecting carbon nanotubes to ultrasonic shearing and oxidation treatment with strong acid, a certain number of hydroxyl and carboxyl active groups can be introduced into the side walls and tops of the carbon nanotubes, thus laying the foundation for reaction sites for subsequent chemical reactions.

[0020] Furthermore, the Gd / PET fiber is prepared by mixing nano-scale gadolinium oxide powder and dry PET chips in a mass ratio of 5-10:30, stirring them evenly with a granulator, and melt-spinning them with a twin-screw extruder.

[0021] Beneficial effects of the present invention:

[0022] The fabric of the present invention is blended from polyester fiber, Gd / PET fiber and wool fiber. Due to the introduction of modified carbon nanotubes in polyester fiber, the fiber not only has uniform, lasting and efficient shielding performance, but also has durable flame retardant and antibacterial properties; due to the addition of Gd in Gd / PET fiber, the fiber has durable and efficient nuclear radiation protection performance, strong stretching performance and thermal stability; the addition of wool fiber makes the fiber have better air permeability. Therefore, the obtained fabric has durable, uniform and efficient nuclear radiation protection performance and shielding performance, and has good antistatic, antibacterial and air permeability, and has important application value in military and industrial fields. 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] Preparation of carboxylated carbon nanotubes:

[0026] Soak 9.65g of carbon nanotubes in HNO3 (mass fraction of 20%) for 14h, filter, wash with water until neutral, and dry to constant weight to obtain purified carbon nanotubes; ultrasonically treat the purified carbon nanotubes in 120mL of HNO3-H2SO4 mixed acid for 5h, wash with water until neutral, filter, and dry at 120°C to obtain carboxylated carbon nanotubes. The volume ratio of nitric acid to sulfuric acid is 1:3.

[0027] Embodiment 2

[0028] Preparation of modified carbon nanotubes:

[0029] S1. Place 9.23 g of cyanuric chloride, deionized water and 50 mL of ethanol in a three-necked flask, stir and cool to 0-5°C, then add 7.11 g of tetramethylguanidine dropwise to the three-necked flask, and after the mixture is completely dripped, stir the mixed solution at 0-5°C for 2 h. Then dry to constant weight to obtain an intermediate.

[0030] S2, 13.20g of intermediate 1 and 60mL of DMF were placed in a three-necked flask, and stirred and cooled to 0°C. Then 9.40g of monomethylphenyl phosphate was added dropwise to the three-necked flask, and after the addition was complete, the system temperature was raised to 10-20°C and stirred for 6-8h, and then concentrated and dried to constant weight to obtain intermediate 2.

[0031] S3. Add 20.80 g of intermediate 2 and 60 mL of DMF into a three-necked flask, heat and stir to 10-15 °C, then add 19.02 g of 2'2-diamino-4'4-(9-fluorenyl)biphenol dropwise into the above three-necked flask. After the mixture is completely added, stir the mixed solution at 15-20 °C for 2 h, then concentrate and dry to constant weight to obtain intermediate 3.

[0032] S4, 31.00g of intermediate 3 and 8.60g of carboxylated carbon nanotubes dispersed by ultrasound for 3h were added to the DMF solution, mixed and placed in a three-necked flask, 10.32g of DCC was added dropwise as a dehydrating agent, the temperature was raised to 65°C, and the reaction was stirred for 24h under the protection of nitrogen. After the reaction was completed, the product was filtered and collected, washed with NMP and DMF for 5-10 times respectively, and then vacuum dried at 60°C for one week to obtain modified carbon nanotubes.

[0033] Embodiment 3

[0034] Preparation of modified carbon nanotubes:

[0035] S1. Place 18.46 g of cyanuric chloride, deionized water and 100 mL of ethanol in a three-necked flask, stir and cool to 0-5°C, then add 14.11 g of tetramethylguanidine dropwise to the three-necked flask, and after the mixture is completely dripped, stir the mixed solution at 0-5°C for 2 h. Then dry to constant weight to obtain an intermediate.

[0036] S2, 26.40g of intermediate 1 and 20mL of DMF were placed in a three-necked flask, and stirred and cooled to 0°C. Then 18.80g of monomethylphenyl phosphate was added dropwise to the three-necked flask, and after the dripping was complete, the system temperature was raised to 10-20°C and continued to stir for 6-8h, and then the reaction solution was concentrated and dried to constant weight to obtain intermediate 2.

[0037] S3. Add 41.60 g of intermediate 2 and 120 mL of DMF into a three-necked flask, heat and stir to 10-15 °C, then add 38.04 g of 2'2-diamino-4'4-(9-fluorenyl)biphenol dropwise into the three-necked flask, and after the mixture is completely added, stir the mixed solution at 15-20 °C for 2 h, then concentrate and dry to constant weight to obtain intermediate 3.

[0038] S4, add 62.00g of intermediate 3 and 17.20g of carboxylated carbon nanotubes dispersed by ultrasound for 3h to the DMF solution, mix and place in a three-necked flask, add 20.64g of DCC dropwise as a dehydrating agent, heat to 65°C, and stir and react for 24h under the protection of nitrogen. After the reaction is completed, filter and collect the product, wash with NMP and DMF for 5-10 times respectively, and then vacuum dry at 60°C for one week to obtain modified carbon nanotubes.

[0039] Embodiment 4

[0040] 600 g of PBT and 60 g of the modified carbon nanotubes prepared in Example 2 were melt-blended and spun to prepare polyester fibers.

[0041] Embodiment 5

[0042] 600 g of PBT and 70 g of the modified carbon nanotubes prepared in Example 3 were melt blended and spun to prepare polyester fibers.

[0043] Embodiment 6

[0044] 600 g of PBT and 80 g of the modified carbon nanotubes prepared in Example 2 were melt-blended and spun to prepare polyester fibers.

[0045] Embodiment 7

[0046] A nuclear radiation protective clothing fabric is obtained by mixed spinning of the polyester fiber, Gd / PET fiber and wool fiber prepared in Example 4, wherein the mass ratio of the three fibers is 80:30:15.

[0047] The filaments of each fiber are wound onto a reel with a winding machine, the filaments on the bobbin are twisted with a do-or-die twister, and then the yarns required for weaving are warped with a single yarn warping machine. The warping is performed by a combined four-layer fabric method in the order of polyester fiber, Gd / PET fiber, wool fiber and polyester fiber. 16 healds are used for sequential drawing, in which the drawing-in yarns are jointly provided by the yarns of two warp beams, and 8 reeds are used for drawing-in to obtain the fabric.

[0048] Embodiment 8

[0049] A nuclear radiation protective clothing fabric is obtained by mixed spinning of the polyester fiber, Gd / PET fiber and wool fiber prepared in Example 5, wherein the mass ratio of the three fibers is 80:33:16.

[0050] The filaments of each fiber are wound onto a reel with a winding machine, the filaments on the bobbin are twisted with a do-or-die twister, and then the yarns required for weaving are warped with a single yarn warping machine. The warping is performed by a combined four-layer fabric method in the order of polyester fiber, Gd / PET fiber, wool fiber and polyester fiber. 16 healds are used for sequential drawing, in which the drawing-in yarns are jointly provided by the yarns of two warp beams, and 8 reeds are used for drawing-in to obtain the fabric.

[0051] Embodiment 9

[0052] A nuclear radiation protective clothing fabric is obtained by mixed spinning of the polyester fiber, Gd / PET fiber and wool fiber prepared in Example 6, with the mass ratio of the three being 80:35:20.

[0053] The filaments of each fiber are wound onto a reel with a winding machine, the filaments on the bobbin are twisted with a do-or-die twister, and then the yarns required for weaving are warped with a single yarn warping machine. The warping is performed by a combined four-layer fabric method in the order of polyester fiber, Gd / PET fiber, wool fiber and polyester fiber. 16 healds are used for sequential drawing, in which the drawing-in yarns are jointly provided by the yarns of two warp beams, and 8 reeds are used for drawing-in to obtain the fabric.

[0054] Comparative Example 1

[0055] The difference from Example 2 is that only polyester fiber is contained.

[0056] Comparative Example 2

[0057] The difference from the second embodiment is that the polyester fiber is composed of PBT and ordinary carbon nanotubes.

[0058] The fabrics obtained in Examples 7 to 9 and Comparative Examples 1 and 2 were cut into test samples and subjected to the following performance tests:

[0059]

[0060] It can be seen from the data in the above table that the prepared fabric has long-lasting, stable and efficient nuclear radiation protection performance. At the same time, it has good antibacterial properties, breathability, flame retardancy and mechanical properties.

[0061] 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.

[0062] 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 nuclear radiation protective clothing fabric, obtained by blending polyester fiber, Gd / PET fiber and wool fiber, characterized in that: The polyester fiber is prepared by melt blending and spinning PBT and modified carbon nanotubes; Wherein, the modified carbon nanotubes are prepared by the following steps: S1. Place cyanuric chloride, deionized water and ethanol in a three-necked flask, stir and cool to 0-5°C, then add tetramethylguanidine dropwise to the three-necked flask, and after the mixture is completely added, stir the mixed solution at 0-5°C for 2h, and then dry to constant weight to obtain intermediate 1. S2, intermediate 1 and DMF are placed in a three-necked flask, and stirred and cooled to 0°C, and then monomethylphenyl phosphate is added dropwise to the three-necked flask. After the dripping is complete, the system temperature is raised to 10-20°C and stirring is continued for 6-8h, and then concentrated and dried to constant weight to obtain intermediate 2; S3, adding intermediate 2 and DMF into a three-necked flask, heating and stirring to 10-15°C, then adding 2'2-diamino-4'4-(9-fluorenyl)biphenol dropwise into the three-necked flask, after the dropwise addition, stirring the mixed solution at 15-20°C for 2h, then concentrating and drying to constant weight to obtain intermediate 3; S4. Add the prepared intermediate 3 and the carboxylated carbon nanotubes dispersed by ultrasound for 3 hours into the DMF solution, mix and place in a three-necked flask, add DCC dropwise as a dehydrating agent, raise the temperature to 65°C, and stir the reaction for 24 hours under the protection of nitrogen. After the reaction is completed, filter and collect the product, wash it with NMP and DMF for 5-10 times respectively, and then vacuum dry it at 60°C for one week to obtain modified carbon nanotubes.

2. The nuclear radiation protective clothing fabric according to claim 1, characterized in that: In step S1, the ratio of cyanuric acid, tetramethylguanidine and ethanol is 9.23 g:7.11 g:50 mL.

3. The nuclear radiation protective clothing fabric according to claim 1, characterized in that: In step S2, the ratio of the amount of intermediate 1, monomethylphenyl phosphate and DMF is 13.20 g:9.40 g:60 mL.

4. The nuclear radiation protective clothing fabric according to claim 1, characterized in that: In step S3, the ratio of the intermediate 2, 2'2-diamino-4'4-(9-fluorenyl)biphenol and DMF is 20.80 g:19.02 g:60 mL.

5. The nuclear radiation protective clothing fabric according to claim 1, characterized in that: In step S4, the ratio of the amount of intermediate 3, carboxylated carbon nanotubes and DCC is 31.00 g:8.60 g:10.32 g.

6. The nuclear radiation protective clothing fabric according to claim 1, characterized in that: In step S4, the carboxylated carbon nanotubes are vacuum dried at 60° C. for 7 days before use.

7. The nuclear radiation protective clothing fabric according to claim 1, characterized in that: The mass ratio of polyester fiber, Gd / PET fiber and wool fiber is 80:30-35:15-20.

8. The nuclear radiation protective clothing fabric according to claim 1, characterized in that: The mass ratio of PBT to modified carbon nanotubes in the polyester fiber is 60:6-8.

Images