Air-permeable far infrared fiber fabric and preparation method thereof

Abstract

The application discloses a kind of breathable far infrared fiber fabric and preparation method thereof, it is related to fiber fabric technical field.The application is prepared when breathable far infrared fiber fabric, phosphorus-containing triamino compound is reacted with double bond modified silane, hydroxypropyl methacrylate, 2-[2-hydroxy-5-[2-(methacryloyloxy) ethyl] phenyl]-2H-benzotriazole to obtain modified liquid;Pre-modified graphene is reacted with 3-bromopropyl-5,5-dimethyl hydantoin to obtain modified graphene;After dispersing modified graphene, fiber, 3-glycidyl ether oxypropyl trimethoxysilane, modified liquid are added, and modified fiber is prepared after reaction;After weaving and spinning modified fiber, soak sodium hypochlorite solution, and prepare breathable far infrared fiber fabric.The breathable far infrared fiber fabric prepared by the application has the advantages of air permeability, far infrared, antibacterial, flame retardant, ultraviolet protection and washing resistance.

Description

Technical Field

[0001] This invention relates to the field of fiber fabric technology, specifically to a breathable far-infrared fiber fabric and its preparation method. Background Technology

[0002] With the continuous improvement of people's material and cultural living standards and the development of science and technology worldwide, functional textiles have become a global trend in textile development, playing a vital role in various sectors of the national economy. The development of functional textiles with comfort, leisure, health, safety, and health benefits provides a strong guarantee for meeting people's demands for comfortable and aesthetically pleasing clothing and for the development of textile enterprises. Against this backdrop, functional textiles such as far-infrared textiles have emerged and achieved significant development. However, current research focuses primarily on far-infrared synthetic fibers, while research on natural fibers mainly employs finishing processes, resulting in drawbacks such as low far-infrared emissivity, poor washability, and significantly reduced breathability. Plant fibers such as cotton and linen, as well as wool and rabbit hair fibers, are prone to bacterial growth without modification, potentially affecting human health. Furthermore, to enhance product competitiveness, properties such as UV protection, flame retardancy, and washability, which are highly valued by consumers, need to be integrated and synergistically incorporated into products.

[0003] Traditional product performance modification is mainly carried out in three ways: first, by simply coating or impregnating functional auxiliaries onto the fabric surface through finishing; second, by incorporating functional particles into the spinning melt or liquid to prepare blended fibers; and third, by using composite spinning, core-sheath structures, or multilayer film lamination technology. Among these methods, when modifying through finishing, most functional auxiliaries adhere to the fabric only through weak physical adsorption, hydrogen bonding, and other interactions, resulting in poor modification effects, low auxiliary utilization, and poor washability. Summary of the Invention

[0004] The purpose of this invention is to provide a breathable far-infrared fiber fabric and its preparation method, 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: a breathable far-infrared fiber fabric, wherein the breathable far-infrared fiber fabric is obtained by spinning and weaving modified fibers and then soaking them in a sodium hypochlorite solution; the modified fiber is obtained by dispersing modified graphene and adding it to fibers, 3-glycidyl etheroxypropyltrimethoxysilane, and a modifying liquid, followed by a reaction; the modified graphene is obtained by reacting pre-modified graphene with 3-bromopropyl-5,5-dimethylhydantoin; the pre-modified graphene is obtained by reacting graphene oxide with (N,N-dimethyl-3-amino) The modified solution is prepared by reacting a phosphorus-containing triamino compound with a double-bond modified silane, hydroxypropyl methacrylate, and 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole; the double-bond modified silane is prepared by reacting methacrylic anhydride with 1,3-di(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane; the phosphorus-containing triamino compound is prepared by reacting 2-amino-2-methyl-1,3-propanediol with (4-aminophenyl)phosphonic acid.

[0006] As an optimization, the fiber is one or more of cotton fiber, lyocell fiber, viscose fiber, hollow polyester fiber, and linen fiber.

[0007] A method for preparing a breathable far-infrared fiber fabric includes the following preparation steps:

[0008] (1) Under a nitrogen atmosphere, 2-amino-2-methyl-1,3-propanediol, (4-aminophenyl)phosphonic acid, p-toluenesulfonic acid, anhydrous magnesium sulfate, and toluene were mixed evenly in a mass ratio of 1:(3.3~3.5):(5.4~5.8):(7~9):(30~40), and refluxed at 90~100℃ and 200~300r / min for 10~12h. The mixture was filtered while hot, and toluene was removed by vacuum distillation. The mixture was recrystallized with isopropanol to obtain a phosphorus-containing triamino compound.

[0009] (2) By mass fraction, under a nitrogen atmosphere, 5-6 parts of 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, 5.6-7.3 parts of triethylamine, and 50-60 parts of dichloromethane are mixed evenly. In an ice-water bath, at 200-300 r / min, 6.2-7.5 parts of methacrylic anhydride are added dropwise over 30-40 min. After the addition is completed, the temperature is raised to 45-50℃ and the reaction is carried out at 200-300 r / min for 10-12 h. The pH is adjusted to 8 with saturated sodium bicarbonate solution, and the mixture is extracted with dichloromethane. After dehydration with anhydrous magnesium sulfate, the dichloromethane is removed by rotary evaporation to obtain double bond modified silane.

[0010] (3) By mass, mix 2-3 parts of phosphorus-containing triamino compound and 4-5 parts of pure water evenly, add 1.5-2.2 parts of triethylamine, react at room temperature at 200-300 r / min for 40-50 min, add 1.95-2.92 parts of double bond modified silane, 0.28-0.42 parts of hydroxypropyl methacrylate, and 0.78-1.17 parts of 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, adjust the pH to 8 with triethylamine, and react at 50-55℃ at 800-1000 r / min for 9-10 h to obtain the modified solution;

[0011] (4) According to the mass fraction, 1~1.2 parts of graphene oxide, 50~60 parts of N,N-dimethylformamide and 2~3 parts of pure water are mixed evenly and ultrasonically dispersed in an ice-water bath for 100~120 min. Under a nitrogen atmosphere, 2~3 parts of (N,N-dimethyl-3-aminopropyl)trimethoxysilane are added and stirred at 55~60℃ and 300~400 r / min for 14~16 h. 80~100 parts of anhydrous ethanol are added to precipitate for 30~40 min. After centrifugation, the supernatant is removed, and the product is washed with pure water by centrifugation and freeze-dried to obtain pre-modified graphene.

[0012] (5) Mix 0.4-0.5 parts of pre-modified graphene and 40-50 parts of pure water evenly by mass, disperse by ultrasonication for 10-12 min, add 0.6-0.7 parts of 3-bromopropyl-5,5-dimethylhydantoin, stir and react at 90-95℃ and 200-300 r / min for 18-20 h, remove the supernatant by centrifugation, wash with pure water by centrifugation, and freeze dry to obtain modified graphene;

[0013] (6) Disperse 0.02-0.03 parts of modified graphene in 40-50 parts of sodium hydroxide solution by mass, and ultrasonically disperse for 10-12 min. Add 2-3 parts of fiber, 0.02-0.03 parts of 3-glycidyl etheroxypropyltrimethoxysilane, and 1-1.2 parts of modified solution. React at 50-60℃ and 200-300 r / min for 8-10 h. Filter, ultrasonically clean with pure water, and vacuum dry at 70-80℃ for 10-12 h to obtain modified fiber.

[0014] (7) The modified fiber is spun into yarn by ring spinning process and then woven into fabric. It is then soaked in 5wt% sodium hypochlorite solution at pH 7 for 60-70 min at 0-4℃ with a bath ratio of 1:(50-70)g / ml. After washing with pure water, it is vacuum dried at 60-70℃ for 10-12 h to obtain breathable far-infrared fiber fabric.

[0015] As an optimization, the reaction process of the phosphorus-containing triamine compound in step (1) is as follows:

[0016] .

[0017] As an optimization, the reaction process of the double bond modified silane in step (2) is as follows:

[0018] .

[0019] As an optimization, the reaction process of the modified liquid in step (3) is as follows:

[0020]

[0021] .

[0022] As an optimization, the reaction process of the pre-modified graphene in step (4) is as follows:

[0023] .

[0024] As an optimization, the reaction process of the modified graphene in step (5) is as follows:

[0025] .

[0026] As an optimization, the pH of the sodium hydroxide solution in step (6) is 8.

[0027] Compared with the prior art, the beneficial effects achieved by the present invention are as follows: In preparing breathable far-infrared fiber fabric, the present invention first reacts 2-amino-2-methyl-1,3-propanediol with (4-aminophenyl)phosphonic acid to obtain a phosphorus-containing triamino compound; then reacts methacrylic anhydride with 1,3-di(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane to obtain a double-bond modified silane; finally, the phosphorus-containing triamino compound is reacted with the double-bond modified silane, hydroxypropyl methacrylate, and 2-[2-hydroxy-5-[2-(methylpropanediol)]... A modified solution was prepared by reacting [(N,N-dimethyl-3-aminopropyl)trimethoxysilane]-2H-benzotriazole; pre-modified graphene was prepared by reacting graphene oxide with (N,N-dimethyl-3-aminopropyl)trimethoxysilane; modified graphene was prepared by reacting the pre-modified graphene with 3-bromopropyl-5,5-dimethylhydantoin; modified graphene was prepared by dispersing the modified graphene and adding it to fibers, 3-glycidyl etheroxypropyltrimethoxysilane, and the modified solution, and then reacting to obtain modified fibers; the modified fibers were spun and woven and then soaked in sodium hypochlorite solution to obtain breathable far-infrared fiber fabric.

[0028] First, the hydroxyl group on 2-amino-2-methyl-1,3-propanediol undergoes an esterification reaction with the phosphate group on (4-aminophenyl)phosphonic acid to obtain a phosphorus-containing triamino compound containing three amino groups and two phosphate groups. Then, methacrylic anhydride undergoes an amidation reaction with the amino group on 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane to obtain a double-bond modified silane with double bonds at both ends. The phosphorus-containing triamino compound then undergoes a Michael addition reaction with the double-bond modified silane, hydroxypropyl methacrylate, and 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole. Under high speed, these components crosslink and polymerize to form nanospheres, which are then suspended in water to form a suspension of the modified silane. The liquid contains a large amount of flame-retardant elements phosphorus, nitrogen, and silicon in the cross-linked nanospheres formed by various compounds. Each flame-retardant element has good synergistic flame-retardant ability, which can effectively improve the flame-retardant performance in subsequent modifications. Hydroxypropyl methacrylate introduces reactive hydroxyl groups into the nanospheres, which work together with the residual phosphate groups to better fix them on the fiber surface and effectively improve the water wash resistance. 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole is also introduced into the nanospheres through Michael addition reaction, and benzotriazole groups with effective UV absorption properties are introduced, which can effectively improve the UV protection performance. The benzotriazole groups can also synergistically improve the antibacterial performance.

[0029] Secondly, by first modifying graphene oxide with a silane coupling agent containing tertiary amine groups to introduce tertiary amine groups, and then reacting it with 3-bromopropyl-5,5-dimethylhydantoin, modified graphene is obtained. In addition to its inherent good far-infrared and UV protection properties, modified graphene can also provide certain antibacterial properties through mechanisms such as physical puncture, oxidative stress, blocking transmembrane transport or inhibiting bacterial growth, and inserting into and destroying cell membrane substances. Subsequently, by introducing quaternary ammonium groups and haloamine groups, the antibacterial properties of modified graphene are further improved. This reduces the amount of modified graphene used through synergistic antibacterial effects, avoiding excessive modified graphene from blocking pores and reducing air permeability during fiber modification.

[0030] Finally, the modified graphene and the modifying solution are dispersed in a weakly alkaline sodium hydroxide solution, and then 3-glycidyl etheroxypropyltrimethoxysilane is added to obtain a modifying solution. The fibers to be modified are then immersed in this solution for modification. Fiber surfaces generally contain reactive hydroxyl groups, such as cotton fibers, lyocell fibers, and viscose fibers. Modified graphene also contains reactive hydroxyl and carboxyl groups. The nanospheres in the modifying solution also retain reactive hydroxyl and phosphate groups. 3-glycidyl etheroxypropyltrimethoxysilane contains both siloxane groups and epoxy groups, both of which can react with hydroxyl and carboxyl groups, thereby covalently bonding the modified graphene with the nanospheres in the modifying solution. Nano-spherical particles are fixed on the fiber surface; at the same time, both the modified graphene and the nano-spherical particles in the modification solution have nanoscale size, which improves performance during modification while avoiding the decrease in air permeability caused by blocking pores. The modified fiber retains its original excellent air permeability and introduces flame retardant, antibacterial, UV protection, and far-infrared functionality. At the same time, because it is fixed by covalent bonds, the fabric woven from this fiber also has good wash resistance and can maintain good functionality after multiple washes. The woven fabric is soaked in sodium hypochlorite solution to halogenate the hydantoin groups, activate the halogen amine groups with antibacterial properties, and thus further improve the antibacterial properties. Detailed Implementation

[0031] 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.

[0032] The following information is provided for all raw materials used in the examples and comparative examples: Graphene oxide: thickness less than 5 nm, oxygen content of about 35%, sheet diameter of 10 μm, product number 102740, serial number XFSG01, purchased from Jiangsu Xianfeng Nanomaterials Technology Co., Ltd.; Fiber: combed fine cotton fiber, length 32 mm, fineness 1.8 dtex.

[0033] The spinning process parameters for all the following examples and comparative examples are as follows: using a two-stage doubling process, the first doubling weight is 20.5 g / 5 m, the second doubling weight is 19 g / 5 m, the roving weight is 5 g / 10 m, the twist coefficient is 58.5, the final yarn linear density is 11.8 tex, and the twist is 90 twists / 10 cm.

[0034] The weaving design for all the following examples and comparative examples is: warp density × weft density is 120 × 100 ends / cm.

[0035] Example 1

[0036] A method for preparing a breathable far-infrared fiber fabric, the method comprising the following steps:

[0037] (1) Under a nitrogen atmosphere, 2-amino-2-methyl-1,3-propanediol, (4-aminophenyl)phosphonic acid, p-toluenesulfonic acid, anhydrous magnesium sulfate and toluene were mixed evenly in a mass ratio of 1:3.3:5.4:7:30 and refluxed at 90°C and 200 r / min for 12 h. The mixture was filtered while hot, and toluene was removed by vacuum distillation. The mixture was recrystallized with isopropanol to obtain a phosphorus-containing triamino compound.

[0038] (2) By mass, under a nitrogen atmosphere, 5 parts of 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, 5.6 parts of triethylamine and 50 parts of dichloromethane were mixed evenly. In an ice-water bath, at 200 r / min, 6.2 parts of methacrylic anhydride were added dropwise over 30 min. After the addition was completed, the temperature was raised to 45℃ and the reaction was carried out at 200 r / min for 12 h. The pH was adjusted to 8 with saturated sodium bicarbonate solution, and the mixture was extracted with dichloromethane. After removing water with anhydrous magnesium sulfate, the dichloromethane was removed by rotary evaporation to obtain double bond modified silane.

[0039] (3) By mass, 2 parts of phosphorus-containing triamino compound and 4 parts of pure water are mixed evenly, 1.5 parts of triethylamine are added, and the mixture is reacted at 200 r / min for 40 min at room temperature. Then, 1.95 parts of double bond modified silane, 0.28 parts of hydroxypropyl methacrylate and 0.78 parts of 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole are added. The pH is adjusted to 8 with triethylamine, and the mixture is reacted at 50℃ and 800 r / min for 10 h to obtain the modified solution.

[0040] (4) By mass fraction, 1 part graphene oxide, 50 parts N,N-dimethylformamide and 2 parts pure water are mixed evenly and ultrasonically dispersed in an ice-water bath for 100 min. Under a nitrogen atmosphere, 2 parts (N,N-dimethyl-3-aminopropyl)trimethoxysilane are added and stirred at 55℃ and 300 r / min for 16 h. 80 parts anhydrous ethanol are added to precipitate for 40 min. After centrifugation, the supernatant is removed, and the mixture is washed with pure water by centrifugation and freeze-dried to obtain pre-modified graphene.

[0041] (5) According to the mass fraction, 0.4 parts of pre-modified graphene and 40 parts of pure water are mixed evenly, ultrasonically dispersed for 10 min, 0.6 parts of 3-bromopropyl-5,5-dimethylhydantoin are added, and the mixture is stirred at 90℃ and 200 r / min for 20 h. The supernatant is removed by centrifugation, washed with pure water by centrifugation, and then freeze-dried to obtain modified graphene.

[0042] (6) By mass, 0.02 parts of modified graphene were dispersed in 40 parts of sodium hydroxide solution and ultrasonically dispersed for 10 min. Then, 2 parts of fiber, 0.02 parts of 3-glycidyl etheroxypropyltrimethoxysilane, and 1 part of modification solution were added. The mixture was reacted at 50°C and 200 r / min for 10 h. After filtration, the mixture was ultrasonically cleaned with pure water and vacuum dried at 70°C for 12 h to obtain modified fiber.

[0043] (7) The modified fiber is spun into yarn by ring spinning process, then woven into fabric. At 0℃, it is soaked in 5wt% sodium hypochlorite solution with pH 7 at a bath ratio of 1:50g / ml for 70min for chlorination. It is then washed with pure water and vacuum dried at 60℃ for 12h to obtain breathable far-infrared fiber fabric.

[0044] Example 2

[0045] A method for preparing a breathable far-infrared fiber fabric, the method comprising the following steps:

[0046] (1) Under a nitrogen atmosphere, 2-amino-2-methyl-1,3-propanediol, (4-aminophenyl)phosphonic acid, p-toluenesulfonic acid, anhydrous magnesium sulfate and toluene were mixed evenly in a mass ratio of 1:3.4:5.6:8:35 and refluxed at 95°C and 250 r / min for 11 h. The mixture was filtered while hot, and toluene was removed by vacuum distillation. The mixture was recrystallized with isopropanol to obtain a phosphorus-containing triamino compound.

[0047] (2) By mass, under a nitrogen atmosphere, 5.5 parts of 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, 6.4 parts of triethylamine and 55 parts of dichloromethane were mixed evenly. In an ice-water bath, at 250 r / min, 6.82 parts of methacrylic anhydride were added dropwise over 35 min. After the addition was completed, the temperature was raised to 48℃ and the reaction was carried out at 250 r / min for 11 h. The pH was adjusted to 8 with saturated sodium bicarbonate solution, and the mixture was extracted with dichloromethane. After removing water with anhydrous magnesium sulfate, the dichloromethane was removed by rotary evaporation to obtain double bond modified silane.

[0048] (3) By mass, 2.5 parts of phosphorus-containing triamino compound and 4.5 parts of pure water were mixed evenly, and 1.9 parts of triethylamine were added. The mixture was reacted at 250 r / min for 45 min at room temperature. Then, 2.43 parts of double bond modified silane, 0.35 parts of hydroxypropyl methacrylate and 0.97 parts of 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole were added. The pH was adjusted to 8 with triethylamine and the mixture was reacted at 55℃ and 900 r / min for 9.5 h to obtain the modified solution.

[0049] (4) By mass, 1.1 parts of graphene oxide, 55 parts of N,N-dimethylformamide and 2.5 parts of pure water were mixed evenly and ultrasonically dispersed in an ice-water bath for 110 min. Under a nitrogen atmosphere, 2.5 parts of (N,N-dimethyl-3-aminopropyl)trimethoxysilane were added and stirred at 60℃ and 350 r / min for 15 h. 90 parts of anhydrous ethanol were added to precipitate for 35 min. After centrifugation, the supernatant was removed, and the mixture was washed with pure water by centrifugation and freeze-dried to obtain pre-modified graphene.

[0050] (5) According to the mass fraction, 0.45 parts of pre-modified graphene and 45 parts of pure water are mixed evenly, ultrasonically dispersed for 11 min, 0.65 parts of 3-bromopropyl-5,5-dimethylhydantoin are added, and the mixture is stirred at 90℃ and 250 r / min for 19 h. The supernatant is removed by centrifugation, washed with pure water by centrifugation, and then freeze-dried to obtain modified graphene.

[0051] (6) By mass, 0.025 parts of modified graphene were dispersed in 45 parts of sodium hydroxide solution and ultrasonically dispersed for 11 min. Then, 2.5 parts of fiber, 0.025 parts of 3-glycidyl etheroxypropyltrimethoxysilane, and 1.1 parts of modification solution were added. The mixture was reacted at 55°C and 250 r / min for 9 h. After filtration, the mixture was ultrasonically cleaned with pure water and vacuum dried at 75°C for 11 h to obtain modified fiber.

[0052] (7) The modified fiber is spun into yarn by ring spinning process, then woven into fabric. At 2°C, it is soaked in 5wt% sodium hypochlorite solution with pH 7 at a bath ratio of 1:60g / ml for 65min for chlorination. It is then washed with pure water and vacuum dried at 65°C for 11h to obtain breathable far-infrared fiber fabric.

[0053] Example 3

[0054] A method for preparing a breathable far-infrared fiber fabric, the method comprising the following steps:

[0055] (1) Under a nitrogen atmosphere, 2-amino-2-methyl-1,3-propanediol, (4-aminophenyl)phosphonic acid, p-toluenesulfonic acid, anhydrous magnesium sulfate and toluene were mixed evenly in a mass ratio of 1:3.5:5.8:9:40 and refluxed at 100℃ and 300r / min for 10h. The mixture was filtered while hot, and toluene was removed by vacuum distillation. The mixture was recrystallized with isopropanol to obtain a phosphorus-containing triamino compound.

[0056] (2) By mass, under a nitrogen atmosphere, 6 parts of 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, 7.3 parts of triethylamine and 60 parts of dichloromethane were mixed evenly. In an ice-water bath, at 300 r / min, 7.5 parts of methacrylic anhydride were added dropwise over 40 min. After the addition was completed, the temperature was raised to 50℃ and the reaction was carried out at 300 r / min for 10 h. The pH was adjusted to 8 with saturated sodium bicarbonate solution, and the mixture was extracted with dichloromethane. After removing water with anhydrous magnesium sulfate, the dichloromethane was removed by rotary evaporation to obtain double bond modified silane.

[0057] (3) By mass, 3 parts of phosphorus-containing triamino compound and 5 parts of pure water are mixed evenly, 2.2 parts of triethylamine are added, and the mixture is reacted at 300 r / min for 50 min at room temperature. Then, 2.92 parts of double bond modified silane, 0.42 parts of hydroxypropyl methacrylate and 1.17 parts of 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole are added. The pH is adjusted to 8 with triethylamine, and the mixture is reacted at 55℃ and 1000 r / min for 9 h to obtain the modified solution.

[0058] (4) By mass fraction, 1.2 parts of graphene oxide, 60 parts of N,N-dimethylformamide and 3 parts of pure water were mixed evenly and ultrasonically dispersed in an ice-water bath for 120 min. Under a nitrogen atmosphere, 3 parts of (N,N-dimethyl-3-aminopropyl)trimethoxysilane were added and stirred at 60°C and 400 r / min for 14 h. 100 parts of anhydrous ethanol were added to precipitate for 30 min. After centrifugation, the supernatant was removed, and the mixture was washed with pure water by centrifugation and freeze-dried to obtain pre-modified graphene.

[0059] (5) According to the mass fraction, 0.5 parts of pre-modified graphene and 50 parts of pure water are mixed evenly, ultrasonically dispersed for 12 min, 0.7 parts of 3-bromopropyl-5,5-dimethylhydantoin are added, and the mixture is stirred at 95℃ and 300 r / min for 18 h. The supernatant is removed by centrifugation, washed with pure water by centrifugation, and then freeze-dried to obtain modified graphene.

[0060] (6) By mass, 0.03 parts of modified graphene were dispersed in 50 parts of sodium hydroxide solution and ultrasonically dispersed for 12 min. Then, 3 parts of fiber, 0.03 parts of 3-glycidyl etheroxypropyltrimethoxysilane, and 1.2 parts of modification solution were added. The mixture was reacted at 60℃ and 300 r / min for 8 h. After filtration, the mixture was ultrasonically cleaned with pure water and vacuum dried at 80℃ for 10 h to obtain modified fiber.

[0061] (7) The modified fiber is spun into yarn by ring spinning process, then woven into fabric. It is then soaked in 5wt% sodium hypochlorite solution at pH 7 for 70 min at 4℃ with a bath ratio of 1:70 g / ml, washed with pure water, and vacuum dried at 70℃ for 10 h to obtain breathable far-infrared fiber fabric.

[0062] Comparative Example 1:

[0063] The difference between the preparation method of the breathable far-infrared fiber fabric of Comparative Example 1 and Example 2 lies in the difference in steps (1) and (3). Step (1) is modified as follows: Under a nitrogen atmosphere, 2-amino-2-methyl-1,3-propanediol, 3-amino-4-phenylbutyric acid, p-toluenesulfonic acid, anhydrous magnesium sulfate, and toluene are mixed evenly in a mass ratio of 1:3.5:5.6:8:35, and refluxed at 95°C and 250 r / min for 11 h. The mixture is filtered while hot, toluene is removed by vacuum distillation, and the mixture is recrystallized with isopropanol to obtain the triamino compound. Step (3) is modified as follows: Mix 2.5 parts of the triamino compound and 4.5 parts of pure water by mass, add 1.9 parts of triethylamine, react at 250 rpm for 45 min at room temperature, then add 2.43 parts of double-bond modified silane, 0.35 parts of hydroxypropyl methacrylate, and 0.97 parts of 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole. Adjust the pH to 8 with triethylamine, and react at 55°C and 900 rpm for 9.5 h to obtain the modified solution. The remaining steps are the same as in Example 2.

[0064] Comparative Example 2:

[0065] The preparation method of the breathable far-infrared fiber fabric in Comparative Example 2 differs from that in Example 2 in that step (2) is omitted, and step (3) is modified as follows: 2.5 parts by mass of a phosphorus-containing triamino compound and 4.5 parts by mass of pure water are mixed evenly, 1.9 parts by mass of triethylamine are added, and the mixture is reacted at 250 r / min for 45 min at room temperature. Then, 1.96 parts by mass of 2-methyl-2-acrylate-1,10-decanediol, 0.35 parts by mass of hydroxypropyl methacrylate, and 0.97 parts by mass of 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole are added. The pH is adjusted to 8 with triethylamine, and the mixture is reacted at 55°C and 900 r / min for 9.5 h to obtain the modified solution. The remaining steps are the same as in Example 2.

[0066] Comparative Example 3:

[0067] The difference between the preparation method of the breathable far-infrared fiber fabric in Comparative Example 3 and Example 2 lies in step (3). Step (3) is modified as follows: 2.5 parts by mass of phosphorus-containing triamino compound and 4.5 parts by mass of pure water are mixed evenly, 1.9 parts by mass of triethylamine are added, and the mixture is reacted at 250 r / min for 45 min at room temperature. Then, 2.89 parts by mass of double-bond modified silane and 0.97 parts by mass of 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole are added. The pH is adjusted to 8 with triethylamine, and the mixture is reacted at 55°C and 900 r / min for 9.5 h to obtain the modified solution. The remaining steps are the same as in Example 2.

[0068] Comparative Example 4:

[0069] The difference between the preparation method of the breathable far-infrared fiber fabric in Comparative Example 4 and Example 2 lies in step (3). Step (3) is modified as follows: 2.5 parts by mass of phosphorus-containing triamine compound and 4.5 parts by mass of pure water are mixed evenly, 1.9 parts by mass of triethylamine are added, and the mixture is reacted at 250 r / min for 45 min at room temperature. Then, 3.01 parts by mass of double-bond modified silane and 0.35 parts by mass of hydroxypropyl methacrylate are added. The pH is adjusted to 8 with triethylamine, and the mixture is reacted at 55°C and 900 r / min for 9.5 h to obtain the modified solution. The remaining steps are the same as in Example 2.

[0070] Comparative Example 5:

[0071] The difference between the preparation method of the breathable far-infrared fiber fabric in Comparative Example 5 and Example 2 lies in step (5). Step (5) is modified as follows: 0.45 parts by mass of pre-modified graphene and 45 parts by mass of pure water are mixed evenly, ultrasonically dispersed for 11 min, 0.44 parts by mass of 1-iodopropane are added, and the mixture is stirred at 90°C and 250 r / min for 19 h. The supernatant is removed by centrifugation, and the mixture is washed with pure water by centrifugation and freeze-dried to obtain modified graphene. The remaining steps are the same as in Example 2.

[0072] Comparative Example 6:

[0073] The preparation method of the breathable far-infrared fiber fabric in Comparative Example 6 differs from that in Example 2 in that steps (4) and (5) are omitted, and step (6) is modified as follows: 0.025 parts by mass of graphene oxide are dispersed in 45 parts by mass of sodium hydroxide solution, ultrasonically dispersed for 11 min, 2.5 parts by mass of fiber, 0.025 parts by mass of 3-glycidyl etheroxypropyltrimethoxysilane, and 1.1 parts by mass of modifying liquid are added, and the mixture is reacted at 55°C and 250 r / min for 9 h. After filtration, the mixture is ultrasonically cleaned with pure water and vacuum dried at 75°C for 11 h to obtain the modified fiber. The remaining steps are the same as in Example 2.

[0074] Comparative Example 7:

[0075] The preparation method of the breathable far-infrared fiber fabric in Comparative Example 7 differs from that in Example 2 in that steps (4) and (5) are omitted, and step (6) is modified as follows: 2.5 parts of fiber, 0.025 parts of 3-glycidyl etheroxypropyltrimethoxysilane, and 1.1 parts of modifying liquid are added to 45 parts of sodium hydroxide solution by mass. The mixture is reacted at 55°C and 250 r / min for 9 h, filtered, ultrasonically cleaned with pure water, and vacuum dried at 75°C for 11 h to obtain the modified fiber. The remaining steps are the same as in Example 2.

[0076] Comparative Example 8:

[0077] The preparation method of the breathable far-infrared fiber fabric in Comparative Example 8 differs from that in Example 2 in that steps (1), (2), and (3) are omitted, and step (6) is modified as follows: 0.025 parts by mass of modified graphene are dispersed in 45 parts by mass of sodium hydroxide solution, ultrasonically dispersed for 11 min, 2.5 parts by mass of fiber and 0.025 parts by mass of 3-glycidyl etheroxypropyltrimethoxysilane are added, and the mixture is reacted at 55°C and 250 r / min for 9 h. After filtration, the mixture is ultrasonically cleaned with pure water and vacuum dried at 75°C for 11 h to obtain the modified fiber. The remaining steps are the same as in Example 2.

[0078] Comparative Example 9:

[0079] The difference between the preparation method of the breathable far-infrared fiber fabric of Comparative Example 9 and Example 2 lies in step (6). Step (6) is modified as follows: 0.025 parts by mass of modified graphene are dispersed in 45 parts by sodium hydroxide solution, ultrasonically dispersed for 11 min, 2.5 parts by fiber and 1.1 parts by modification liquid are added, and the mixture is reacted at 55°C and 250 r / min for 9 h. After filtration, the mixture is ultrasonically cleaned with pure water and vacuum dried at 75°C for 11 h to obtain the modified fiber. The remaining steps are the same as in Example 2.

[0080] Comparative Example 10:

[0081] The difference between the preparation method of the breathable far-infrared fiber fabric of Comparative Example 10 and Example 2 lies in the different step (7). Step (7) is modified as follows: the modified fiber is spun into yarn by ring spinning, then woven into fabric, and soaked in pure water at pH 7 at 2°C with a bath ratio of 1:60 g / ml for 65 min. After washing with pure water, it is vacuum dried at 65°C for 11 h to obtain the breathable far-infrared fiber fabric. The remaining steps are the same as in Example 2.

[0082] Test Example 1:

[0083] Breathability, far-infrared, UV protection, and flame retardant performance tests: The breathability, far-infrared emissivity, UV absorption value, and limiting oxygen index of the prepared breathable far-infrared fiber fabric were tested to evaluate its breathability, far-infrared, UV protection, and flame retardant performance. The specific test methods are as follows: Breathability: The breathability of the prepared breathable far-infrared fiber fabric was tested according to GB / T 5453-1997, with a test area of ​​20 cm². 2The pressure drop was 100 Pa, and each group was tested in parallel for 5 times, with the average value recorded. Far-infrared performance: The far-infrared emissivity of the prepared breathable far-infrared fiber fabric was tested according to GB / T 30127-2013, with a detection wavelength of 5~14 μm. A TIR 100-2 infrared thermal emissivity meter was used to test the far-infrared emissivity. Each group was tested in parallel for 5 times, with the average value recorded. Ultraviolet protection performance: The ultraviolet protection factor (UPF) of the prepared breathable far-infrared fiber fabric was tested according to GB / T 18830-2009, with a test wavelength of 280~400 nm and a wavelength resolution of 1 nm. Each group was tested in parallel for 5 times, with the average value recorded. Flame retardant performance: The limiting oxygen index of the prepared breathable far-infrared fiber fabric was tested according to GB / T 5454-1997, with a sample size of 158 mm × 58 mm. 15 samples were tested in each group, and the average value was recorded.

[0084] The results are shown in Table 1.

[0085]

[0086] A comparison of the experimental data from Examples 1-3 and Comparative Examples 1-10 in Table 1 reveals that the breathable far-infrared fiber fabric prepared by this invention has good breathability, far-infrared performance, UV protection performance, and flame retardant performance.

[0087] By comparing the data in the table, the data in Comparative Example 1 shows that the flame-retardant element phosphorus was successfully introduced into the modified liquid, thereby effectively improving the flame-retardant performance.

[0088] By comparing the data in the table, the data in Comparative Example 2 shows that the use of double-bond modified silane successfully introduced silicon into the modified liquid, which can synergistically enhance the flame retardant properties of phosphorus.

[0089] By comparing the data in the table, the data in Comparative Example 3 shows that the introduction of hydroxypropyl methacrylate brings reactive hydroxyl groups, which allow the nano-spherical particles in the modified liquid to be fixed on the fibers during the finishing process through the hydroxyl groups. Although it will slightly reduce the air permeability, it will not have too much of an impact. Because the nano-spherical particles in the modified liquid have groups with UV protection properties and a large number of flame retardant elements, the presence of hydroxyl reactive groups greatly improves the modification effect of the modified liquid on the fibers, thereby effectively improving the UV protection and flame retardant properties.

[0090] By comparing the data in the table, the data in Comparative Example 4 shows that the addition of 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole to the modification solution successfully introduced a benzotriazole structure with ultraviolet absorption properties, which can effectively improve the UV protection effect. At the same time, this compound also contains a large amount of flame retardant element nitrogen, which can improve the flame retardant performance through synergy with phosphorus and silicon elements.

[0091] By comparing the data in the table, the data in Comparative Example 7 shows that the modified graphene was successfully modified and fixed on the fiber surface. The modified graphene has good far-infrared properties and UV protection capabilities, and it also promotes the formation of carbon layers. It can also work synergistically with phosphorus, nitrogen, and silicon elements to further improve the flame retardant effect. Although it will slightly reduce air permeability, it is acceptable.

[0092] By comparing the data in the table, the data in Comparative Example 8 shows that the nanospheres in the modified liquid were successfully modified and fixed on the fiber surface. The nanospheres contain structures with UV protection properties and a large number of flame retardant elements, which can effectively improve UV protection and flame retardant properties.

[0093] By comparing the data in the table, the data in Comparative Example 9 shows that the addition of 3-glycidyl etheroxypropyltrimethoxysilane successfully immobilized a large amount of modified graphene and nanospheres in the modification solution onto the fiber surface during the modification stage through the hydrolysis and condensation reaction of siloxane and the ring-opening reaction of epoxy groups. This significantly improved the modification effect. Otherwise, the modified graphene and nanospheres could only be fixed on the fiber surface through physical adsorption, hydrogen bonding, etc., resulting in a small amount of fixation, weak fixation, and limited performance improvement.

[0094] Test Example 2:

[0095] Antibacterial performance test: The shaking method in GB / T 20944.3-2008 was adopted. 0.75±0.05g of the prepared breathable far-infrared fiber fabric was cut off and mixed with bacterial solution and shaken for 5min. The shaken bacterial solution was then cultured in agar medium. The inhibition rate of the breathable far-infrared fiber fabric against Escherichia coli and Staphylococcus aureus was determined by the number of colonies. Each group of samples was tested 5 times and the average value was recorded.

[0096] The results are shown in Table 2.

[0097]

[0098] A comparison of the experimental data from Examples 1-3 and Comparative Examples 1-10 in Table 2 reveals that the breathable far-infrared fiber fabric prepared by this invention has good antibacterial properties.

[0099] Comparing the data in the table, Comparative Examples 3 and 4 show that the addition of 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole introduces a benzotriazole group, which assists in adsorption onto the bacterial surface, thereby promoting a better antibacterial effect. The addition of hydroxypropyl methacrylate enhances the modification effect of the modifying solution and increases the loading on the fiber surface. Comparative Examples 5 and 6 show that 3-bromopropyl-5,5-dimethylhydantoin successfully reacted on the pre-modified graphene surface, forming a quaternary ammonium structure. The quaternary ammonium salt and haloamine synergistically enhance the antibacterial properties by oxidizing the graphene itself. Comparative Example 7 shows that graphene oxide itself also has good antibacterial properties, and synergistically with the modified quaternary ammonium salt and haloamine on it, forms a better antibacterial effect. Comparative Example 8 shows that the benzotriazole group assists in adsorption onto the bacterial surface, thereby promoting a better antibacterial effect by the antibacterial structure. Comparative Example 9 data demonstrates that 3-glycidyl etheroxypropyltrimethoxysilane enhances the modification effect by connecting modified graphene to nanospheres in the modification solution and fixing them to the fiber surface, thereby improving the antibacterial effect. Comparative Example 10 data demonstrates that the chlorination step successfully halogenated the haloamine; the haloamine structure exhibits good antibacterial effects and, synergistically, provides even better antibacterial performance with graphene oxide and quaternary ammonium salt.

[0100] Test Example 3:

[0101] Washability test: The prepared breathable far-infrared fiber fabric was washed and dried multiple times according to GB / T 8629-2017. A washing machine that meets the A1 standard was used. The 4G washing program in Appendix B was selected. Standard detergent 2 was added at a rate of 20g. The sample size was 50cm×50cm. The fabric was hung to dry using the A drying program. One wash and one dry cycle was counted as one cycle. A total of 50 cycles were performed. Then, the antibacterial, far-infrared and UV protection performance were tested again according to the test methods in Test Examples 1 and 2. Each group was tested in parallel 5 times. The average value was compared with the data before washing. The reduction rate of each performance was recorded.

[0102] The results are shown in Table 3.

[0103]

[0104] A comparison of the experimental data from Examples 1-3 and Comparative Examples 1-10 in Table 3 reveals that the breathable far-infrared fiber fabric prepared by this invention has good water-washing resistance.

[0105] By comparing the data in the table, the data in Comparative Example 3 shows that the addition of hydroxypropyl methacrylate to the modifying solution introduces reactive hydroxyl groups onto the nanospheres in the modifying solution, allowing them to be covalently linked to the fiber surface, thereby effectively improving the water washability.

[0106] By comparing the data in the table, the data in Comparative Example 9 shows that the addition of 3-glycidyl etheroxypropyltrimethoxysilane successfully immobilized and loaded a large amount of modified graphene and nanospheres in the modification solution onto the fiber surface during the modification stage through the hydrolysis and condensation reaction of siloxane and the ring-opening reaction of epoxy groups. Moreover, this method of fixation through covalent bonds has excellent water wash resistance and maintains good performance even after multiple water washes. The performance durability is much higher than that of loading through physical adsorption, hydrogen bonding, etc.

[0107] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A breathable far-infrared fiber fabric, characterized in that, The breathable far-infrared fiber fabric is obtained by spinning and weaving modified fibers and then soaking them in a sodium hypochlorite solution; the modified fiber is obtained by dispersing modified graphene and adding it to fibers, 3-glycidyl etheroxypropyltrimethoxysilane, and a modifying solution, followed by a reaction; the modified graphene is obtained by reacting pre-modified graphene with 3-bromopropyl-5,5-dimethylhydantoin; the pre-modified graphene is obtained by reacting graphene oxide with (N,N-dimethyl-3-aminopropyl)trimethoxysilane; the modified... The solution is prepared by reacting a phosphorus-containing triamino compound with a double-bond modified silane, hydroxypropyl methacrylate, and 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole; the double-bond modified silane is prepared by reacting methacrylic anhydride with 1,3-di(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane; the phosphorus-containing triamino compound is prepared by reacting 2-amino-2-methyl-1,3-propanediol with (4-aminophenyl)phosphonic acid.

2. The breathable far-infrared fiber fabric according to claim 1, characterized in that, The fiber is one or more of cotton fiber, lyocell fiber, viscose fiber, hollow polyester fiber, and hemp fiber.

3. The breathable far-infrared fiber fabric according to claim 1, characterized in that, The preparation method of the modified liquid includes the following steps: (1) Under a nitrogen atmosphere, 2-amino-2-methyl-1,3-propanediol, (4-aminophenyl)phosphonic acid, p-toluenesulfonic acid, anhydrous magnesium sulfate and toluene were mixed evenly, refluxed and stirred to react, filtered, distilled under reduced pressure and recrystallized to obtain a phosphorus-containing triamino compound. (2) Under a nitrogen atmosphere, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, triethylamine and dichloromethane were mixed evenly, and methacrylic anhydride was added dropwise in an ice-water bath. After the addition was completed, the reaction was stirred, the pH was adjusted, the mixture was extracted, water was removed, and the mixture was rotary evaporated to obtain double bond modified silane. (3) Mix the phosphorus-containing triamino compound and pure water evenly, add triethylamine, react at room temperature, add double bond modified silane, hydroxypropyl methacrylate, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, adjust the pH, stir the reaction, and obtain the modified solution.

4. The breathable far-infrared fiber fabric according to claim 3, characterized in that, The modified solution is prepared by mixing 2-3 parts of a phosphorus-containing triamino compound and 4-5 parts of pure water by mass, adding 1.5-2.2 parts of triethylamine, stirring at room temperature for 40-50 min, adding 1.95-2.92 parts of double-bond modified silane, 0.28-0.42 parts of hydroxypropyl methacrylate, and 0.78-1.17 parts of 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, adjusting the pH with triethylamine, and stirring at 50-55℃ for 9-10 h.

5. The breathable far-infrared fiber fabric according to claim 4, characterized in that, The phosphorus-containing triamino compound is prepared by mixing 2-amino-2-methyl-1,3-propanediol, (4-aminophenyl)phosphonic acid, p-toluenesulfonic acid, anhydrous magnesium sulfate, and toluene in a mass ratio of 1:(3.3~3.5):(5.4~5.8):(7~9):(30~40) under a nitrogen atmosphere, stirring and refluxing at 90~100℃ for 10~12 h, filtering while hot, removing toluene by vacuum distillation, and recrystallizing.

6. The breathable far-infrared fiber fabric according to claim 4, characterized in that, The double-bond modified silane is prepared by mixing 5-6 parts by mass of 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, 5.6-7.3 parts by mass of triethylamine, and 50-60 parts by mass of dichloromethane under a nitrogen atmosphere. Then, 6.2-7.5 parts by mass of methacrylic anhydride are added dropwise over 30-40 minutes in an ice-water bath. After the addition is complete, the temperature is raised to 45-50°C, and the mixture is stirred for 10-12 hours. The pH is adjusted with saturated sodium bicarbonate solution, and the mixture is extracted with dichloromethane. After removing water, the dichloromethane is removed by rotary evaporation.

7. The breathable far-infrared fiber fabric according to claim 1, characterized in that, The method for preparing the modified graphene includes the following steps: by mass, 0.4-0.5 parts of pre-modified graphene and 40-50 parts of pure water are mixed evenly, ultrasonically dispersed for 10-12 min, 0.6-0.7 parts of 3-bromopropyl-5,5-dimethylhydantoin are added, and the mixture is stirred and reacted at 90-95℃ for 18-20 h. The supernatant is removed by centrifugation, washed, and freeze-dried to obtain the modified graphene.

8. The breathable far-infrared fiber fabric according to claim 7, characterized in that, The pre-modified graphene is prepared by mixing 1-1.2 parts by mass of graphene oxide, 50-60 parts by mass of N,N-dimethylformamide, and 2-3 parts by mass of pure water, ultrasonically dispersing the mixture in an ice-water bath for 100-120 min, adding 2-3 parts by mass of (N,N-dimethyl-3-aminopropyl)trimethoxysilane under a nitrogen atmosphere, stirring at 55-60°C and 300-400 r / min for 14-16 h, adding 80-100 parts by mass of anhydrous ethanol to precipitate the mixture for 30-40 min, centrifuging to remove the supernatant, washing by centrifugation, and freeze-drying.

9. The breathable far-infrared fiber fabric according to claim 1, characterized in that, The preparation method of the modified fiber includes the following steps: by mass, 0.02-0.03 parts of modified graphene are dispersed in 40-50 parts of sodium hydroxide solution, ultrasonically dispersed for 10-12 min, 2-3 parts of fiber, 0.02-0.03 parts of 3-glycidyl etheroxypropyltrimethoxysilane, and 1-1.2 parts of modification liquid are added, and the mixture is stirred and reacted at 50-60℃ for 8-10 h, filtered, ultrasonically cleaned, and vacuum dried for 10-12 h to obtain the modified fiber.

10. A method for preparing a breathable far-infrared fiber fabric according to any one of claims 1 to 9, characterized in that, The preparation steps include: the modified fiber is spun into yarn by ring spinning, then woven into fabric, and then soaked in a 5wt% sodium hypochlorite solution at pH 7 for 60-70 min at 0-4℃ with a bath ratio of 1:(50-70) g / ml, washed, and vacuum dried for 10-12 h to obtain a breathable far-infrared fiber fabric.

Images