A modified textile material, its preparation method and application

Abstract

The present invention relates to the technical field of functional textiles, and particularly relates to a graft-modified textile material, a preparation method thereof, and an application thereof in the field of textiles. The modified textile material includes modified cotton thread / cloth material, modified regenerated fiber cloth material, modified polyester cloth / filling material, or modified nylon cloth material, which is mainly prepared by a chemical grafting reaction using quaternized graphene with active functional groups and a fiber substrate as the main raw materials; it has antibacterial, deodorant, and acaricidal functions and excellent mechanical properties, and can be widely used as a raw material in textiles such as socks, towels, bath towels, underwear, lining materials for suits, lining materials for coats, four-piece sets for beds, filling materials for pillow cores, and filling materials for quilt cores.

Description

Technical Field

[0001] The present invention relates to the technical field of functional textiles, and particularly to a graft-modified textile material, a preparation method thereof, and an application thereof in the textile field. Background Art

[0002] As a high-performance 2D material, graphene has excellent optical, electrical, thermal stability, and mechanical properties, and also has excellent biocompatibility, making it have a bright application prospect in the biomedical field. Graphene oxide (GO) retains most of the complete SP 2 hybrid skeleton structure of graphene. GO has a high specific surface area and can be used as a good antibacterial carrier. At the same time, the high specific surface area can effectively adsorb odor small molecules to play a deodorizing role; in addition, the excellent mechanical properties of GO itself can effectively improve the abrasion resistance of textiles. However, GO has poor dispersibility in aqueous solution and is prone to agglomeration, resulting in poor processability. It is difficult to compound with textiles by post-treatment, which limits the wider application of GO in the textile industry.

[0003] The invention patent with the application number 202011048045.8 discloses a textile with wear-resistant and self-cleaning functions and its application. Its graphene composite is obtained by modifying graphene with tetraethyl orthosilicate and octadecyltrimethoxysilane. Its long-chain alkyl groups are intertwined with the alkyl chains in ionic liquid and polyvinylidene fluoride, increasing the curing speed of the curable composition on the textile and enabling it to stably adhere to the textile. The combination of the graphene composite and the textile has no chemical bond and no antibacterial effect.

[0004] The invention patent with the application number 202010026219.4 discloses an antibacterial graphene oxide nano-composite fabric and a preparation method thereof. Polyethyleneimine is grafted on the surface of graphene oxide for modification, and nano-silver is loaded on the surface of the modified graphene to obtain an antibacterial graphene oxide nano-composite material. By using the electrospinning technology, the antibacterial graphene oxide nano-composite material is sprayed on a layer of cotton net to obtain antibacterial cotton yarn, which can be woven into a fabric. The modification method uses electrospinning, with low efficiency and difficulty in achieving batch preparation.

[0005] The invention patent with the application number 201811602932.8 discloses a preparation method of a graphene-based antibacterial fabric. Benzyl benzoate and castor oil polyoxyethylene ether are used as organic cross-linking agents to increase the bonding strength between graphene and the fabric. In the post-treatment stage, finishing is carried out by padding method. The method is simple, but organic cross-linking agents need to be added, and the bonding force between the fabric and graphene is weak, and the wash fastness does not meet the requirements.

[0006] The invention patent with the application number 202110140122.0 discloses a preparation method of modified bamboo original fiber, modified bamboo original fiber and antibacterial and moisture-proof fabric. The bamboo original fiber is first modified by an oxidant, then graphene oxide is grafted with the bamboo original fiber through ultrasonic dispersion, and then rosin-based quaternary ammonium salt and aliphatic polyurethane are successively grafted with graphene oxide to obtain the modified bamboo original fiber. This method first grafts graphene oxide onto the surface of bamboo original fiber, and then grafts and modifies graphene oxide by ultrasonic method. The reaction conditions are not easy to be popularized and the difficulty is relatively high. Summary of the Invention

[0007] Based on this, the purpose of the present invention is to provide a modified textile material with antibacterial, deodorizing and acaricidal functions and excellent mechanical properties. The present invention also provides a preparation method of a modified textile material, which enhances its antibacterial performance by quaternary ammonium salt-modified graphene oxide, grafts a silane coupling agent onto the surface of graphene to increase its reaction sites, and makes the quaternized graphene combine with the fiber substrate in the form of chemical bonds through post-finishing to increase the fastness and realize a wash-resistant antibacterial textile material.

[0008] To achieve the above purpose, the present invention adopts the following technical solutions:

[0009] The present invention provides a modified textile material, which is characterized in that it includes a modified cotton thread / cloth material, a modified regenerated fiber cloth material, a modified polyester cloth / filling material or a modified nylon cloth material, and uses quaternized graphene with active functional groups and a fiber substrate as the main raw materials, and is mainly prepared by chemical grafting reaction; it has antibacterial, deodorizing and acaricidal functions and excellent mechanical properties, wherein:

[0010] The quaternized graphene with active functional groups mainly uses graphene oxide, modified quaternary ammonium salt and silane coupling agent as the main raw materials. Under certain conditions, a quaternized graphene oxide intermediate is first prepared by reacting the modified quaternary ammonium salt with graphene oxide according to an addition ratio of 8-3:1 by weight, and then the quaternized graphene oxide intermediate reacts with the silane coupling agent according to an addition ratio of 1:1-7 by weight to obtain it;

[0011] The fiber substrate includes any one of cotton fiber, regenerated fiber, polyester fiber and nylon fiber.

[0012] Furthermore, the present invention also provides a modified material with cotton fiber as the substrate, including modified cotton thread or cotton cloth, which has antibacterial function. After washing 50 times, the antibacterial rates against Staphylococcus aureus and Escherichia coli are >99%, and the antibacterial rate against Candida albicans is >90%; it has deodorizing function, and the elimination rates of ammonia and acetic acid are respectively >90%; it has acaricidal function, and the repellency rate against mites is >60%; it has excellent mechanical properties, the pilling resistance performance reaches level 4, and the breaking strength in the warp and weft directions is >60N.

[0013] Further, the present invention also provides a modified material based on regenerated fiber, including a modified regenerated fiber cloth material, which has antibacterial function. After washing 50 times, the antibacterial rate against Staphylococcus aureus and Escherichia coli is > 99%, and the antibacterial rate against Candida albicans is > 90%.

[0014] Further, the present invention also provides a modified polyester fiber cloth or a modified polyester fiber filling material based on polyester fiber, which has antibacterial function. After washing 50 times, it still meets the antibacterial requirement of AAA level.

[0015] Further, the present invention also provides a modified nylon cloth material based on nylon fiber, which has antibacterial function. After washing 50 times, it still meets the antibacterial requirement of AAA level.

[0016] Further, the present invention provides a method for preparing a modified textile material, which is characterized by comprising the following steps:

[0017] A: Pretreatment of fiber substrate:

[0018] According to the characteristics of the fiber substrate, the fiber substrate is pretreated by methods such as alkali washing and soaking or plasma treatment. Among them, when the cotton fiber or regenerated fiber is used as the substrate, the fiber does not need to be pretreated, so the step A is not an essential step.

[0019] B: Preparation of quaternized graphene oxide intermediate:

[0020] Ultrasonically disperse graphene oxide in an ethanol solution, place the modified quaternary ammonium salt in the graphene oxide, react at 65 °C - 70 °C for 24 h. After the reaction ends, centrifuge to remove the supernatant, and ultrasonically wash three times with 75% ethanol solution and purified water respectively to fully remove the unreacted modified quaternary ammonium salt, obtaining the quaternized graphene oxide intermediate;

[0021] Among them, the addition ratio of the modified quaternary ammonium salt to graphene oxide is 8 - 3:1, calculated by weight ratio;

[0022] The modified quaternary ammonium salt includes any one or several of 3-(trimethoxysilylpropyl) dimethyloctadecylammonium chloride, 3-(triethoxysilylpropyl) dimethyloctadecylammonium chloride, and 3-(trihydroxysilylpropyl) dimethyloctadecylammonium chloride;

[0023] The graphene oxide includes any one of graphene oxide powder, 0.5 mg / mL graphene oxide dispersion, 1 mg / mL graphene oxide dispersion, and 2 mg / mL graphene oxide dispersion; in the preparation process, a self-made graphene oxide dispersion can be used. Specifically, ethanol is used as a solvent, and graphene oxide powder is added in proportion, and different concentrations of dispersions can be prepared after ultrasonic dispersion; or commercially available graphene oxide dispersions of different specifications can be directly purchased, such as 0.5 mg / mL graphene oxide dispersion, 1 mg / mL graphene oxide dispersion, and 2 mg / mL graphene oxide dispersion.

[0024] C: Preparation of quaternized graphene with active functional groups:

[0025] The quaternized graphene oxide intermediate prepared in step B is ultrasonically dispersed in an ethanol solution, a silane coupling agent is added, and the reaction is carried out at 65 °C - 70 °C for 24 h. After the reaction is completed, the supernatant is removed by centrifugation, and it is ultrasonically washed three times with 75% ethanol solution and purified water respectively to fully remove the unreacted silane coupling agent, and then vacuum dried to obtain quaternized graphene with active functional groups;

[0026] Among them, the addition ratio of the quaternized graphene oxide intermediate to the silane coupling agent is 1:1 - 7, calculated by weight ratio; the silane coupling agent includes any one or several of γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane.

[0027] D: Chemical grafting reaction:

[0028] First, the quaternized graphene with active functional groups prepared in step C is dispersed in an aqueous solution and hydrolyzed in the aqueous solution for 24 h to form a hydrolysis solution. Secondly, the untreated or pre-treated fiber substrate in step A is impregnated and rolled in the hydrolysis solution to prepare a modified textile material.

[0029] Furthermore, the present invention provides a modified material based on cotton fiber or regenerated fiber, including a preparation method for modified cotton thread, modified cotton cloth or modified regenerated fiber cloth material. It is characterized in that pretreatment through step A is not required; among them, the concentration of the quaternized graphene with active functional groups in step D is 0.5 - 1.5 wt%, the dispersion time is 10 - 20 min, the impregnation time is 1 - 30 min, the fiber weight gain after rolling is 40% - 70%, the curing temperature is 110 - 140 °C, and the curing time is 3 - 8 min.

[0030] Furthermore, the present invention also provides a method for preparing a modified polyester fiber cloth or a modified polyester fiber filling material based on polyester fibers, characterized in that the pretreatment in step A is specifically as follows: alkali hydrolysis is carried out in a 0.1M alkaline aqueous solution, the reaction conditions are 50-70°C, the reaction time is 0.5-3h, and after the reaction is completed, it is washed with a 1M acidic solution until the pH is neutral; in step D, the concentration of quaternized graphene with active functional groups is 0.6-2wt%, the dispersion time is 20-30min, the impregnation time is 1-30 min, the weight gain of the polyester fiber cloth after rolling is 10%-30%, the curing temperature is 100-120°C, and the curing time is 6-10 min.

[0031] Furthermore, the present invention also provides a method for preparing a modified nylon cloth material based on nylon fibers, characterized in that the pretreatment in step A is specifically as follows: treatment is carried out in a plasma device, oxygen is introduced into the device, the vacuum degree is 50-60Pa, the power is 400w, and the treatment time is 15-30min; in step D, the concentration of quaternized graphene with active functional groups is 1-3wt%, the dispersion time is 20-30min, the impregnation time is 1-30 min, the weight gain of the nylon fiber cloth after rolling is 5%-20%, the curing temperature is 80-100°C, and the curing time is 10-15 min.

[0032] Furthermore, the modified cotton thread, modified cotton cloth or modified regenerated fiber cloth materials provided by the present invention can be widely used as raw materials in textiles such as socks, towels, and bath towels; the provided modified regenerated fiber cloth materials can be widely used as raw materials in textiles such as underwear, lining for suits, and lining for coats; the provided modified polyester fiber cloth, modified polyester fiber filling materials or modified nylon cloth materials can be widely used as raw materials in textiles such as four-piece sets for beds, pillow core fillers, and quilt core fillers.

[0033] The beneficial effects of the present invention are:

[0034] 1. The high specific surface area of graphene oxide can effectively adsorb small odor molecules and play a deodorizing role; the excellent mechanical properties of graphene oxide can also improve the wear resistance of textiles. Quaternized graphene can not only pierce or electrostatically suck and damage the phospholipid bilayer of the bacterial envelope through the hydrophobic molecular chain of the quaternary ammonium salt, causing the dissolution of the bacterial envelope and the leakage of cell fluid, ultimately leading to the death of bacteria; it can also effectively kill fungi such as Aspergillus repens. Mites survive by eating dandruff and need the help of fungi such as Aspergillus repens to decompose and soften it before they can digest it, thus blocking the process of converting dandruff into food for mites and achieving the effect of repelling mites.

[0035] 2. Quaternary ammonium salt-modified graphene cotton fibers and their textiles have excellent antibacterial, deodorizing, mite-repelling, wear-resistant, and mechanical properties.

[0036] 3. The quaternized graphene with active functional groups improves the antibacterial performance of graphene oxide, and at the same time endows the material with new active sites, which can undergo chemical reactions with the substrate.

[0037] 4. The modified fibers prepared by chemical grafting reaction of quaternized graphene with active functional groups with regenerated fibers, pretreated polyester fibers and nylon fibers have strong covalent bonds and are wash-resistant, and can achieve AAA-level antibacterial.

[0038] 5. The surface of polyester fibers pretreated by alkali hydrolysis has active functional groups such as generated hydroxyl groups and carboxyl groups, and esterification reactions or condensation reactions can be carried out on this basis to achieve the purpose of graft modification.

[0039] 6. Oxygen-containing functional groups such as hydroxyl groups, ether groups and carbonyl groups will be generated on the surface of nylon fibers pretreated by plasma. The quaternized graphene with active functional groups reacts with them, and there are covalent bond binding forces, van der Waals forces, electrostatic binding forces, etc. between them, making its antibacterial property more wash-resistant and not easy to fall off. Brief Description of the Drawings

[0040] In order to more clearly illustrate the technical solutions of the present invention, the drawings required for use in the following embodiments or the description of the prior art will be briefly introduced. Obviously, the drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0041] Attached Figure 1 It is a schematic diagram of the route for preparing quaternized graphene with active functional groups.

[0042] Attached Figure 2 It is an infrared spectrum of the quaternized graphene with active functional groups prepared in Example 1.

[0043] Attached Figure 3 It is a schematic diagram of the grafting reaction of cotton fibers in Example 1.

[0044] Attached Figure 4 It is an eosin identification diagram of the cotton cloth washed 50 times in Example 1. Among them, the left side is the untreated cotton cloth, and the right side is the cotton cloth washed 50 times after treatment.

[0045] Attached Figure 5 It is a schematic diagram of the grafting reaction of regenerated fibers, polyester fibers and nylon fibers in Examples 8-10. Embodiments

[0046] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the accompanying drawings. All the described embodiments are implemented on the premise of the technical solutions of the present invention, and the detailed implementation processes are given. However, it should be stated that the protection scope of the present invention is not limited to the following embodiments. Example 1

[0047] Take 50 mL of 2 mg / mL graphene oxide (GO) dispersion and place it in a round-bottom flask. Ultrasonically disperse it for 15 min. After it is evenly dispersed, add 0.5 g of modified quaternary ammonium salt (3-(trimethoxysilyl)propyl octadecyl ammonium chloride), and react at 65 °C for 24 h. After the reaction is completed, centrifuge to remove the upper layer solution. The residual solid is washed with 75% ethanol solution and purified water respectively until the pH is neutral, and then placed in a vacuum oven and dried overnight at 60 °C to obtain the quaternized graphene oxide intermediate GO-QAC powder.

[0048] Take 100 mg of GO-QAC and disperse it in 50 mL of ethanol solvent. Ultrasonically disperse it for 10 min. After it is evenly dispersed, add 0.6 g of γ-aminopropyltriethoxysilane (KH550), and react at 65 °C for 24 h. After the reaction is completed, centrifuge to remove the upper layer solution. The residual solid is washed with 75% ethanol solution and purified water respectively until the pH is neutral, and then placed in a vacuum oven and dried overnight at 60 °C to obtain the quaternized graphene oxide with active functional groups GO-QAC-KH550 powder.

[0049] After the quaternized graphene oxide with active functional groups was synthesized, infrared characterization was carried out on it, as Figure 2 shown. In the figure, a, b, and c are the infrared spectra of GO, GO-QAC, and GO-QAC-KH550 respectively. In Figure 2 (a), there is a relatively wide and strong absorption peak near 3407 cm -1 , which belongs to the stretching vibration peak of -OH in graphene oxide. The C=O stretching vibration peak, C-OH bending vibration absorption peak, and C-O-C vibration absorption peak on the carboxyl group are near 1734 cm -1 , 1637 cm -1 , and 1090 cm -1 respectively, all of which are characteristic absorption peaks of graphene oxide. In Figure 2 (b), for GO-QAC, there are peaks at 2931 cm -1 , 2856 cm -1 , 1466 cm -1 , and 958 cm -1New characteristic absorption peaks appear, which respectively belong to the stretching vibration peaks of methyl and methylene groups on the quaternary ammonium salt, the antisymmetric bending vibration absorption peaks of methyl / methylene groups, and the characteristic absorption peaks of the quaternary ammonium salt, indicating that the quaternary ammonium salt has been successfully grafted onto the surface of graphene oxide. At Figure 2 In (c), the C=O stretching vibration peak of graphene oxide at 1734 cm -1 is significantly weakened, indicating that the -COOH of graphene oxide reacts with the amino group of KH550. In addition, a strong Si-O-CH3(CH2-) absorption peak appears at 1192 cm -1 , further verifying that the silane coupling agent KH550 has a grafting reaction with GO-QAC. The above infrared results show that the present invention has successfully prepared quaternized graphene with active functional groups through the quaternary ammonium salt and the coupling agent KH550.

[0050] Take 1 g of quaternized graphene with active functional groups and disperse it in 100 mL of ethanol solvent, and ultrasonically disperse for 15 min. Immerse ordinary cotton cloth in this solution, take it out after soaking for 2 min, remove the excess water, and dry it in an oven at 120 °C for 3 - 5 min to obtain the cotton cloth modified with quaternized graphene with active functional groups. Example 2

[0051] Take 100 mL of 1 mg / ml graphene oxide (GO) dispersion and place it in a round-bottom flask, ultrasonically disperse for 25 min. After it is evenly dispersed, add 0.4 g of modified quaternary ammonium salt (3-(triethoxysilylpropyl)dimethyloctadecylammonium chloride), and react at 70 °C for 24 h. After the reaction is completed, centrifuge to remove the upper solution, and wash the residual solid with 75% ethanol solution and purified water respectively until the pH is neutral, and place it in a vacuum box and dry overnight at 60 °C to obtain the quaternized graphene oxide intermediate GO-QAC powder.

[0052] Take 100 mg of GO-QAC and disperse it in 50 mL of ethanol solvent, ultrasonically disperse for 10 min. After it is evenly dispersed, add 0.3 g of γ-aminopropyltriethoxysilane (KH550), and react at 65 °C for 24 h. After the reaction is completed, centrifuge to remove the upper solution, and wash the residual solid with 75% ethanol solution and purified water respectively until the pH is neutral, and place it in a vacuum box and dry overnight at 60 °C to obtain the quaternized graphene GO-QAC-KH550 powder with active functional groups.

[0053] Take 1 g of quaternized graphene with active functional groups and disperse it in 100 mL of ethanol solvent, and ultrasonically disperse for 15 min. Immerse ordinary cotton cloth in this solution, take it out after soaking for 2 min, remove the excess water, and dry it in an oven at 120 °C for 3 - 5 min to obtain the cotton cloth modified with quaternized graphene with active functional groups. Example 3

[0054] Take 100 mg of graphene oxide (GO) and disperse it in 50 mL of ethanol solvent. Ultrasonically disperse for 45 min, add 0.3 g of modified quaternary ammonium salt (3-(trihydroxysilylpropyl)dimethyloctadecylammonium chloride), and react at 70 °C for 24 h. After the reaction is completed, centrifuge to remove the upper layer solution. Wash the remaining solid with 75% ethanol solution and purified water respectively until the pH is neutral. Place it in a vacuum oven and dry overnight at 60 °C to obtain quaternized graphene oxide intermediate GO-QAC powder.

[0055] Take 100 mg of GO-QAC and disperse it in 50 mL of ethanol solvent. Ultrasonically disperse for 10 min. After it is evenly dispersed, add 0.1 g of γ-aminopropyltriethoxysilane (KH550), and react at 65 °C for 24 h. After the reaction is completed, centrifuge to remove the upper layer solution. Wash the remaining solid with 75% ethanol solution and purified water respectively until the pH is neutral. Place it in a vacuum oven and dry overnight at 60 °C to obtain quaternized graphene with active functional groups GO-QAC-KH550 powder.

[0056] Take 1 g of quaternized graphene with active functional groups and disperse it in 100 mL of ethanol solvent. Ultrasonically disperse for 15 min. Immerse ordinary cotton cloth in this solution, take it out after soaking for 2 min, remove the excess moisture, and dry it in an oven at 120 °C for 3 - 5 min to obtain cotton cloth modified with quaternized graphene with active functional groups. Example 4

[0057] Take 200 mL of 0.5 mg / ml graphene oxide (GO) dispersion and place it in a round-bottom flask. Ultrasonically disperse for 35 min. After it is evenly dispersed, add 0.5 g of modified quaternary ammonium salt (3-(trimethoxysilyl)propyl octadecylammonium chloride), and react at 70 °C for 24 h. After the reaction is completed, centrifuge to remove the upper layer solution. Wash the remaining solid with 75% ethanol solution and purified water respectively until the pH is neutral. Place it in a vacuum oven and dry overnight at 60 °C to obtain quaternized graphene oxide intermediate GO-QAC powder.

[0058] Take 100 mg of GO-QAC and disperse it in 50 mL of ethanol solvent. Ultrasonically disperse for 10 min. After it is evenly dispersed, add 0.4 g of γ-aminopropyltriethoxysilane (KH550), and react at 65 °C for 24 h. After the reaction is completed, centrifuge to remove the upper layer solution. Wash the remaining solid with 75% ethanol solution and purified water respectively until the pH is neutral. Place it in a vacuum oven and dry overnight at 60 °C to obtain quaternized graphene with active functional groups GO-QAC-KH550 powder.

[0059] Take 1 g of quaternized graphene with active functional groups and disperse it in 100 mL of ethanol solvent, and ultrasonically disperse for 15 min. Immerse ordinary cotton cloth in this solution, take it out after soaking for 2 min, remove the excess water, and dry it in an oven at 120 °C for 3 - 5 min to obtain the cotton cloth modified with quaternized graphene with active functional groups. Example 5

[0060] Take 50 mL of 2 mg / ml graphene oxide (GO) dispersion and place it in a round-bottom flask, ultrasonically disperse for 15 min. After it is evenly dispersed, add 0.5 g of modified quaternary ammonium salt (3-(trimethoxysilyl)propyl octadecyl ammonium chloride), and react at 70 °C for 24 h. After the reaction is completed, centrifuge to remove the upper layer solution, and wash the residual solid with 75% ethanol solution and purified water respectively until the pH is neutral, and place it in a vacuum box to dry overnight at 60 °C to obtain the quaternized graphene oxide intermediate GO-QAC powder.

[0061] Take 100 mg of GO-QAC and disperse it in 50 mL of ethanol solvent, ultrasonically disperse for 10 min. After it is evenly dispersed, add 0.5 g of γ-aminopropyltriethoxysilane (KH550), and react at 65 °C for 24 h. After the reaction is completed, centrifuge to remove the upper layer solution, and wash the residual solid with 75% ethanol solution and purified water respectively until the pH is neutral, and place it in a vacuum box to dry overnight at 60 °C to obtain the quaternized graphene with active functional groups GO-QAC-KH550 powder.

[0062] Take 1 g of quaternized graphene with active functional groups and disperse it in 100 mL of ethanol solvent, and ultrasonically disperse for 15 min. Immerse ordinary cotton cloth in this solution, take it out after soaking for 2 min, remove the excess water, and dry it in an oven at 120 °C for 3 - 5 min to obtain the cotton cloth modified with quaternized graphene with active functional groups. Example 6

[0063] Take 50 mL of 2 mg / ml graphene oxide (GO) dispersion and place it in a round-bottom flask, ultrasonically disperse for 15 min. After it is evenly dispersed, add 0.5 g of modified quaternary ammonium salt (3-(trimethoxysilyl)propyl octadecyl ammonium chloride), and react at 70 °C for 24 h. After the reaction is completed, centrifuge to remove the upper layer solution, and wash the residual solid with 75% ethanol solution and purified water respectively until the pH is neutral, and place it in a vacuum box to dry overnight at 60 °C to obtain the quaternized graphene oxide intermediate GO-QAC powder.

[0064] Disperse 100 mg of GO-QAC in 50 mL of ethanol solvent, and ultrasonically disperse for 10 min. After it is evenly dispersed, add 0.5 g of γ-glycidoxypropyltrimethoxysilane (KH560), and react at 40 °C for 12 h. After the reaction is completed, centrifuge to remove the upper layer solution, and wash the residual solid with 75% ethanol solution and purified water respectively until the pH is neutral. Place it in a vacuum oven and dry overnight at 60 °C to obtain quaternized graphene oxide GO-QAC-KH560 powder with active functional groups.

[0065] Disperse 1 g of quaternized graphene oxide with active functional groups in 100 mL of ethanol solvent, and ultrasonically disperse for 15 min. Immerse ordinary cotton cloth in this solution, take it out after soaking for 2 min, remove the excess water, and dry it in an oven at 120 °C for 3 - 5 min to obtain cotton cloth modified with quaternized graphene oxide with active functional groups. Example 7

[0066] Place 50 mL of 2 mg / ml graphene oxide (GO) dispersion in a round-bottom flask, ultrasonically disperse for 15 min. After it is evenly dispersed, add 0.5 g of modified quaternary ammonium salt (3-(trimethoxysilyl)propyl octadecyl ammonium chloride), and react at 70 °C for 24 h. After the reaction is completed, centrifuge to remove the upper layer solution, and wash the residual solid with 75% ethanol solution and purified water respectively until the pH is neutral. Place it in a vacuum oven and dry overnight at 60 °C to obtain quaternized graphene oxide intermediate GO-QAC powder.

[0067] Disperse 100 mg of GO-QAC in 50 mL of ethanol solvent, and ultrasonically disperse for 10 min. After it is evenly dispersed, add 0.5 g of γ-methacryloxypropyltrimethoxysilane (KH570), and react at 60 °C for 8 h. After the reaction is completed, centrifuge to remove the upper layer solution, and wash the residual solid with 75% ethanol solution and purified water respectively until the pH is neutral. Place it in a vacuum oven and dry overnight at 60 °C to obtain quaternized graphene oxide GO-QAC-KH570 powder with active functional groups.

[0068] Disperse 1 g of quaternized graphene oxide with active functional groups in 100 mL of ethanol solvent, and ultrasonically disperse for 15 min. Immerse ordinary cotton cloth in this solution, take it out after soaking for 2 min, remove the excess water, and dry it in an oven at 120 °C for 3 - 5 min to obtain cotton cloth modified with quaternized graphene oxide with active functional groups. Example 8

[0069] The preparation method of the quaternized graphene oxide with active functional groups is the same as that in Example 1.

[0070] Disperse 100 mg of quaternized graphene with active functional groups in 100 mL of ethanol solvent and ultrasonically disperse for 15 min. Immerse ordinary regenerated fiber fabric into this solution, take it out after soaking for 30 s, remove the excess moisture, and dry it in an oven at 120 °C for 3 - 5 min to obtain the regenerated fiber fabric modified with quaternized graphene with active functional groups. Example 9

[0071] The preparation method of the quaternized graphene with active functional groups is the same as that in Example 1.

[0072] Disperse 120 mg of quaternized graphene with active functional groups in 100 mL of ethanol solvent and ultrasonically disperse for 20 min.

[0073] Put ordinary polyester fiber fabric into 1 mol / L NaOH solution, react at 70 °C for 30 min at a rotation speed of 500 rpm, and then take out the polyester fabric. Wash it with 1 mol / L HCl until the pH is neutral, then wash it with water and dry it under reduced pressure at 30 °C to obtain the polyester fabric with surface hydrolysis. Immerse it into the quaternized graphene solution with active functional groups, take it out after soaking for 90 s, remove the excess moisture, and dry it in an oven at 110 °C for 6 - 10 min to obtain the polyester fiber fabric modified with quaternized graphene with active functional groups. Example 10

[0074] The preparation method of the quaternized graphene with active functional groups is the same as that in Example 1.

[0075] Disperse 150 mg of quaternized graphene with active functional groups in 100 mL of ethanol solvent and ultrasonically disperse for 25 min.

[0076] Put ordinary nylon fiber fabric into a plasma device, fill it with oxygen, the vacuum degree is 50 - 60 Pa, process it at a power of 400 w for 900 s, and take out the processed nylon fabric. Immerse it into the quaternized graphene solution with active functional groups, take it out after soaking for 120 s, remove the excess moisture, and dry it in an oven at 90 °C for 10 - 15 min to obtain the nylon fiber fabric modified with quaternized graphene with active functional groups.

[0077] Comparative Example 1:

[0078] Ordinary cotton fabric without any treatment.

[0079] Comparative Example 2:

[0080] Take 50 mL of 2 mg / mL graphene oxide (GO) dispersion and place it in a round-bottom flask. Ultrasonically disperse it for 15 min. After it is evenly dispersed, immerse ordinary cotton cloth into the solution. Take it out after soaking for 30 s, remove the excess water, and dry it in an oven at 120 °C for 3 - 5 min to obtain the cotton cloth treated with graphene oxide.

[0081] The properties of the modified textile materials described in the present invention are tested by the following methods:

[0082] Test 1: Antibacterial property test

[0083] The test objects for bacteria and fungi include: The experiment is carried out in accordance with "GB / T 20944.3 - 2008 Textiles - Evaluation of antibacterial properties - Part 3: Oscillation method", and the test bacterial strains are Escherichia coli 8099, Staphylococcus aureus ATCC 6538, and Candida albicans ATCC 10231.

[0084] Sample treatment: Take 3 samples from each of the fabrics in Examples 1 - 10 and Comparative Examples 1 - 2, wash them 50 times according to the method in Appendix C of the standard "FZ / T 73023 - 2006 Antibacterial knitted fabrics" using AATCC 1993WOB detergent, and then dry them for standby.

[0085] Test steps: Sterilize the samples after washing 50 times in the examples, put them into Erlenmeyer flasks, add PBS buffer solution and inoculate the bacterial solution, shake and dilute on a constant temperature shaker, transfer the liquid in the flask into a sterilized petri dish, pour nutrient agar medium or Sabouraud agar medium, invert the plate after solidifying at room temperature, and culture at 37 °C ± 1 °C for 24 h - 48 h (48 h - 72 h for Candida albicans), record the number of colonies in each plate, and calculate the antibacterial rate according to the formula in the standard.

[0086] The antibacterial rates of Examples 1 - 7 and Comparative Examples 1 - 2 are shown in Table 1.

[0087] Table 1 Antibacterial rate results of Examples 1 - 7 and Comparative Examples 1 - 2

[0088] Sample (washed 50 times) Inhibitory rate against Staphylococcus aureus Inhibitory rate against Escherichia coli Inhibitory rate against Candida albicans Example 1 99.97% 99.90% 98.20% Example 2 99.27% 99.55% 94.30% Example 3 99.18% 99.53% 91.90% Example 4 99.95% 99.87% 96.80% Example 5 99.73% 99.80% 95.40% Example 6 98.30% 98.63% 90.72% Example 7 98.51% 98.82% 91.30% Comparative Example 1 0% 0% 0% Comparative Example 2 65.74% 58.5% 43.5%

[0089] Compared with the antibacterial data of untreated cotton cloth and cotton cloth treated with ordinary graphene oxide, the quaternized graphene grafted and modified cotton fibers still have good antibacterial effects on Staphylococcus aureus, Escherichia coli, and Candida albicans after multiple washings.

[0090] The antibacterial rates of Examples 8 - 10 are shown in Table 2.

[0091] Table 2 Antibacterial rate results of Examples 8 - 10

[0092] Sample (washed 50 times) Inhibitory rate against Staphylococcus aureus Inhibitory rate against Escherichia coli Inhibitory rate against Candida albicans Example 8 99.88% 99.3% 89.34% Example 9 91.30% 85.76% 80.85% Example 10 92.8% 87.85% 82.88%

[0093] According to the definition of the standard "FZ / T 73023-2006 Antibacterial Knitted Fabrics", after 50 washes, if the antibacterial rate against Staphylococcus aureus is ≥80%, the antibacterial rate against Escherichia coli is ≥70%, and the antibacterial rate against Candida albicans is ≥60%, it can be determined that the product has an AAA-level antibacterial grade.

[0094] Quaternized graphene graft-modified regenerated fiber, polyester fiber and nylon fiber still have good antibacterial effects against Staphylococcus aureus, Escherichia coli and Candida albicans after multiple washes.

[0095] Test 2: Deodorization performance test

[0096] The deodorization performance of the sample against ammonia and acetic acid was tested according to "GB / T 33610.2-2017 Textiles - Determination of deodorization performance - Part 2: Detecting tube method".

[0097] The deodorization performance data of Example 1 and Comparative Example 1 are shown in Table 3.

[0098] Table 3 Deodorization performance data of examples and comparative examples

[0099] Sample Ammonia elimination rate Acetic acid elimination rate Example 1 94% 90.5% Comparative Example 1 87.7% 66.7%

[0100] Compared with the deodorization performance data of the untreated cotton cloth in Comparative Example 1, the quaternized graphene graft-modified cotton cloth has good deodorization effects against ammonia and acetic acid. It not only has good antibacterial properties but also has excellent deodorization performance.

[0101] Test 3: Anti-mite performance test

[0102] The anti-mite performance of the sample was tested according to the repellency method in "GB / T 24253-2009 Textiles - Evaluation of anti-mite performance".

[0103] After testing, the repellency rate of the quaternized graphene graft-modified cotton cloth in Example 1 against mites is 64%. According to the standard, the repellency rate >60%, indicating that the sample has an anti-mite effect.

[0104] Test 4: Pilling resistance test

[0105] The pilling and fuzzing performance and surface changes of the sample were determined according to "GB / T 4802.2-2008 Textiles - Determination of fabric fuzzing and pilling performance - Part 2: Modified Martindale method".

[0106] The pilling resistance data of Example 1 and Comparative Example 1 are shown in Table 4.

[0107] Table 4 Pilling resistance data of examples and comparative examples

[0108] Sample Appearance change Grade Example 1 There is slight pilling on the surface of the specimen Grade 4 Comparative Example 1 The pilling on the surface of the specimen is obvious and belongs to moderate pilling Grade 3

[0109] Compared with the pilling resistance performance data of the untreated cotton cloth in Comparative Example 1, after the quaternized graphene graft-modified cotton cloth is treated, its surface is more wear-resistant and not prone to pilling.

[0110] Test 5: Mechanical property test

[0111] The mechanical properties of the samples were determined in accordance with "GB / T 3923.1-2013 Textiles - Tensile properties of fabrics - Part 1: Determination of breaking force and elongation at break (strip method)". The size of the test specimen was 100 mm × 20 mm, and the tensile speed was 100 mm / min.

[0112] The mechanical property data of Example 1 and Comparative Example 1 are shown in Table 5.

[0113] Table 5 Mechanical property data of examples and comparative examples

[0114]

[0115] Compared with the mechanical property data of the untreated cotton cloth in Comparative Example 1, after the quaternized graphene graft-modified cotton cloth is treated, the breaking strength in the warp and weft directions increases, and the increase ratio is 5% - 17%; the elongation at break decreases slightly, and the decrease ratio is 7% - 9.4%. Generally speaking, its breaking strength is improved, especially the breaking strength in the warp direction is improved significantly.

[0116] It can be seen from the test data of the examples that after the modified graphene is used to treat cotton fibers, regenerated fibers, polyester fibers and nylon fibers, it has good antibacterial properties and is wash-resistant. Moreover, due to its high specific surface area and other characteristics, it can endow the material with better adsorption properties, thus improving the deodorization effect. At the same time, for cotton fibers, its wear resistance and mechanical properties can also be improved after treatment, greatly improving its application and popularization prospects.

[0117] The above description of the disclosed embodiments enables those skilled in the art to implement or use the present invention. Various modifications to these embodiments will be obvious to those skilled in the art, and the general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to these embodiments shown herein, but will be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A preparation method of a modified textile material, characterized in that: It includes the following steps: A: Pretreatment of fiber substrate: According to the characteristics of the fiber substrate, the fiber substrate is pretreated by alkali washing and soaking or plasma treatment method; among them, the step A is not an essential step; Among them, the fiber substrate includes any one of cotton fiber, regenerated fiber, polyester fiber, and nylon fiber; B: Preparation of quaternized graphene oxide intermediate: Ultrasonically disperse graphene oxide in an ethanol solution, place the modified quaternary ammonium salt in the graphene oxide, react at 65°C - 70°C for 24 h, after the reaction is completed, centrifuge to remove the supernatant, and ultrasonically wash three times with 75% ethanol solution and purified water respectively to fully remove the unreacted modified quaternary ammonium salt to obtain the quaternized graphene oxide intermediate; Among them, the addition ratio of the modified quaternary ammonium salt to graphene oxide is 8 - 3:1, calculated by weight ratio, and the modified quaternary ammonium salt includes any one or several of 3-(trimethoxysilylpropyl) dimethyloctadecylammonium chloride, 3-(triethoxysilylpropyl) dimethyloctadecylammonium chloride, and 3-(trihydroxysilylpropyl) dimethyloctadecylammonium chloride; The graphene oxide is selected from any one of graphene oxide powder, 0.5mg / mL graphene oxide dispersion, 1mg / mL graphene oxide dispersion, and 2mg / mL graphene oxide dispersion; C: Preparation of quaternized graphene with active functional groups: Ultrasonically disperse the quaternized graphene oxide intermediate prepared in step B in an ethanol solution, add a silane coupling agent, react at 65°C - 70°C for 24 h, after the reaction is completed, centrifuge to remove the supernatant, and ultrasonically wash three times with 75% ethanol solution and purified water respectively to fully remove the unreacted silane coupling agent, and vacuum dry to obtain quaternized graphene with active functional groups; Among them, the silane coupling agent includes γ-aminopropyltriethoxysilane; Among them, the addition ratio of the quaternized graphene oxide intermediate to the silane coupling agent is 1:1 - 7, calculated by weight ratio; D: Chemical grafting reaction: First, disperse the quaternized graphene with active functional groups prepared in step C in an aqueous solution, hydrolyze in the aqueous solution for 24 h to form a hydrolysis solution, and then prepare a modified textile material by impregnating and rolling the untreated or pretreated fiber substrate in step A in the hydrolysis solution; Among them, when the fiber substrate is cotton fiber or regenerated fiber, the concentration of the quaternized graphene with active functional groups is 0.5 - 1.5wt%, the dispersion time is 10 - 20min, the impregnation time is 1 - 30 min, the fiber weight gain after rolling is 40% - 70%, the curing temperature is 110 - 140°C, and the curing time is 3 - 8 min; Or when the fiber substrate is polyester fiber, the concentration of the quaternized graphene with active functional groups is 0.6 - 2wt%, the dispersion time is 20 - 30min, the impregnation time is 1 - 30 min, the weight gain of the polyester fiber fabric after rolling is 10% - 30%, the curing temperature is 100 - 120°C, and the curing time is 6 - 10 min; Or the fiber substrate is nylon fiber; the concentration of quaternized graphene with active functional groups is 1-3 wt%, the dispersion time is 20-30 min, the impregnation time is 1-30 min, the weight gain of the nylon fiber fabric after rolling is 5%-20%, the curing temperature is 80-100 °C, and the curing time is 10-15 min.

2. The preparation method according to claim 1, characterized in that, The fiber substrate is cotton fiber or regenerated fiber and does not need to be pretreated through step A.

3. The preparation method according to claim 1, characterized in that, The fiber substrate is polyester fiber; wherein, the pretreatment in step A is specifically: alkali hydrolysis is carried out in a 0.1 M alkaline aqueous solution, the reaction conditions are 50-70 °C, the reaction time is 0.5-3 h, and after the reaction is completed, it is washed with a 1 M acidic solution until the pH is neutral.

4. The preparation method according to claim 1, wherein The fiber substrate is nylon fiber; wherein, the pretreatment in step A is specifically: treatment is carried out in a plasma device, oxygen is introduced into the device, the vacuum degree is 50-60 Pa, the power is 400 w, and the treatment time is 15-30 min.

5. A modified textile material prepared by the preparation method according to any one of claims 1-4.

6. The modified textile material according to claim 5, characterized in that: Including modified cotton thread / cloth material, modified regenerated fiber cloth material, modified polyester cloth / filling material or modified nylon cloth material, having antibacterial, deodorizing and acaricidal functions and excellent mechanical properties.

7. The modified textile material according to claim 5, characterized in that: Having antibacterial function, after washing 50 times, the antibacterial rates against Staphylococcus aureus and Escherichia coli are >99%, and the antibacterial rate against Candida albicans is >90%; having deodorizing function, the elimination rates of ammonia and acetic acid are respectively >90%; having acaricidal function, the repellency rate against mites is >60%; having excellent mechanical properties, the pilling resistance performance reaches grade 4, and the breaking strength in the warp and weft directions is >60 N; the fiber substrate is cotton fiber.

8. The modified textile material according to claim 5, characterized in that: Having antibacterial function, after washing 50 times, the antibacterial rates against Staphylococcus aureus and Escherichia coli are >99%, and the antibacterial rate against Candida albicans is >90%; the fiber substrate is regenerated fiber.

9. The modified textile material according to claim 5, characterized in that: Having antibacterial function, still meeting the AAA-level antibacterial requirements after washing 50 times; the fiber substrate is any one of polyester fiber or nylon fiber.

10. Application of a modified textile material according to claim 7 as a raw material in textiles such as socks, towels, and bath towels.

11. Application of a modified textile material according to claim 8 as a raw material in textiles such as underwear, lining of suits, and lining of overcoats.

12. Application of a modified textile material according to claim 9 as a raw material in textiles such as four-piece sets for beds, pillow core fillers, and quilt core fillers.

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