Antibacterial warm-keeping fabric and preparation method thereof

Abstract

The invention discloses a preparation method of an antibacterial warm-keeping fabric, and relates to the technical field of textiles. When the antibacterial warm-keeping fabric is prepared, firstly, (E)-butyl-2-ene-1, 4-diamine, glyoxal, formaldehyde and butyric acid are used as raw materials to synthesize a polyimidazolium salt antibacterial agent, then the polyimidazolium salt antibacterial agent is copolymerized with polytetrahydrofuran ether glycol and diphenylmethane diisocyanate to prepare an antibacterial polyurethane spinning solution, and the antibacterial fabric is obtained through wet spinning and weaving. The preparation method comprises the following steps: reacting L-cysteine with 3-amino propyl triethoxy silane to prepare cysteamine acyl propyl triethoxy silane, reacting with formaldehyde and phosphorous acid to obtain flame-retardant modified silane, and further preparing a silicon dioxide solution from the flame-retardant modified silane and sol-gel such as methyltrimethoxysilane; finally, the antibacterial fabric is treated with a benzophenone solution and then soaked with a silicon dioxide solution, and the antibacterial thermal fabric is prepared through ultraviolet irradiation, standing gelation, aging and hexane washing. The prepared fabric has excellent antibacterial property, heat retention property and flame retardant property.

Description

Technical Field

[0001] This invention relates to the field of textile technology, specifically to an antibacterial and warm fabric and its preparation method. Background Technology

[0002] Polyether ester elastic fibers are high-performance polymers with excellent overall properties. Their molecular chains combine the flexibility of the polyether segment with the toughness of the polyester segment, resulting in superior elastic recovery, creep resistance, and mechanical strength. They are widely used in high-end textiles and apparel, medical pressure products, sports protective equipment, and industrial yarns. However, traditional polyether ester fibers lack effective antibacterial properties, easily becoming carriers for microbial growth during use. This can lead to problems such as odor, discoloration, and even skin allergies, severely impacting their application value and development potential. Furthermore, adding small-molecule antibacterial agents through finishing processes suffers from drawbacks such as easy dissolution and poor durability, while drastic chemical modification may damage the fiber's original elastic structure.

[0003] In recent years, with the rapid growth in demand for the integration of comfort and functionality in industries such as healthcare and smart wearables, the market's call for durable antibacterial elastic textile materials has been increasing. The lack of antibacterial function in traditional polyether ester fibers under complex usage environments not only shortens product lifespan but also poses potential environmental pressure due to their non-biodegradable nature. Therefore, constructing an efficient and durable antibacterial functional system while maintaining the high elasticity of the fiber itself through molecular structure design and surface engineering technology has become an important research direction for enhancing product added value and promoting green industrial upgrading. Summary of the Invention

[0004] The purpose of this invention is to provide an antibacterial and thermal insulation fabric, its preparation method, and its application, so as to solve the problems existing in the prior art.

[0005] To solve the above-mentioned technical problems, the present invention provides the following technical solution: An antibacterial and thermal fabric is prepared by treating an antibacterial fabric with benzophenone solution, impregnating it with silica solution, and then subjecting it to ultraviolet light irradiation, static gelation, aging, and hexane washing.

[0006] As an optimization, the antibacterial fabric is made by copolymerizing polytetrahydrofuran ether diol, diphenylmethane diisocyanate and polyimidazolium salt antibacterial agent, and then wet spinning and weaving it.

[0007] As an optimization, the polyimide salt antibacterial agent is prepared by reacting (E)-but-2-ene-1,4-diamine, glyoxal, formaldehyde and butyric acid.

[0008] As an optimization, the silica solution is prepared by reacting L-cysteine ​​with 3-aminopropyltriethoxysilane to obtain cysteamine propyltriethoxysilane, then reacting it with formaldehyde and phosphorous acid to obtain flame-retardant modified silane, and further preparing it with methyltrimethoxysilane sol-gel.

[0009] A method for preparing an antibacterial and thermal fabric includes the following preparation steps: (1) Weigh (E)-but-2-ene-1,4-diamine, glyoxal solution, formaldehyde solution, butyric acid, and deionized water in a mass ratio of 1:(0.95~1.1):(0.5~0.55):(1.1~1.4):(0.5~1); mix (E)-but-2-ene-1,4-diamine, butyric acid, and deionized water, stir at 0~5℃ and 200~400r / min for 20~30min, add glyoxal solution and formaldehyde solution, continue stirring for 10~20min, adjust pH to 6.5~7.5 with 1mol / L sodium hydroxide, raise temperature to 70~80℃, continue stirring for 12~24h, dialyze, and freeze dry to obtain polyimidazolium salt antibacterial agent; in a mass ratio of 1:0 .27:0.04:(2.5~3) Weigh out polytetrahydrofuran ether diol, diphenylmethane diisocyanate, polyimidazolium salt antibacterial agent and N,N-dimethylacetamide; stir polytetrahydrofuran ether diol under vacuum at 90~110℃ and 200~400r / min for 2~3h, add diphenylmethane diisocyanate and continue stirring for 1~3h, add N,N-dimethylacetamide and continue stirring for 10~20min, add polyimidazolium salt antibacterial agent at 700~800r / min and stir for 20~40min to obtain antibacterial polyurethane spinning solution; wet spin the antibacterial polyurethane spinning solution to obtain antibacterial spandex fiber; weave the antibacterial spandex fiber into antibacterial fabric on a multi-functional knitting flat knitting machine.

[0010] (2) Weigh L-cysteine, N-hydroxysuccinimide, EDC·HCl, 3-aminopropyltriethoxysilane, 2,6-dimethylpyridine, and anhydrous DMF in a mass ratio of 1:(1~1.1):(1.7~1.85):(1.95~2.1):(0.7~0.9):(160~180); mix L-cysteine, N-hydroxysuccinimide, EDC·HCl, and anhydrous DMF, and stir at 0~5℃ and 200~400r / min for 20~30min. Add 2,6-dimethylpyridine and continue stirring for 5~10min. Add 3-aminopropyltriethoxysilane dropwise, raise the temperature to 25~30℃, and continue stirring for 12~16h. Use ice-cold ether. Cysteine-propyltriethoxysilane was obtained by precipitating and washing with cold diethyl ether. Cysteine-propyltriethoxysilane, formaldehyde, and phosphorous acid were mixed uniformly in a mass ratio of 1:(0.5~0.55):(0.5~0.55) and stirred at 100~120℃ and 200~400 r / min for 2~4 h to obtain flame-retardant modified silane. Methyltrimethoxysilane, flame-retardant modified silane, methanol, and ammonium hydroxide solution were weighed in a mass ratio of 1:(0.03~0.07):(2~3):(0.3~0.5). Methyltrimethoxysilane, flame-retardant modified silane, and methanol were mixed and stirred at 25~30℃ and 50~150 r / min for 20~40 min. Ammonium hydroxide solution was added to obtain a silica solution. (3) Immerse the antibacterial fabric in a 0.4~0.6mol / L benzophenone / acetone solution for 20~40min, take it out and dry it, then immerse it in a silica solution for 10~15min, take it out and irradiate it with ultraviolet light for 2~5min, let it stand for 12~24h, then place it in an oven at 90~110℃ for 24~48h, take it out and place it in hexane, stir it at 25~30℃ and 50~150r / min for 24~48h, and dry it to obtain the antibacterial and warm fabric.

[0011] As an optimization, the wet spinning process of the antibacterial polyurethane spinning solution in step (1) is as follows: the antibacterial polyurethane solution is defoamed and filtered, and extruded into deionized water at a speed of 0.35 mL / min through a porous spinneret to obtain nascent fibers; the nascent fibers are introduced into a 55℃ hot water bath for 3.5 times stretching, washed, oiled and then wound at a speed of 0.05 m / s to obtain antibacterial spandex fibers with a linear density of 22.2 dtex / 12f.

[0012] As an optimization, the surface density of the antibacterial fabric in step (1) is 165±10g / m², and the thickness is 0.45±0.05mm.

[0013] As an optimization, the flame-retardant modified silane reaction process in step (2) is as follows: .

[0014] Compared with the prior art, the beneficial effects achieved by the present invention are: In preparing the antibacterial and thermal fabric, this invention involves reacting (E)-but-2-ene-1,4-diamine, glyoxal, formaldehyde, and butyric acid to synthesize a polyimide salt antibacterial agent. This agent is then copolymerized with polytetrahydrofuran ether diol and diphenylmethane diisocyanate to obtain an antibacterial polyurethane spinning solution. The solution is then wet-spun and woven to obtain the antibacterial fabric. L-cysteine ​​is reacted with 3-aminopropyltriethoxysilane to obtain cysteamide propyltriethoxysilane, which is then reacted with formaldehyde and phosphorous acid to obtain a flame-retardant modified silane. This silane is further reacted with methyltrimethoxysilane and other solvent-gel agents to prepare a silica solution. The antibacterial fabric is treated with benzophenone solution and then impregnated with the silica solution. The fabric is then subjected to ultraviolet light irradiation, static gelation, aging, and hexane washing to obtain the antibacterial and thermal fabric.

[0015] First, antibacterial spandex fibers were prepared by blending polyimide salt antibacterial agents with polyurethane spinning solution, giving the fabric durable antibacterial properties and good elasticity and warmth retention. The carbon-carbon double bonds retained in the polyimide salt molecule provide reaction sites for a strong bond with the subsequent functional coating, while the butyrate structure creates conditions for ion exchange reactions. During the functional finishing process, after initiation with benzophenone, the thiol groups in the silica aerogel layer and the double bonds of the polyimide salt in the antibacterial fiber form a covalent bond under ultraviolet light. This strong interaction creates a strong interfacial bond between the functional coating and the fiber matrix, significantly improving the coating's durability and the fabric's mechanical properties.

[0016] Secondly, the phosphate groups in the prepared silica aerogel layer undergo an ion exchange reaction with the butyrate groups in the polyimide salt to generate polyimide phosphate with better thermal stability. This electrostatic ion bonding not only further enhances the interfacial bonding force, but the phosphate groups also act as a highly efficient acid source, promoting the formation of a dense carbon layer on the fiber surface when heated, significantly enhancing the flame retardant properties of the silica aerogel layer. The synergistic effect of the dual bonding mechanism of covalent and ionic bonds ensures the durability of the flame retardant and heat insulation functions, improves the mechanical strength of the fabric, and enhances the antibacterial efficiency, jointly endowing the fabric with excellent antibacterial and heat-insulating properties and flame retardant effects. Detailed Implementation

[0017] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0018] To more clearly illustrate the method provided by the present invention, the following embodiments will be described in detail.

[0019] Example 1: A method for preparing an antibacterial and thermal fabric, mainly including the following preparation steps: (1) Weigh (E)-but-2-ene-1,4-diamine, glyoxal solution, formaldehyde solution, butyric acid, and deionized water in a mass ratio of 1:0.95:0.5:1.1:0.5; mix (E)-but-2-ene-1,4-diamine, butyric acid, and deionized water, stir at 0℃ and 200r / min for 20min, add glyoxal solution and formaldehyde solution, continue stirring for 10min, adjust pH to 6.5 with 1mol / L sodium hydroxide, raise temperature to 70℃, continue stirring for 12h, dialyze, and freeze dry to obtain polyimidazolium salt antibacterial agent; in a mass ratio of 1:0.27:0.04:2 5. Weigh out polytetrahydrofuran ether diol, diphenylmethane diisocyanate, polyimide salt antibacterial agent, and N,N-dimethylacetamide; stir the polytetrahydrofuran ether diol at 90℃ and 200r / min for 2h under vacuum, add diphenylmethane diisocyanate and continue stirring for 1h, add N,N-dimethylacetamide and continue stirring for 10min, add polyimide salt antibacterial agent at 700r / min and stir for 20min to obtain antibacterial polyurethane spinning solution; wet spin the antibacterial polyurethane spinning solution to obtain antibacterial spandex fiber; weave the antibacterial spandex fiber into antibacterial fabric on a multi-functional knitting flat knitting machine.

[0020] (2) Weigh L-cysteine, N-hydroxysuccinimide, EDC·HCl, 3-aminopropyltriethoxysilane, 2,6-dimethylpyridine, and anhydrous DMF in a mass ratio of 1:1:1.7:1.95:0.7:160; mix L-cysteine, N-hydroxysuccinimide, EDC·HCl, and anhydrous DMF, stir at 0℃ and 200r / min for 20min, add 2,6-dimethylpyridine, continue stirring for 5min, add 3-aminopropyltriethoxysilane dropwise, heat to 25℃ and continue stirring for 12h, and use ice-ethanol. Cysteinepropyltriethoxysilane was prepared by ether precipitation and washing with cold diethyl ether. Cysteinepropyltriethoxysilane, formaldehyde, and phosphorous acid were mixed uniformly in a mass ratio of 1:0.5:0.5 and stirred at 100℃ and 200 r / min for 2 h to obtain a flame-retardant modified silane. Methyltrimethoxysilane, flame-retardant modified silane, methanol, and ammonium hydroxide solution were weighed in a mass ratio of 1:0.05:2:0.3. Methyltrimethoxysilane, flame-retardant modified silane, and methanol were mixed and stirred at 25℃ and 50 r / min for 20 min. Ammonium hydroxide solution was then added to obtain a silica solution. (3) The antibacterial fabric was immersed in 0.4mol / L benzophenone / acetone solution for 20min, then removed and dried. After immersion in silica solution for 10min, it was removed and irradiated with ultraviolet light for 2min. After standing for 12h, it was placed in a 90℃ oven for 24h. After removal, it was placed in hexane and stirred at 25℃ and 50r / min for 24h. After drying, the antibacterial and warm fabric was obtained.

[0021] Example 2: A method for preparing an antibacterial and thermal fabric, mainly including the following preparation steps: (1) Weigh (E)-but-2-ene-1,4-diamine, glyoxal solution, formaldehyde solution, butyric acid, and deionized water in a mass ratio of 1:1:0.53:1.3:0.8; mix (E)-but-2-ene-1,4-diamine, butyric acid, and deionized water, stir at 3℃ and 300r / min for 25min, add glyoxal solution and formaldehyde solution, continue stirring for 15min, adjust pH to 7 with 1mol / L sodium hydroxide, raise temperature to 75℃, continue stirring for 18h, dialyze, and freeze dry to obtain polyimide salt antibacterial agent; weigh in a mass ratio of 1:0.27:0.04:2.7 Polytetrahydrofuran ether diol, diphenylmethane diisocyanate, polyimide salt antibacterial agent, and N,N-dimethylacetamide were prepared. The polytetrahydrofuran ether diol was stirred at 100°C and 300 rpm for 2.5 h under vacuum. Diphenylmethane diisocyanate was added and stirring continued for 2 h. N,N-dimethylacetamide was added and stirring continued for 15 min. Polyimide salt antibacterial agent was added at 750 rpm and stirring for 30 min to obtain an antibacterial polyurethane spinning solution. The antibacterial polyurethane spinning solution was wet-spun to obtain antibacterial spandex fiber. The antibacterial spandex fiber was woven into an antibacterial fabric on a multi-functional flat knitting machine.

[0022] (2) Weigh L-cysteine, N-hydroxysuccinimide, EDC·HCl, 3-aminopropyltriethoxysilane, 2,6-dimethylpyridine, and anhydrous DMF in a mass ratio of 1:1.05:1.8:2.05:0.8:170; mix L-cysteine, N-hydroxysuccinimide, EDC·HCl, and anhydrous DMF, stir at 3℃ and 300r / min for 25min, add 2,6-dimethylpyridine, continue stirring for 7min, add 3-aminopropyltriethoxysilane dropwise, heat to 27℃ and continue stirring for 14h, and use ice-cold ether. Cysteine-propyltriethoxysilane was obtained by precipitating and washing with cold diethyl ether. Cysteine-propyltriethoxysilane, formaldehyde, and phosphorous acid were mixed uniformly in a mass ratio of 1:0.52:0.53 and stirred at 110℃ and 300 r / min for 3 h to obtain a flame-retardant modified silane. Methyltrimethoxysilane, flame-retardant modified silane, methanol, and ammonium hydroxide solution were weighed in a mass ratio of 1:0.05:2.5:0.4. Methyltrimethoxysilane, flame-retardant modified silane, and methanol were mixed and stirred at 27℃ and 100 r / min for 30 min. Ammonium hydroxide solution was then added to obtain a silica solution. (3) The antibacterial fabric was immersed in 0.5mol / L benzophenone / acetone solution for 30min, then removed and dried. After immersion in silica solution for 12min, it was removed and irradiated with ultraviolet light for 4min. After standing for 18h, it was placed in a 100℃ oven for 36h. After removal, it was placed in hexane and stirred at 27℃ and 100r / min for 36h. After drying, the antibacterial and warm fabric was obtained.

[0023] Example 3: A method for preparing an antibacterial and thermal fabric, mainly including the following preparation steps: (1) Weigh (E)-but-2-ene-1,4-diamine, glyoxal solution, formaldehyde solution, butyric acid, and deionized water in a mass ratio of 1:1.1:0.55:1.4:1; mix (E)-but-2-ene-1,4-diamine, butyric acid, and deionized water, stir at 5℃ and 400r / min for 30min, add glyoxal solution and formaldehyde solution, continue stirring for 20min, adjust pH to 7.5 with 1mol / L sodium hydroxide, raise temperature to 80℃, continue stirring for 24h, dialyze, and freeze dry to obtain polyimidazolium salt antibacterial agent; in a mass ratio of 1:0.27:0.04:3 Weigh out polytetrahydrofuran ether diol, diphenylmethane diisocyanate, polyimide salt antibacterial agent, and N,N-dimethylacetamide; stir the polytetrahydrofuran ether diol at 110℃ and 400r / min for 3h under vacuum, add diphenylmethane diisocyanate and continue stirring for 3h, add N,N-dimethylacetamide and continue stirring for 20min, add polyimide salt antibacterial agent at 800r / min and stir for 40min to obtain an antibacterial polyurethane spinning solution; wet spin the antibacterial polyurethane spinning solution to obtain antibacterial spandex fiber; weave the antibacterial spandex fiber into antibacterial fabric on a multi-functional knitting flat knitting machine.

[0024] (2) Weigh L-cysteine, N-hydroxysuccinimide, EDC·HCl, 3-aminopropyltriethoxysilane, 2,6-dimethylpyridine, and anhydrous DMF in a mass ratio of 1:1.1:1.85:2.1:0.9:180; mix L-cysteine, N-hydroxysuccinimide, EDC·HCl, and anhydrous DMF, stir at 5℃ and 400r / min for 30min, add 2,6-dimethylpyridine, continue stirring for 10min, add 3-aminopropyltriethoxysilane dropwise, heat to 30℃ and continue stirring for 16h, and use ice-ethanol. Cysteine-propyltriethoxysilane was prepared by ether precipitation and washing with cold diethyl ether. Cysteine-propyltriethoxysilane, formaldehyde, and phosphorous acid were mixed uniformly in a mass ratio of 1:0.55:0.55 and stirred at 120℃ and 400 r / min for 4 h to obtain a flame-retardant modified silane. Methyltrimethoxysilane, flame-retardant modified silane, methanol, and ammonium hydroxide solution were weighed in a mass ratio of 1:0.05:3:0.5. Methyltrimethoxysilane, flame-retardant modified silane, and methanol were mixed and stirred at 30℃ and 150 r / min for 40 min. Ammonium hydroxide solution was then added to obtain a silica solution. (3) The antibacterial fabric was immersed in 0.6 mol / L benzophenone / acetone solution for 40 min, then removed and dried. After immersing in silica solution for 15 min, it was removed and irradiated with ultraviolet light for 5 min. After standing for 24 h, it was placed in an oven at 110 ℃ for 48 h. After removing it, it was placed in hexane and stirred at 30 ℃ and 150 r / min for 48 h. After drying, the antibacterial and warm fabric was obtained.

[0025] Comparative Example 1: The difference from Example 2 is only in step (2), where “weigh methyltrimethoxysilane, flame-retardant modified silane, methanol and ammonium hydroxide solution in a mass ratio of 1:0.05:3:0.5” is changed to “weigh methyltrimethoxysilane, flame-retardant modified silane, methanol and ammonium hydroxide solution in a mass ratio of 1:0.03:3:0.5”.

[0026] Comparative Example 2: The only difference from Example 2 is step (2), where “weigh methyltrimethoxysilane, flame-retardant modified silane, methanol and ammonium hydroxide solution in a mass ratio of 1:0.05:3:0.5” is changed to “weigh methyltrimethoxysilane, flame-retardant modified silane, methanol and ammonium hydroxide solution in a mass ratio of 1:0.04:3:0.5”.

[0027] Comparative Example 3: The only difference from Example 2 is the step (2), where “weigh methyltrimethoxysilane, flame-retardant modified silane, methanol and ammonium hydroxide solution in a mass ratio of 1:0.05:3:0.5” is changed to “weigh methyltrimethoxysilane, flame-retardant modified silane, methanol and ammonium hydroxide solution in a mass ratio of 1:0.06:3:0.5”.

[0028] Comparative Example 4: The only difference from Example 2 is the step (2), where “weigh methyltrimethoxysilane, flame-retardant modified silane, methanol and ammonium hydroxide solution in a mass ratio of 1:0.05:3:0.5” is changed to “weigh methyltrimethoxysilane, flame-retardant modified silane, methanol and ammonium hydroxide solution in a mass ratio of 1:0.07:3:0.5”.

[0029] Comparative Example 5: A method for preparing an antibacterial and thermal fabric mainly includes the following preparation steps: (1) Weigh ethylenediamine, glyoxal solution, formaldehyde solution, butyric acid and deionized water in a mass ratio of 1:1:0.53:1.3:0.8; mix ethylenediamine, butyric acid and deionized water, stir at 300 r / min for 25 min at 3℃, add glyoxal solution and formaldehyde solution, continue stirring for 15 min, adjust pH to 7 with 1 mol / L sodium hydroxide, raise temperature to 75℃, continue stirring for 18 h, dialyze and freeze dry to obtain polyimide salt antibacterial agent; weigh polytetrahydrofuran ether diol and diphenyl ether diol in a mass ratio of 1:0.27:0.04:2.7. Methane diisocyanate, polyimide salt antibacterial agent, and N,N-dimethylacetamide were used to prepare an antibacterial polyurethane spinning solution. Polytetrahydrofuran ether diol was stirred at 100°C and 300 rpm for 2.5 h under vacuum. Diphenylmethane diisocyanate was added and stirring continued for 2 h. N,N-dimethylacetamide was added and stirring continued for 15 min. Polyimide salt antibacterial agent was added at 750 rpm and stirring for 30 min to obtain the antibacterial polyurethane spinning solution. The antibacterial polyurethane spinning solution was wet-spun to obtain antibacterial spandex fiber. The antibacterial spandex fiber was then woven into an antibacterial fabric on a multi-functional flat knitting machine.

[0030] (2) Weigh L-cysteine, N-hydroxysuccinimide, EDC·HCl, 3-aminopropyltriethoxysilane, 2,6-dimethylpyridine, and anhydrous DMF in a mass ratio of 1:1.05:1.8:2.05:0.8:170; mix L-cysteine, N-hydroxysuccinimide, EDC·HCl, and anhydrous DMF, stir at 3℃ and 300r / min for 25min, add 2,6-dimethylpyridine, continue stirring for 7min, add 3-aminopropyltriethoxysilane dropwise, heat to 27℃ and continue stirring for 14h, and use ice-cold ether. Cysteine-propyltriethoxysilane was obtained by precipitating and washing with cold diethyl ether. Cysteine-propyltriethoxysilane, formaldehyde, and phosphorous acid were mixed uniformly in a mass ratio of 1:0.52:0.53 and stirred at 110℃ and 300 r / min for 3 h to obtain a flame-retardant modified silane. Methyltrimethoxysilane, flame-retardant modified silane, methanol, and ammonium hydroxide solution were weighed in a mass ratio of 1:0.05:2.5:0.4. Methyltrimethoxysilane, flame-retardant modified silane, and methanol were mixed and stirred at 27℃ and 100 r / min for 30 min. Ammonium hydroxide solution was then added to obtain a silica solution. (3) The antibacterial fabric was immersed in silica solution for 12 minutes and then taken out. After standing for 18 hours, it was placed in an oven at 100°C for 36 hours. After taking it out, it was placed in hexane and stirred at 27°C and 100 r / min for 36 hours. After drying, the antibacterial and warm fabric was obtained.

[0031] Comparative Example 6: A method for preparing an antibacterial and thermal fabric mainly includes the following preparation steps: (1) Weigh (E)-but-2-ene-1,4-diamine, glyoxal solution, formaldehyde solution, butyric acid, and deionized water in a mass ratio of 1:1:0.53:1.3:0.8; mix (E)-but-2-ene-1,4-diamine, butyric acid, and deionized water, stir at 3℃ and 300r / min for 25min, add glyoxal solution and formaldehyde solution, continue stirring for 15min, adjust pH to 7 with 1mol / L sodium hydroxide, raise temperature to 75℃, continue stirring for 18h, dialyze, and freeze dry to obtain polyimide salt antibacterial agent; weigh in a mass ratio of 1:0.27:0.04:2.7 Polytetrahydrofuran ether diol, diphenylmethane diisocyanate, polyimide salt antibacterial agent, and N,N-dimethylacetamide were prepared. The polytetrahydrofuran ether diol was stirred at 100°C and 300 rpm for 2.5 h under vacuum. Diphenylmethane diisocyanate was added and stirring continued for 2 h. N,N-dimethylacetamide was added and stirring continued for 15 min. Polyimide salt antibacterial agent was added at 750 rpm and stirring for 30 min to obtain an antibacterial polyurethane spinning solution. The antibacterial polyurethane spinning solution was wet-spun to obtain antibacterial spandex fiber. The antibacterial spandex fiber was woven into an antibacterial fabric on a multi-functional flat knitting machine.

[0032] (2) Weigh L-cysteine, N-hydroxysuccinimide, EDC·HCl, 3-aminopropyltriethoxysilane, 2,6-dimethylpyridine, and anhydrous DMF in a mass ratio of 1:1.05:1.8:2.05:0.8:170; mix L-cysteine, N-hydroxysuccinimide, EDC·HCl, and anhydrous DMF, stir at 3℃ and 300r / min for 25min, add 2,6-dimethylpyridine, continue stirring for 7min, and dropwise add 3-aminopropyltriethoxysilane. Cysteine-propyltriethoxysilane was prepared by heating propyltriethoxysilane to 27°C and stirring for 14 hours, precipitating with ice-cold diethyl ether, and washing with cold diethyl ether. Methyltrimethoxysilane, cysteyltriethoxysilane, methanol, and ammonium hydroxide solution were weighed in a mass ratio of 1:0.05:2.5:0.4. Methyltrimethoxysilane, cysteyltriethoxysilane, and methanol were mixed and stirred at 27°C and 100 r / min for 30 min. Ammonium hydroxide solution was then added to prepare a silica solution. (3) The antibacterial fabric was immersed in 0.5mol / L benzophenone / acetone solution for 30min, then removed and dried. After immersion in silica solution for 12min, it was removed and irradiated with ultraviolet light for 4min. After standing for 18h, it was placed in a 100℃ oven for 36h. After removal, it was placed in hexane and stirred at 27℃ and 100r / min for 36h. After drying, the antibacterial and warm fabric was obtained.

[0033] Comparative Example 7: A method for preparing an antibacterial and thermal fabric mainly includes the following preparation steps: (1) Weigh (E)-but-2-ene-1,4-diamine, glyoxal solution, formaldehyde solution, butyric acid, and deionized water in a mass ratio of 1:1:0.53:1.3:0.8; mix (E)-but-2-ene-1,4-diamine, butyric acid, and deionized water, stir at 3℃ and 300r / min for 25min, add glyoxal solution and formaldehyde solution, continue stirring for 15min, adjust pH to 7 with 1mol / L sodium hydroxide, raise temperature to 75℃, continue stirring for 18h, dialyze, and freeze dry to obtain polyimide salt antibacterial agent; weigh in a mass ratio of 1:0.27:0.04:2.7 Polytetrahydrofuran ether diol, diphenylmethane diisocyanate, polyimide salt antibacterial agent, and N,N-dimethylacetamide were prepared. The polytetrahydrofuran ether diol was stirred at 100°C and 300 rpm for 2.5 h under vacuum. Diphenylmethane diisocyanate was added and stirring continued for 2 h. N,N-dimethylacetamide was added and stirring continued for 15 min. Polyimide salt antibacterial agent was added at 750 rpm and stirring for 30 min to obtain an antibacterial polyurethane spinning solution. The antibacterial polyurethane spinning solution was wet-spun to obtain antibacterial spandex fiber. The antibacterial spandex fiber was woven into an antibacterial fabric on a multi-functional flat knitting machine.

[0034] (2) Weigh methyltrimethoxysilane, methanol and ammonium hydroxide solution in a mass ratio of 1:2.5:0.4; mix methyltrimethoxysilane and methanol, stir at 27℃ and 100r / min for 30min, add ammonium hydroxide solution to obtain silicon dioxide solution; (3) The antibacterial fabric was immersed in silica solution for 12 minutes and then taken out. After standing for 18 hours, it was placed in an oven at 100°C for 36 hours. After taking it out, it was placed in hexane and stirred at 27°C and 100 r / min for 36 hours. After drying, the antibacterial and warm fabric was obtained.

[0035] Comparative Example 8: A method for preparing a thermal insulation fabric mainly includes the following preparation steps: (1) Weigh polytetrahydrofuran ether diol, diphenylmethane diisocyanate, and N,N-dimethylacetamide in a mass ratio of 1:0.27:2.7; stir polytetrahydrofuran ether diol at 100°C and 300r / min for 2.5h under vacuum, add diphenylmethane diisocyanate and continue stirring for 2h, add N,N-dimethylacetamide and continue stirring for 15min to obtain polyurethane spinning solution; spin the polyurethane spinning solution by wet spinning to obtain spandex fiber; weave spandex fabric on a multi-functional knitting flat knitting machine.

[0036] (2) Weigh L-cysteine, N-hydroxysuccinimide, EDC·HCl, 3-aminopropyltriethoxysilane, 2,6-dimethylpyridine, and anhydrous DMF in a mass ratio of 1:1.05:1.8:2.05:0.8:170; mix L-cysteine, N-hydroxysuccinimide, EDC·HCl, and anhydrous DMF, stir at 3℃ and 300r / min for 25min, add 2,6-dimethylpyridine, continue stirring for 7min, add 3-aminopropyltriethoxysilane dropwise, heat to 27℃ and continue stirring for 14h, and use ice-cold ether. Cysteine-propyltriethoxysilane was obtained by precipitating and washing with cold diethyl ether. Cysteine-propyltriethoxysilane, formaldehyde, and phosphorous acid were mixed uniformly in a mass ratio of 1:0.52:0.53 and stirred at 110℃ and 300 r / min for 3 h to obtain a flame-retardant modified silane. Methyltrimethoxysilane, flame-retardant modified silane, methanol, and ammonium hydroxide solution were weighed in a mass ratio of 1:0.05:2.5:0.4. Methyltrimethoxysilane, flame-retardant modified silane, and methanol were mixed and stirred at 27℃ and 100 r / min for 30 min. Ammonium hydroxide solution was then added to obtain a silica solution. (3) Immerse the spandex fabric in a 0.5 mol / L benzophenone / acetone solution for 30 min, take it out and dry it, then immerse it in a silica solution for 12 min, take it out and irradiate it with ultraviolet light for 4 min, let it stand for 18 h, then place it in a 100℃ oven for 36 h, take it out and place it in hexane, stir it at 27℃ and 100 r / min for 36 h, and dry it to obtain the thermal insulation fabric.

[0037] Experimental Example 1: Determination of the optimal addition amount of flame-retardant modified silane; Test method: Determined by thermal insulation performance. The thermal insulation performance of the antibacterial thermal insulation fabric was tested according to GB / T11048-1989 "Test Methods for Thermal Insulation Performance of Textiles". The antibacterial thermal insulation fabric was cut into 8×8cm squares, and the thermal conductivity was tested using a Fox200 thermal conductivity meter. The results are shown in Table 1.

[0038] Table 1: ; By comparing Example 2 with Comparative Examples 1-4, it can be found that the thermal conductivity of the fabric first decreases and then increases with the increase of the amount of flame-retardant modified silane added. This is because when the amount of flame-retardant modified silane added is small, the hydrophobic methyltrimethoxysilane hydrolysis and condensation in the system dominates, quickly forming a rigid network. However, the participation of flame-retardant modified silane containing cysteine ​​groups and phosphorus-based flame-retardant structures is insufficient. The resulting silica network has a high cross-linking density but a wide pore size distribution, which is not conducive to constructing an effective nanoscale porous thermal insulation structure. When the amount of flame-retardant modified silane added is too high, the excessive polar groups introduced into its molecules significantly enhance the hydrophilicity of the system, exacerbating the phase separation tendency in the sol-gel process. This leads to local aggregation of the gel network, a decrease in pore size uniformity, and the collapse of some nanoporous structures, resulting in an increase in the solid thermal conduction path. Therefore, selecting an amount of flame-retardant modified silane of 0.05% can enable the fabric to obtain the optimal thermal insulation performance.

[0039] Experimental Example 2: Tests were conducted on antibacterial properties, warmth retention, coating washability, and flame retardancy. Antibacterial performance test method: The antibacterial and thermal insulation fabrics obtained in each example and the fabrics of comparative examples 5 to 7 were tested for antibacterial effect according to GB / T20944.3-2008 "Evaluation of antibacterial properties of textiles - Part 3: Vibration method".

[0040] Thermal insulation performance test method: The thermal insulation performance of the antibacterial thermal insulation fabrics obtained in each example and the fabrics of comparative examples 5 to 7 were tested according to GB / T11048-1989 "Test Method for Thermal Insulation Performance of Textiles". The antibacterial thermal insulation fabrics were cut into 8×8cm squares and thermal conductivity was tested using a Fox200 thermal conductivity meter.

[0041] Washability test method: The antibacterial and thermal insulation fabrics obtained in each example and the fabrics of comparative examples 5-7 were washed for 60 minutes in a weak acid detergent with a concentration of 5 g / L. The thermal insulation performance of the antibacterial and thermal insulation fabrics was tested according to GB / T11048-1989 "Test Method for Thermal Insulation Performance of Textiles". The antibacterial and thermal insulation fabrics were cut into 8×8 cm squares and the thermal conductivity was tested using a Fox200 thermal conductivity meter.

[0042] Flame retardant performance test method: The antibacterial and thermal insulation fabrics obtained in each example and the fabrics of comparative examples 5 to 7 were tested for limiting oxygen index (LOI) according to GB / T5454-1997 "Textiles - Test for Burning Performance - Oxygen Index Method".

[0043] The results are shown in Table 2.

[0044] Table 2: ; A comparison of the experimental data from Examples 1-3 and Comparative Examples 5-8 in Table 2 reveals that the antibacterial and thermal fabric prepared by this invention has good antibacterial, thermal, washable, and flame-retardant properties.

[0045] By comparing Examples 1-3 and Comparative Example 5, it can be found that the preparation of polyimidazolium salt antibacterial agent using (E)-but-2-ene-1,4-diamine containing double bonds introduces reactive carbon-carbon double bonds into its molecular chain. Under ultraviolet light irradiation, these double bonds undergo efficient thiol-ene click chemical reactions with the mercapto groups of flame-retardant modified silanes in the silica coating, forming a strong covalent bond interface between the antibacterial fiber body and the surface silica coating, thereby significantly improving the fabric's long-lasting warmth retention performance.

[0046] By comparing Examples 1-3 and Comparative Example 6, it can be found that modifying cysteamide propyltriethoxysilane with phosphorous acid and formaldehyde successfully introduces a phosphorus-nitrogen synergistic flame-retardant structure into its molecule, significantly improving the flame-retardant performance of the fabric. At the same time, the phosphate groups in the flame-retardant modified silane undergo an ion exchange reaction with the butyrate group in the polyimide salt to generate polyimide phosphate with better thermal stability. This electrostatic ion bonding further enhances the interfacial bonding force, giving the fabric excellent washability and long-lasting warmth retention.

[0047] A comparison of Examples 1-3 and Comparative Example 7 reveals that the preparation of a silica aerogel coating by co-hydrolysis condensation of flame-retardant modified silane and methyltrimethoxysilane significantly improves the flame-retardant and wash-resistant properties of the fabric. This is because the phosphorus-nitrogen synergistic structure introduced in the flame-retardant modified silane can catalyze the char formation of the fiber matrix and promote the formation of an expanded char layer when heated, while methyltrimethoxysilane constructs a stable silicon network framework. The two work synergistically to enhance the flame-retardant effect in both the gas phase and the condensed phase. At the same time, the silica aerogel coating generates a synergistic enhancement effect through the electrostatic ion-electrostatic combination between the mercapto-olefin covalent network and the phosphate groups and polyimidazolium salt cations, enabling it to effectively resist mechanical friction and chemical erosion during washing, thereby ensuring the durability of the flame-retardant and heat-insulating functions.

[0048] By comparing Examples 1-3 and Comparative Example 8, it can be found that adding polyimide salt antibacterial agent during the preparation of spandex can effectively improve the antibacterial properties of the fabric.

[0049] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from its spirit or essential characteristics. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, all variations falling within the meaning and scope of equivalents of the claims are intended to be included within the present invention. No markings in the claims should be construed as limiting the scope of the claims.

Claims

1. An antibacterial and warm fabric, characterized in that, The antibacterial and warm fabric is made by treating antibacterial fabric with benzophenone solution, impregnating it with silica solution, and then subjecting it to ultraviolet light irradiation, static gelation, aging, and hexane washing.

2. The antibacterial and thermal fabric according to claim 1, characterized in that, The antibacterial fabric is made by copolymerizing polytetrahydrofuran ether diol, diphenylmethane diisocyanate and polyimide salt antibacterial agent, followed by wet spinning and weaving.

3. The antibacterial and thermal fabric according to claim 2, characterized in that, The polyimide salt antibacterial agent is prepared by reacting (E)-but-2-ene-1,4-diamine, glyoxal, formaldehyde and butyric acid.

4. The antibacterial and thermal fabric according to claim 1, characterized in that, The silica solution is prepared by reacting L-cysteine ​​with 3-aminopropyltriethoxysilane to obtain cysteamine propyltriethoxysilane, then reacting it with formaldehyde and phosphorous acid to obtain flame-retardant modified silane, and further preparing it with methyltrimethoxysilane sol-gel.

5. A method for preparing an antibacterial and thermally insulating fabric, characterized in that, The preparation steps include the following: (1) Weigh (E)-but-2-ene-1,4-diamine, glyoxal solution, formaldehyde solution, butyric acid, and deionized water in a mass ratio of 1:(0.95~1.1):(0.5~0.55):(1.1~1.4):(0.5~1); mix (E)-but-2-ene-1,4-diamine, butyric acid, and deionized water, stir at 0~5℃ and 200~400r / min for 20~30min, add glyoxal solution and formaldehyde solution, continue stirring for 10~20min, adjust pH to 6.5~7.5 with 1mol / L sodium hydroxide, raise temperature to 70~80℃, continue stirring for 12~24h, dialyze, and freeze dry to obtain polyimidazolium salt antibacterial agent; in a mass ratio of 1:0 .27:0.04:(2.5~3) Weigh out polytetrahydrofuran ether diol, diphenylmethane diisocyanate, polyimidazolium salt antibacterial agent, and N,N-dimethylacetamide; stir the polytetrahydrofuran ether diol under vacuum at 90~110℃ and 200~400r / min for 2~3h, add diphenylmethane diisocyanate and continue stirring for 1~3h, add N,N-dimethylacetamide and continue stirring for 10~20min, add polyimidazolium salt antibacterial agent at 700~800r / min and stir for 20~40min to obtain antibacterial polyurethane spinning solution; wet spin the antibacterial polyurethane spinning solution to obtain antibacterial spandex fiber; weave the antibacterial spandex fiber into antibacterial fabric on a multi-functional knitting flat knitting machine; (2) Weigh L-cysteine, N-hydroxysuccinimide, EDC·HCl, 3-aminopropyltriethoxysilane, 2,6-dimethylpyridine, and anhydrous DMF in a mass ratio of 1:(1~1.1):(1.7~1.85):(1.95~2.1):(0.7~0.9):(160~180); mix L-cysteine, N-hydroxysuccinimide, EDC·HCl, and anhydrous DMF, and stir at 0~5℃ and 200~400r / min for 20~30min. Add 2,6-dimethylpyridine and continue stirring for 5~10min. Add 3-aminopropyltriethoxysilane dropwise, raise the temperature to 25~30℃, and continue stirring for 12~16h. Use ice-cold ether. Cysteine-propyltriethoxysilane was obtained by precipitating and washing with cold diethyl ether. Cysteine-propyltriethoxysilane, formaldehyde, and phosphorous acid were mixed uniformly in a mass ratio of 1:(0.5~0.55):(0.5~0.55) and stirred at 100~120℃ and 200~400 r / min for 2~4 h to obtain flame-retardant modified silane. Methyltrimethoxysilane, flame-retardant modified silane, methanol, and ammonium hydroxide solution were weighed in a mass ratio of 1:(0.03~0.07):(2~3):(0.3~0.5). Methyltrimethoxysilane, flame-retardant modified silane, and methanol were mixed and stirred at 25~30℃ and 50~150 r / min for 20~40 min. Ammonium hydroxide solution was added to obtain a silica solution. (3) Immerse the antibacterial fabric in a 0.4~0.6mol / L benzophenone / acetone solution for 20~40min, take it out and dry it, then immerse it in a silica solution for 10~15min, take it out and irradiate it with ultraviolet light for 2~5min, let it stand for 12~24h, then place it in an oven at 90~110℃ for 24~48h, take it out and place it in hexane, stir it at 25~30℃ and 50~150r / min for 24~48h, and dry it to obtain the antibacterial and warm fabric.

6. The method for preparing an antibacterial and thermal fabric according to claim 5, characterized in that, The wet spinning process of the antibacterial polyurethane spinning solution in step (1) is as follows: the antibacterial polyurethane solution is defoamed and filtered, and extruded into deionized water at a speed of 0.35 mL / min through a porous spinneret to obtain nascent fibers; the nascent fibers are introduced into a 55℃ hot water bath for 3.5 times stretching, washed, oiled and then wound at a speed of 0.05 m / s to obtain antibacterial spandex fibers with a linear density of 22.2 dtex / 12f.

7. The method for preparing an antibacterial and thermal fabric according to claim 5, characterized in that, The surface density of the antibacterial fabric in step (1) is 165±10g / m², and the thickness is 0.45±0.05mm.

8. The method for preparing an antibacterial and thermal fabric according to claim 5, characterized in that, The flame-retardant modified silane reaction process in step (2) is as follows: 。

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