Anti-radiation fabric and preparation method thereof

Abstract

The invention discloses an anti-radiation fabric and a preparation method thereof, and relates to the technical field of fabric preparation. When the anti-radiation fabric is prepared, bismuth powder is pre-modified with (3-chloropropyl) trimethoxysilane and then reacts with an anti-aging agent to prepare modified bismuth powder; the preparation method comprises the following steps: enabling 4-aminophenylethanol and 4-(2-ethoxyl) benzaldehyde to react to prepare a flame-retardant monomer, and then enabling the flame-retardant monomer to react with isophorone diisocyanate and 1, 4-butylene glycol to prepare polyurethane; the preparation method comprises the following steps: reacting dimethylallylamine with 1, 3-bis (chloromethyl)-1, 1, 3, 3-tetramethyldisiloxane to obtain an antibacterial cross-linking agent; the modified bismuth powder, N, N-dimethylformamide, polyurethane, an antibacterial cross-linking agent and benzoyl peroxide are mixed to prepare a polyurethane coating, the outer side surface of polyester base cloth is coated with the polyurethane coating, drying is conducted, and the anti-radiation coating fabric is prepared. The anti-radiation fabric prepared by the invention has good anti-radiation, anti-light aging, flame-retardant and antibacterial properties.

Description

Technical Field

[0001] The present invention relates to the technical field of fabric preparation, and particularly relates to a radiation-proof fabric and a preparation method thereof. Background Art

[0002] With the rapid development of technology, various electronic devices such as televisions, computers, mobile phones, microwave ovens, and numerous medical and industrial electronic instruments have been widely popularized in people's lives and work. However, these devices continuously emit electromagnetic wave radiation of different intensities during operation. People who are in a radiation environment for a long time are prone to health problems such as insomnia, memory loss, physical weakness, and decreased immunity. Therefore, radiation-proof fabrics have emerged and gradually become an important means for people to protect against the hazards of electromagnetic radiation.

[0003] Currently, there are various technologies for preparing radiation-proof fabrics in the market. People's requirements for the performance of radiation-proof fabrics are becoming increasingly diverse. In addition to high-efficiency radiation-proof performance, they also expect good anti-photoaging, flame retardancy, and antibacterial properties. Traditional radiation-proof fabrics often only focus on the single function of radiation protection and perform poorly in other performance aspects. For example, most fabrics lack an effective flame retardant mechanism and cannot provide additional safety protection for users in case of dangerous situations such as open flames; in terms of antibacterial properties, ordinary fabrics are prone to bacterial growth, affecting wearing hygiene and health. To solve the above problems, the present invention aims to prepare a high-performance fabric that combines good radiation protection, anti-photoaging, flame retardancy, and antibacterial properties to meet people's multi-faceted requirements for functional fabrics in a complex living environment. Summary of the Invention

[0004] The purpose of the present invention is to provide a radiation-proof fabric and a preparation method thereof to solve the problems existing in the prior art. To solve the above technical problems, the present invention provides the following technical solutions:

[0005] A radiation-proof fabric, wherein the radiation-proof fabric is prepared by mixing modified bismuth powder, N-N-dimethylformamide, polyurethane, antibacterial crosslinking agent, and benzoyl peroxide to obtain a polyurethane coating, and coating and drying it on the outer surface of a polyester base fabric to obtain a radiation-proof coated fabric.

[0006] As an optimization, the modified bismuth powder is prepared by pre-modifying bismuth powder with (3-chloropropyl)trimethoxysilane and then reacting it with an anti-aging agent.

[0007] As an optimization, the polyurethane is prepared by reacting 4-aminophenylethanol and 4-(2-hydroxyethyl)benzaldehyde to obtain a flame retardant monomer, and then reacting it with isophorone diisocyanate and 1,4-butenediol.

[0008] As an optimization, the antibacterial crosslinking agent is prepared by reacting dimethylallylamine with 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane.

[0009] A method for preparing a radiation-proof fabric, comprising the following steps:

[0010] (1) Mix intermediate 1, anhydrous aluminum trichloride, and chlorobenzene evenly according to a mass ratio of 1:(0.4 - 0.6):(7 - 9), stir at 300 - 500 r / min for 25 - 35 min at 0 - 5 °C, add resorcinol in an amount 0.20 - 0.25 times the mass of intermediate 1, and react at 80 - 85 °C for 3 - 5 h to obtain an anti-aging agent;

[0011] (2) Mix the anti-aging agent, sodium hydroxide, and N,N-dimethylformamide evenly according to a mass ratio of 1:(0.07 - 0.09):(9 - 11), stir at 400 - 500 r / min for 25 - 35 min at 48 - 52 °C, and uniformly add a pre-modified bismuth powder mixture in an amount 0.6 - 0.8 times the mass of the anti-aging agent dropwise within 2 - 3 min, raise the temperature to 70 - 90 °C, react for 6 - 7 h, and cool and filter to obtain modified bismuth powder;

[0012] (3) Mix isophorone diisocyanate, a flame retardant monomer, 1,4-butenediol, and dibutyltin dilaurate evenly according to a mass ratio of 1:(0.3 - 0.7):(0.8 - 1.2):(0.03 - 0.05), stir at 300 - 500 r / min for 2 - 4 h at 83 - 87 °C to obtain polyurethane;

[0013] (4) Weigh 10 - 15 parts of modified bismuth powder, 28 - 30 parts of N,N-dimethylformamide, 40 - 50 parts of polyurethane, 2 - 3 parts of antibacterial crosslinking agent, and 0.8 - 1.2 parts of benzoyl peroxide by mass; mix the modified bismuth powder and dimethylformamide evenly, ultrasonically disperse for 25 - 35 min, then add polyurethane, antibacterial crosslinking agent, and benzoyl peroxide, and stir at 600 - 800 r / min at room temperature for 5 - 7 min to obtain a polyurethane coating, coat it on the outer surface of a polyester base fabric, react at 60 - 100 °C for 20 - 24 h, and then dry at 50 - 70 °C for 1 - 2 h to make a radiation-proof coated fabric with a surface density of 2 - 3 kg / m 2 ².

[0014] As an optimization, Intermediate 1 in step (1) is prepared by uniformly mixing cyanuric chloride and (2,2,6,6-tetramethyl-piperidin-4-yl)-methylamine at a molar ratio of 1:2, adding toluene in an amount 10 - 12 times the mass of cyanuric chloride, stirring and reacting at 300 - 400 r / min at 0 - 5°C for 2 - 3 h, adding an aqueous solution of 28 wt% sodium hydroxide in an amount 1.4 - 1.6 times the mass of cyanuric chloride, heating to 60 - 80°C and reacting for 12 - 16 h, and drying in vacuo at 50 - 60°C to obtain Intermediate 1.

[0015] As an optimization, the pre-modified bismuth powder in step (2) is prepared by uniformly mixing a bismuth powder suspension, (3-chloropropyl)trimethoxysilane, and deionized water at a mass ratio of 1:(0.1 - 0.3):(0.5 - 1.5), stirring at 300 - 500 r / min at 10 - 30°C for 2 - 3 h, centrifuging, washing 3 - 5 times with absolute ethanol, and drying in vacuo at 60 - 70°C to obtain the pre-modified bismuth powder.

[0016] As an optimization, the bismuth powder suspension is prepared by uniformly mixing bismuth powder and absolute ethanol at a mass ratio of 1:(13 - 19), adjusting the pH value to 5 - 6 by adding acetic acid, ultrasonically dispersing for 25 - 35 min, oscillating at 150 - 250 r / min at 70 - 80°C for 1 - 2 h, and cooling to room temperature to obtain the bismuth powder suspension. The purity of the bismuth powder is 99.9%, and it is purchased from Anhui Kerun Nano Technology Co., Ltd.

[0017] As an optimization, the pre-modified bismuth powder mixture in step (2) is prepared by uniformly mixing the pre-modified bismuth powder and N,N-dimethylformamide at a mass ratio of 1:2 at room temperature.

[0018] As an optimization, the reaction process of the anti-aging agent in step (2) is as follows:

[0019]

[0020] As an optimization, the flame retardant monomer in step (3) is prepared by uniformly mixing 4-aminophenethyl alcohol and 4-(2-hydroxyethyl)benzaldehyde at a molar ratio of 1:1, adding methanol in an amount 70 - 90 times the mass of 4-aminophenethyl alcohol, stirring at 300 - 500 r / min at 40 - 60°C under a nitrogen atmosphere for 4 - 6 h, dropwise adding diethyl phosphite in an amount 1.6 - 1.8 times the mass of 4-aminophenethyl alcohol and methanol in an amount 15 - 25 times the mass of 4-aminophenethyl alcohol within 20 - 30 min, reacting at 45 - 55°C for 10 - 12 h, and drying at 70 - 90°C to obtain the flame retardant monomer.

[0021] As an optimization, the antibacterial crosslinking agent described in step (4) is prepared by uniformly mixing dimethylallylamine, 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane, sodium iodide and toluene in a mass ratio of 1:(1.1 - 1.3):(0.01 - 0.03):(4 - 8), stirring and reacting at 70 - 80 °C and 400 - 500 r / min for 24 - 38 h under a nitrogen atmosphere, and drying in vacuo at 60 - 70 °C for 4 - 6 h to obtain the antibacterial crosslinking agent.

[0022] As an optimization, the reaction process of the antibacterial crosslinking agent described in step (4) is as follows:

[0023]

[0024] As an optimization, the polyester base fabric described in step (4) is woven with polyester filaments having a linear density of 0.8 - 2.2 dtex in a plain weave and has a grammage of 120 - 150 g / m 2 Plain weave.

[0025] Compared with the prior art, the beneficial effects achieved by the present invention are as follows:

[0026] When preparing a radiation-proof fabric, the present invention pre-modifies bismuth powder with (3-chloropropyl)trimethoxysilane and then reacts it with an anti-aging agent to obtain modified bismuth powder; reacts 4-aminophenethyl alcohol and 4-(2-hydroxyethyl)benzaldehyde to obtain a flame retardant monomer, and then reacts it with isophorone diisocyanate and 1,4-butenediol to obtain polyurethane; reacts dimethylallylamine and 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane to obtain an antibacterial crosslinking agent; mixes the modified bismuth powder, dimethylformamide, polyurethane, antibacterial crosslinking agent, and benzoyl peroxide to obtain a polyurethane coating, which is coated on the outer surface of the polyester base fabric and dried to obtain a radiation-proof coated fabric.

[0027] First, bismuth powder is treated with (3-chloropropyl)trimethoxysilane to obtain pre-modified bismuth powder, and then reacted with an anti-aging agent to obtain modified bismuth powder. As a "green metal" with soft texture and brittle nature, bismuth has good protection ability against X-rays, and its high atomic number enables it to have a strong scattering effect on electromagnetic waves. After modification, a special chemical structure is formed on its surface. On the one hand, it expands the interaction area with electromagnetic waves, causing more electromagnetic waves to scatter on the material surface; on the other hand, the functional groups generated by modification and the change in electron cloud distribution enhance the absorption and conversion ability of electromagnetic waves, converting electromagnetic energy into heat energy dissipation, thus significantly improving the radiation protection performance of the fabric. The silane coupling agent (3-chloropropyl)trimethoxysilane is used to modify the surface of bismuth powder, effectively solving the powder self-aggregation effect and improving the compatibility of bismuth powder with polyurethane. The modified bismuth powder is uniformly dispersed in the polyurethane coating and tightly combined with the matrix, avoiding the problems of easy shedding and oxidation of traditional metal materials and ensuring the long-term effectiveness of the radiation protection effect. Using cyanuric chloride and (2,2,6,6-tetramethyl-piperidin-4-yl)-methylamine as starting materials, after double substitution to obtain intermediate 1, and then reacting with resorcinol to construct intramolecular hydrogen bonds to obtain an anti-aging agent, and finally etherifying the meta-hydroxy group in the structure through chloropropyl to obtain a propyl-modified functional additive. The structure contains piperidineamine groups and intramolecular hydrogen bonds, making the prepared compound have high-efficiency anti-photoaging function.

[0028] Secondly, 4-aminophenethyl alcohol and 4-(2-hydroxyethyl)benzaldehyde are reacted to obtain a flame retardant monomer, and then reacted with isophorone diisocyanate and 1,4-butenediol to obtain polyurethane. The phosphorus-containing group of the flame retardant monomer decomposes when heated to generate polyphosphoric acid, forming a dense heat-insulating layer on the fabric surface through dehydration and carbonization to isolate oxygen and combustible gases; at the same time, phosphorus-containing free radicals capture combustion active free radicals to interrupt the chain reaction, achieving double flame retardancy in the condensed phase and gas phase. The aromatic ring structure in the monomer enhances the strength of the carbonized layer by virtue of its high thermal stability, and the polyhydroxy structure and phosphorus-containing compounds synergistically promote carbonization. The hydroxyl group of the flame retardant monomer polymerizes with the isocyanate group of isophorone diisocyanate to form intermolecular chemical cross-linking bonds, enhancing the degree of intermolecular cross-linking and achieving double optimization of flame retardancy and mechanical properties.

[0029] Finally, dimethylallylamine and 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane are reacted to obtain an antibacterial cross-linking agent. The siloxane structure and amine group in the antibacterial cross-linking agent act synergistically to be able to destroy the bacterial cell membrane structure and inhibit bacterial growth; it is firmly combined with polyurethane through cross-linking reaction to form a persistent antibacterial layer on the fabric surface, avoiding the migration and loss of antibacterial components. Specific implementation mode

[0030] Next, in combination with the embodiments of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0031] Example 1:

[0032] A radiation-proof fabric and a preparation method thereof. The preparation method of the radiation-proof fabric mainly includes the following preparation steps:

[0033] (1) Cyanuric chloride and (2,2,6,6-tetramethyl-piperidin-4-yl)-methylamine are mixed evenly according to a molar ratio of 1:2, toluene 10 times the mass of cyanuric chloride is added, and the mixture is stirred and reacted at 300 r / min at 0 °C for 2 h. Then, an aqueous solution of 28 wt% sodium hydroxide 1.4 times the mass of cyanuric chloride is added, and the temperature is raised to 85 °C for reaction for 12 h, and then vacuum dried at 60 °C to obtain Intermediate 1;

[0034] (2) Bismuth powder and absolute ethanol are mixed evenly according to a mass ratio of 1:13, acetic acid is added to adjust the pH value to 5, and ultrasonic dispersion is carried out for 25 min. Then, the mixture is shaken at 150 r / min at 80 °C for 1 h and cooled to room temperature to obtain a bismuth powder suspension. The bismuth powder suspension, (3-chloropropyl)trimethoxysilane, and deionized water are mixed evenly according to a mass ratio of 1:0.1:0.5, stirred at 300 r / min at 30 °C for 2 h, centrifuged and separated, washed 3 times with absolute ethanol, and vacuum dried at 70 °C to obtain pre-modified bismuth powder. Intermediate 1, anhydrous aluminum trichloride, and chlorobenzene are mixed evenly according to a mass ratio of 1:0.4:7, stirred at 300 r / min at 5 °C for 25 min, resorcinol 0.20 times the mass of Intermediate 1 is added, and the reaction is carried out at 80 °C for 3 - 5 h to obtain an anti-aging agent. The anti-aging agent, sodium hydroxide, and N,N-dimethylformamide are mixed evenly according to a mass ratio of 1:0.07:9, stirred at 400 r / min at 52 °C for 25 min, and a mixed solution of pre-modified bismuth powder 0.6 times the mass of the anti-aging agent is added dropwise uniformly within 2 min. Then, the temperature is raised to 90 °C, and the reaction is carried out for 6 h, and then cooled and filtered to obtain modified bismuth powder;

[0035] (3) Mix 4 - aminophenethyl alcohol and 4-(2 - hydroxyethyl)benzaldehyde evenly at a molar ratio of 1:1, add methanol which is 70 times the mass of 4 - aminophenethyl alcohol, stir at 60 °C and 300 r / min for 4 h under a nitrogen atmosphere, dropwise add diethyl phosphite which is 1.6 times the mass of 4 - aminophenethyl alcohol and 15 times the mass of methanol respectively within 20 min, react at 55 °C for 10 h, and dry at 90 °C to obtain a flame - retardant monomer; Mix isophorone diisocyanate, the flame - retardant monomer, 1,4 - butanediol and dibutyltin dilaurate evenly at a mass ratio of 1:0.3:0.8:0.03, stir at 90 °C and 300 r / min for 2 h to obtain polyurethane;

[0036] (4) Mix dimethylallylamine, 1,3 - bis(chloromethyl)-1,1,3,3 - tetramethyldisiloxane, sodium iodide and toluene evenly at a mass ratio of 1:1.1:0.01:4, stir and react at 80 °C and 400 r / min for 24 h under a nitrogen atmosphere, vacuum - dry at 70 °C for 4 h to obtain an antibacterial cross - linker; By mass fraction, weigh 10 parts of modified bismuth powder, 28 parts of N,N - dimethylformamide, 40 parts of polyurethane, 2 parts of antibacterial cross - linker, and 0.8 part of benzoyl peroxide; Mix the modified bismuth powder and N,N - dimethylformamide evenly, ultrasonically disperse for 25 min, then add polyurethane, antibacterial cross - linker and benzoyl peroxide, stir at room temperature and 600 r / min for 5 min to obtain a polyurethane coating, and coat it on the outer surface of a polyester base fabric with a linear density of 0.8 dtex and a grammage of 120 g / m 2 and react at 100 °C for 20 h, dry at 70 °C for 1 h to make a radiation - resistant coating fabric with a surface density of 2 kg / m 2 2.

[0037] Example 2:

[0038] A radiation - resistant fabric and its preparation method. The preparation method of the radiation - resistant fabric mainly includes the following preparation steps:

[0039] (1) Mix cyanuric chloride and (2,2,6,6 - tetramethyl - piperidin - 4 - yl)-methylamine evenly at a molar ratio of 1:2, add toluene which is 11 times the mass of cyanuric chloride, stir and react at 3 °C and 350 r / min for 2.5 h, add a 28 wt% aqueous sodium hydroxide solution which is 1.5 times the mass of cyanuric chloride, heat up to 70 °C and react for 14 h, and vacuum - dry at 55 °C to obtain Intermediate 1;

[0040] (2) Mix bismuth powder and absolute ethanol evenly at a mass ratio of 1:16, add acetic acid to adjust the pH value to 5.5, disperse ultrasonically for 30 min, shake at 75 °C and 200 r / min for 1.5 h, and cool to room temperature to obtain a bismuth powder suspension; Mix the bismuth powder suspension, (3-chloropropyl)trimethoxysilane and deionized water evenly at a mass ratio of 1:0.2:1, stir at 20 °C and 400 r / min for 2.5 h, centrifuge and separate, wash 4 times with absolute ethanol, and dry in vacuum at 65 °C to obtain pre-modified bismuth powder; Mix intermediate 1, anhydrous aluminum trichloride and chlorobenzene evenly at a mass ratio of 1:0.5:8, stir at 3 °C and 400 r / min for 30 min, add resorcinol which is 0.23 times the mass of intermediate 1, and react at 83 °C for 4 h to obtain an anti-aging agent; Mix the anti-aging agent, sodium hydroxide and N,N-dimethylformamide evenly at a mass ratio of 1:0.08:10, stir at 50 °C and 450 r / min for 30 min, dropwise add the pre-modified bismuth powder mixture which is 0.7 times the mass of the anti-aging agent uniformly within 2.5 min, raise the temperature to 80 °C, react for 6.5 h, cool and filter to obtain modified bismuth powder;

[0041] (3) Mix 4-aminophenethyl alcohol and 4-(2-hydroxyethyl)benzaldehyde evenly at a molar ratio of 1:1, add methanol which is 80 times the mass of 4-aminophenethyl alcohol, stir at 50 °C and 400 r / min for 5 h under a nitrogen atmosphere, dropwise add diethyl phosphite which is 1.7 times the mass of 4-aminophenethyl alcohol and 20 times the mass of methanol respectively within 25 min, react at 50 °C for 11 h, and dry at 80 °C to obtain a flame retardant monomer; Mix isophorone diisocyanate, the flame retardant monomer, 1,4-butenediol and dibutyltin dilaurate evenly at a mass ratio of 1:0.5:1:0.04, stir at 85 °C and 400 r / min for 3 h to obtain a polyurethane;

[0042] (4) Mix dimethylallylamine, 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane, sodium iodide and toluene evenly at a mass ratio of 1:1.2:0.02:6, stir and react at 75 °C and 450 r / min for 31 h under a nitrogen atmosphere, and dry in vacuum at 65 °C for 5 h to obtain an antibacterial crosslinking agent; By mass, weigh 12.5 parts of modified bismuth powder, 29 parts of N,N-dimethylformamide, 45 parts of polyurethane, 2.5 parts of antibacterial crosslinking agent, and 1 part of benzoyl peroxide; Mix the modified bismuth powder and dimethylformamide evenly, disperse ultrasonically for 30 min, then add polyurethane, antibacterial crosslinking agent and benzoyl peroxide, and stir at room temperature and 700 r / min for 6 min to obtain a polyurethane coating, and coat it on the outer surface of a polyester base fabric with a linear density of 1.6 dtex and a grammage of 135 g / m 2 and react at 80 °C for 22 h, and dry at 60 °C for 1.5 h to make a radiation-proof coating fabric with a surface density of 2.5 kg / m 2 ​

[0043] Example 3:

[0044] An anti-radiation fabric and a preparation method thereof. The preparation method of the anti-radiation fabric mainly includes the following preparation steps:

[0045] (1) Cyanuric chloride and (2,2,6,6-tetramethyl-piperidin-4-yl)-methylamine are mixed evenly according to a molar ratio of 1:2, toluene 12 times the mass of cyanuric chloride is added, and the mixture is stirred and reacted at 400 r / min at 0 °C for 3 h. A 28 wt% sodium hydroxide aqueous solution 1.6 times the mass of cyanuric chloride is added, and the temperature is raised to 60 °C and reacted for 16 h, and then vacuum dried at 50 °C to obtain Intermediate 1;

[0046] (2) Bismuth powder and absolute ethanol are mixed evenly according to a mass ratio of 1:19, acetic acid is added to adjust the pH value to 6, and ultrasonic dispersion is carried out for 35 min. At 70 °C, it is shaken at 250 r / min for 2 h, and then cooled to room temperature to obtain a bismuth powder suspension; the bismuth powder suspension, (3-chloropropyl)trimethoxysilane and deionized water are mixed evenly according to a mass ratio of 1:0.3:1.5, and stirred at 10 °C and 500 r / min for 3 h, then centrifuged and separated, washed 5 times with absolute ethanol, and vacuum dried at 60 °C to obtain pre-modified bismuth powder; Intermediate 1, anhydrous aluminum trichloride and chlorobenzene are mixed evenly according to a mass ratio of 1:0.6:9, and stirred at 500 r / min at 0 °C for 35 min, resorcinol 0.25 times the mass of Intermediate 1 is added, and the reaction is carried out at 80 °C for 5 h to obtain an anti-aging agent; the anti-aging agent, sodium hydroxide, and N,N-dimethylformamide are mixed evenly according to a mass ratio of 1:0.09:11, and stirred at 500 r / min at 48 °C for 35 min. A pre-modified bismuth powder mixture 0.8 times the mass of the anti-aging agent is added dropwise uniformly within 3 min, the temperature is raised to 70 °C, and the reaction is carried out for 7 h, and then cooled and filtered to obtain modified bismuth powder;

[0047] (3) 4-Aminophenethyl alcohol and 4-(2-hydroxyethyl)benzaldehyde are mixed evenly according to a molar ratio of 1:1, methanol 90 times the mass of 4-aminophenethyl alcohol is added, and the mixture is stirred at 40 °C and 500 r / min for 6 h under a nitrogen atmosphere. Diethyl phosphite 1.8 times the mass of 4-aminophenethyl alcohol and 25 times the mass of methanol are respectively added dropwise within 30 min, and the reaction is carried out at 45 °C for 12 h, and then dried at 70 °C to obtain a flame retardant monomer; isophorone diisocyanate, the flame retardant monomer, 1,4-butenediol and dibutyltin dilaurate are mixed evenly according to a mass ratio of 1:0.7:1.2:0.05, and stirred at 80 °C and 500 r / min for 4 h to obtain polyurethane;

[0048] (4) Mix dimethylallylamine, 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane, sodium iodide, and toluene evenly in a mass ratio of 1:1.3:0.03:8. Under a nitrogen atmosphere, stir and react at 70 °C and 500 r / min for 38 h, and then vacuum dry at 60 °C for 6 h to obtain an antibacterial crosslinking agent. By mass, weigh 15 parts of modified bismuth powder, 30 parts of N,N-dimethylformamide, 50 parts of polyurethane, 3 parts of antibacterial crosslinking agent, and 1.2 parts of benzoyl peroxide. Mix the modified bismuth powder and N,N-dimethylformamide evenly, ultrasonically disperse for 35 min, then add polyurethane, antibacterial crosslinking agent, and benzoyl peroxide, and stir at room temperature and 800 r / min for 7 min to obtain a polyurethane coating. After removing bubbles, coat the polyurethane coating on the outer surface of a polyester base fabric with a linear density of 2.2 dtex and a gram weight of 150 g / m 2 On the outer surface, react at 60 °C for 24 h and dry at 50 °C for 2 h to make a radiation-proof coating fabric with a surface density of 3 kg / m 2 .

[0049] Comparative Example 1:

[0050] The preparation method of a radiation-proof fabric in Comparative Example 1 is different from that in Example 2 in that steps (1) and (2) are not carried out, and step (4) is modified as follows: Mix dimethylallylamine, 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane, sodium iodide, and toluene evenly in a mass ratio of 1:1.2:0.02:6. Under a nitrogen atmosphere, stir and react at 75 °C and 450 r / min for 31 h, and then vacuum dry at 65 °C for 5 h to obtain an antibacterial crosslinking agent. By mass, weigh 45 parts of polyurethane, 2.5 parts of antibacterial crosslinking agent, and 1 part of benzoyl peroxide. Stir at room temperature and 700 r / min for 6 min to obtain a polyurethane coating, and coat it on the outer surface of a polyester base fabric with a linear density of 1.6 dtex and a gram weight of 135 g / m 2 On the outer surface, react at 80 °C for 22 h and dry at 60 °C for 1.5 h to make a radiation-proof coating fabric with a surface density of 2.5 kg / m 2 . The remaining steps are the same as those in Example 2.

[0051] Comparative Example 2:

[0052] The difference between a radiation-proof fabric of Comparative Example 2 and its preparation method and those of Example 2 lies in that step (1) is not carried out, and step (2) is modified as follows: Bismuth powder and absolute ethanol are mixed evenly at a mass ratio of 1:16, acetic acid is added to adjust the pH value to 5.5, ultrasonic dispersion is carried out for 30 min, shaking is carried out at 75 °C and 200 r / min for 1.5 h, and after cooling to room temperature, a bismuth powder suspension is prepared; the bismuth powder suspension, (3-chloropropyl)trimethoxysilane and deionized water are mixed evenly at a mass ratio of 1:0.2:1, stirring is carried out at 20 °C and 400 r / min for 2.5 h, centrifugal separation is carried out, and washing is carried out 4 times with absolute ethanol, and vacuum drying is carried out at 65 °C to obtain modified bismuth powder. The remaining steps are the same as those of Example 2.

[0053] Comparative Example 3:

[0054] The difference between the preparation method of a radiation-proof fabric of Comparative Example 3 and that of Example 2 lies in the difference in step (3). Step (3) is modified as follows: Isophorone diisocyanate, 1,4-butenediol and dibutyltin dilaurate are mixed evenly at a mass ratio of 1:1:0.04, and stirring is carried out at 85 °C and 400 r / min for 3 h to obtain polyurethane. The remaining steps are the same as those of Example 2.

[0055] Comparative Example 4:

[0056] The difference between the preparation method of a radiation-proof fabric of Comparative Example 4 and that of Example 2 lies in the difference in step (4). Step (4) is modified as follows: By mass, 12.5 parts of modified bismuth powder, 29 parts of N,N-dimethylformamide and 45 parts of polyurethane are weighed. The modified bismuth powder and dimethylformamide are mixed evenly, ultrasonic dispersion is carried out for 30 min, then polyurethane is added, and stirring is carried out at room temperature and 700 r / min for 6 min to obtain a polyurethane coating, which is coated on the outer surface of a polyester base fabric with a linear density of 1.6 dtex and a grammage of 135 g / m 2 and a reaction is carried out at 80 °C for 22 h and drying is carried out at 60 °C for 1.5 h to prepare a radiation-proof coated fabric with a surface density of 2.5 kg / m 2 . The remaining steps are the same as those of Example 2.

[0057] Test Example 1

[0058] Testing of radiation-proof performance

[0059] Testing method: Referring to GBZ / T147—2002 Determination of Attenuation Performance of X-ray Protection Materials, a standard device for X-ray air kerma (protection level) is used to carry out radiation-proof testing on the coated surface of the prepared coated fabric, and the measurement range is 1.0×10 -5 -1.0 Gy / h. The results are shown in Table 1.

[0060] Table 1

[0061] Protection efficiency / % Protection efficiency / % Example 1 76.5 Comparative Example 1 10.2 Example 2 75.4 Comparative Example 2 69.5 Example 3 76.9 Comparative Example 3 74.8 Comparative Example 4 76.3

[0062] From the comparison of the experimental data of Examples 1-3 and Comparative Examples 1-4 in Table 1, it can be found that a radiation-proof fabric prepared by the present invention has good radiation-proof performance.

[0063] By comparison, the protection efficiency of Examples 1-3 is higher than that of Comparative Example 1, indicating that bismuth, as a "green metal" with soft texture and brittle nature, has good protection ability against X-rays. Its high atomic number enables it to have a strong scattering effect on electromagnetic waves. After modification, a special chemical structure is formed on its surface. On the one hand, it expands the interaction area with electromagnetic waves, causing more electromagnetic waves to scatter on the material surface; on the other hand, the functional groups generated by modification and the change in electron cloud distribution enhance the absorption and conversion ability of electromagnetic waves, converting electromagnetic energy into heat energy and dissipating it, thus significantly improving the radiation-proof performance of the fabric. The silane coupling agent (3-chloropropyl) trimethoxysilane is used to modify the surface of bismuth powder, effectively solving the problem of powder self-agglomeration effect, improving the compatibility of bismuth powder and polyurethane. The modified bismuth powder is evenly dispersed in the polyurethane coating, tightly combined with the matrix, avoiding the problems of easy shedding and oxidation of traditional metal materials, ensuring the long-term effectiveness of the radiation-proof effect, and endowing a radiation-proof fabric with excellent radiation-proof performance.

[0064] Test Example 2

[0065] Test of anti-photoaging performance

[0066] Test method: Refer to the national standard GB / T 16422.3-2022 for the anti-oxidation performance test; under the condition of 70 °C, the coated surface of the prepared coated fabric is irradiated with ultraviolet light, the irradiation intensity is 0.76 W / (m 2 ·nm), the power of the ultraviolet lamp is 40 W, the irradiation time is 7 days. After the irradiation, the tensile strength is tested and the tensile strength retention rate is calculated; the tensile strength is tested using the shear strip method according to the standard ASTM D5035-1995(2003); the results are shown in Table 2.

[0067] Table 2

[0068]

[0069] From the comparison of the experimental data of Examples 1-3 and Comparative Examples 1-4 in Table 2, it can be found that a radiation-proof fabric prepared by the present invention has good anti-photoaging performance.

[0070] By comparison, the tensile strength retention rates of Examples 1-3 are higher than that of Comparative Example 2, indicating that using cyanuric chloride and (2,2,6,6-tetramethyl-piperidin-4-yl)-methylamine as starting materials, disubstitution is carried out to obtain Intermediate 1, and then a substitution reaction with resorcinol is carried out to construct an intramolecular hydrogen bond to obtain an anti-aging agent. Finally, etherification of the meta-hydroxy group in the structure with chloropropyl gives a propyl-modified functional additive. The structure contains piperidineamine groups and intramolecular hydrogen bonds in the light, making the prepared compound have high-efficient anti-photoaging function and endowing a radiation-proof fabric with excellent anti-photoaging performance.

[0071] Test Example 3

[0072] Test of flame retardant performance

[0073] Test method: According to GB / T5454 "Textiles - Burning performance - Determination of oxygen index", the limiting oxygen index of the coated fabrics prepared in the examples and comparative examples was tested with an oxygen index instrument. The results are shown in Table 3.

[0074] Table 3

[0075]

[0076] From the comparison of the experimental data of Examples 1-3 and Comparative Examples 1-4 in Table 3, it can be found that a radiation-proof fabric prepared by the present invention has good flame retardant performance.

[0077] By comparison, the limiting oxygen index of Examples 1-3 is greater than that of Comparative Example 3, indicating that a flame retardant monomer is prepared by reacting 4-aminophenylethanol and 4-(2-hydroxyethyl)benzaldehyde, and then reacting with isophorone diisocyanate and 1,4-butanediol to obtain a polyurethane. The phosphorus-containing group of the flame retardant monomer decomposes when heated to generate polyphosphoric acid, forming a dense heat-insulating layer on the fabric surface through dehydration and carbonization to isolate oxygen and combustible gases; at the same time, phosphorus-containing free radicals capture combustion active free radicals to interrupt the chain reaction, realizing double flame retardancy in the condensed phase and gas phase. The aromatic ring structure in the monomer enhances the strength of the carbonized layer with high thermal stability, and the polyhydroxy structure and phosphorus-containing compounds synergistically promote carbonization. The hydroxyl group of the flame retardant monomer polymerizes with the isocyanate group of isophorone diisocyanate to form intermolecular chemical cross-linking bonds, enhancing the degree of intermolecular cross-linking, realizing double optimization of flame retardancy and mechanical properties, and endowing a radiation-proof fabric with excellent flame retardant performance.

[0078] Test Example 4

[0079] Test of antibacterial performance

[0080] Test method: The oscillation method GB / T20944.3 was adopted. By comparing the number of colonies of Escherichia coli cultured in agar medium for 16 h, the antibacterial rate was calculated, so as to analyze the performance of the coated fabrics prepared by the examples and comparative examples for antibacterial preparation. The results are shown in Table 4.

[0081] Table 4

[0082] Bacteriostatic rate (%) Bacteriostatic rate (%) Example 1 99.83 Comparative Example 1 99.62 Example 2 99.85 Comparative Example 2 99.64 Example 3 99.79 Comparative Example 3 99.67 Comparative Example 4 81.24

[0083] From the comparison of the experimental data of Examples 1-3 and Comparative Examples 1-4 in Table 4, it can be found that a radiation-proof fabric prepared by the present invention has good antibacterial properties.

[0084] By comparison, the bacteriostatic rate of Examples 1-3 is greater than that of Comparative Example 4, indicating that an antibacterial crosslinking agent is prepared by reacting dimethylallylamine with 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane. The synergistic effect of the siloxane structure and amino group in the antibacterial crosslinking agent can destroy the cell membrane structure of bacteria and inhibit the growth of bacteria; it is firmly combined with polyurethane through a crosslinking reaction to form a durable antibacterial layer on the fabric surface, avoiding the migration and loss of antibacterial components, and endowing a radiation-proof fabric with excellent antibacterial properties.

[0085] The specific embodiments described above further elaborate on the purpose, technical solution and beneficial effects of the present invention. It should be understood that the above description is only the specific embodiments of the present invention and is not used to limit the protection scope of the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A radiation-proof fabric, characterized in that, The radiation protection fabric is prepared by mixing modified bismuth powder, N-N-dimethylformamide, polyurethane, antibacterial crosslinking agent, and benzoyl peroxide to obtain a polyurethane coating, which is coated on the outer surface of a polyester base fabric and dried to obtain a radiation protection coated fabric; The modified bismuth powder is prepared by pre-modifying bismuth powder with (3-chloropropyl) trimethoxysilane and then reacting with an anti-aging agent; The polyurethane is prepared by reacting 4-aminophenylethanol and 4-(2-hydroxyethyl) benzaldehyde to obtain a flame retardant monomer, and then reacting with isophorone diisocyanate and 1,4-butenediol; The antibacterial crosslinking agent is prepared by reacting dimethylallylamine and 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane; 2. A preparation method of a radiation-proof fabric, characterized in that, The preparation method of the radiation protection fabric includes the following preparation steps: (1) Mix intermediate 1, anhydrous aluminum trichloride, and chlorobenzene evenly according to the mass ratio of 1:(0.4-0.6):(7-9), stir at 300-500 r / min for 25-35 min at 0-5 °C, add resorcinol with a mass 0.20-0.25 times that of intermediate 1, and react at 80-85 °C for 3-5 h to obtain an anti-aging agent; (2) Mix the anti-aging agent, sodium hydroxide, and N,N-dimethylformamide evenly according to the mass ratio of 1:(0.07-0.09):(9-11), stir at 400-500 r / min for 25-35 min at 48-52 °C, dropwise add a pre-modified bismuth powder mixture with a mass 0.6-0.8 times that of the anti-aging agent evenly within 2-3 min, raise the temperature to 70-90 °C, react for 6-7 h, and cool and filter by suction to obtain modified bismuth powder; (3) Mix isophorone diisocyanate, flame retardant monomer, 1,4-butenediol, and dibutyltin dilaurate evenly according to the mass ratio of 1:(0.3-0.7):(0.8-1.2):(0.03-0.05), stir at 300-500 r / min for 2-4 h at 83-87 °C to obtain polyurethane; (4) By mass parts, weigh 10 - 15 parts of modified bismuth powder, 28 - 30 parts of N,N-dimethylformamide, 40 - 50 parts of polyurethane, 2 - 3 parts of antibacterial crosslinking agent, and 0.8 - 1.2 parts of benzoyl peroxide; mix the modified bismuth powder and dimethylformamide evenly, ultrasonically disperse for 25 - 35 min, then add polyurethane, antibacterial crosslinking agent, and benzoyl peroxide, and stir at 600 - 800 r / min for 5 - 7 min at room temperature to obtain a polyurethane coating. Coat it on the outer surface of the polyester base fabric, react at 60 - 100 °C for 20 - 24 h, and then dry at 50 - 70 °C for 1 - 2 h to make a radiation-proof coating fabric with a surface density of 2 - 3 kg / m 2 2.

3. The preparation method of a radiation-proof fabric according to claim 2, characterized in that, Intermediate 1 in step (1) is prepared by mixing cyanuric chloride and (2,2,6,6-tetramethyl-piperidin-4-yl)-methylamine evenly according to the molar ratio of 1:2, adding toluene with a mass 10-12 times that of cyanuric chloride, stirring and reacting at 300-400 r / min at 0-5 °C for 2-3 h, adding a 28 wt% sodium hydroxide aqueous solution with a mass 1.4-1.6 times that of cyanuric chloride, raising the temperature to 60-80 °C and reacting for 12-16 h, and drying in vacuum at 50-60 °C to obtain intermediate 1.

4. The preparation method of a radiation-proof fabric according to claim 2, characterized in that, The pre-modified bismuth powder in step (2) is prepared by mixing a bismuth powder suspension, (3-chloropropyl) trimethoxysilane, and deionized water evenly according to the mass ratio of 1:(0.1-0.3):(0.5-1.5), stirring at 300-500 r / min at 10-30 °C for 2-3 h, centrifuging, washing 3-5 times with absolute ethanol, and drying in vacuum at 60-70 °C to obtain pre-modified bismuth powder.

5. The preparation method of a radiation-proof fabric according to claim 4, characterized in that, The bismuth powder suspension is prepared by mixing bismuth powder and absolute ethanol in a mass ratio of 1:(13 - 19), adding acetic acid to adjust the pH value to 5 - 6, ultrasonically dispersing for 25 - 35 min, shaking at 70 - 80 °C and 150 - 250 r / min for 1 - 2 h, and then cooling to room temperature.

6. The preparation method of a radiation-proof fabric according to claim 2, wherein, The pre-modified bismuth powder mixture in step (2) is prepared by mixing pre-modified bismuth powder and N,N-dimethylformamide evenly at room temperature in a mass ratio of 1:

2.

7. The preparation method of a radiation-proof fabric according to claim 2, wherein, The flame retardant monomer in step (3) is prepared by mixing 4-aminophenethyl alcohol and 4-(2-hydroxyethyl)benzaldehyde evenly in a molar ratio of 1:1, adding methanol which is 70 - 90 times the mass of 4-aminophenethyl alcohol, stirring at 40 - 60 °C and 300 - 500 r / min for 4 - 6 h under a nitrogen atmosphere, respectively dropping diethyl phosphite which is 1.6 - 1.8 times the mass of 4-aminophenethyl alcohol and methanol which is 15 - 25 times the mass of 4-aminophenethyl alcohol within 20 - 30 min, reacting at 45 - 55 °C for 10 - 12 h, and drying at 70 - 90 °C.

8. The preparation method of a radiation-proof fabric according to claim 2, characterized in that, The antibacterial crosslinking agent in step (4) is prepared by mixing dimethylallylamine, 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane, sodium iodide and toluene evenly in a mass ratio of 1∶(1.1 - 1.3)∶(0.01 - 0.03):(4 - 8), stirring and reacting at 70 - 80 °C and 400 - 500 r / min for 24 - 38 h under a nitrogen atmosphere, and vacuum drying at 60 - 70 °C for 4 - 6 h.

9. The preparation method of a radiation-proof fabric according to claim 2, characterized in that, The polyester base fabric described in step (4) is woven with a plain weave using polyester filaments with a linear density of 0.8 - 2.2 dtex, and has a gram weight of 120 - 150 g / m 2 .

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