Graphene skin-friendly warm fabric and preparation method thereof

Abstract

The application provides a graphene skin-friendly warm-keeping fabric and a preparation method thereof, raw materials of the graphene skin-friendly warm-keeping fabric include a fabric and a sizing material, the sizing material includes components with mass fractions as follows: 30-60 parts of organic resin, 1-10 parts of modified graphene, 1-5 parts of amino-modified titanium dioxide, 2-10 parts of chitosan, 0.2-2 parts of a crosslinking agent, 0.1-2 parts of an additive, 50-100 parts of a solvent; wherein the modified graphene is a product of reaction of polyethyleneimine and graphene oxide. The application effectively enhances the heat preservation, bacteriostasis and stability of the fabric, endows the product with excellent comprehensive performance, meets the performance requirements of the market on the warm-keeping fabric, and has a good application prospect in cold-proof and warm-keeping clothes.

Description

Technical Field

[0001] This invention relates to the field of textile materials technology, and in particular to a graphene-based skin-friendly and warm fabric and its preparation method. Background Technology

[0002] With the improvement of people's living standards, the market demand for skin-friendly and warm fabrics is growing, especially for multifunctional fabrics that combine warmth, antibacterial properties, washability, and skin-friendliness. Currently, the warming finishing of textile fabrics mostly adopts traditional fiber blending or coating processes, which have problems such as insufficient warmth, poor breathability, and short-lived antibacterial effects, making it difficult to meet consumers' comprehensive requirements for high-quality fabrics.

[0003] Graphene, as a novel nanomaterial, possesses excellent thermal conductivity, heat retention, antibacterial properties, and mechanical properties, showing broad application prospects in the textile field. However, unmodified graphene is prone to agglomeration and has poor compatibility with fabric fibers, resulting in its inability to fully realize its functions and insufficient stability. Titanium dioxide has good antibacterial and UV protection properties, while chitosan possesses excellent skin affinity, biocompatibility, and antibacterial effects. Both are often used for fabric functional modification, but when used alone, they suffer from limitations such as limited functionality and weak bonding with fibers, restricting their application scope.

[0004] Aerogels have extremely high porosity, lightweight properties and excellent thermal insulation performance, which can effectively improve the warmth of fabrics. Existing technologies have attempted to apply aerogels to the textile field, but single-component aerogels or unmodified composite aerogels have problems such as weak bonding with fabrics, poor washability and insufficient functionality.

[0005] Currently, most fabric finishing agents use a single functional component mixed with resin and solvent. Although they can temporarily impart some functions to the fabric after coating, they have defects such as rapid functional decay and poor overall performance. The combination effect of each component in the system is also not ideal, making it difficult to meet the needs of the market and consumers.

[0006] Therefore, developing a technology that can effectively improve the warmth retention and antibacterial properties of fabrics has become an urgent technical problem to be solved in the current textile fabric industry. Summary of the Invention

[0007] Based on this, the present invention provides a graphene-based skin-friendly thermal fabric and its preparation method. The present invention prepares an aerogel by modifying graphene, amino-modified titanium dioxide, and chitosan with good biocompatibility, and then coats the fabric with it, which effectively enhances the thermal insulation and antibacterial properties of the fabric, endows the product with excellent comprehensive performance, meets the market's performance requirements for thermal fabric products, and has good application prospects in down jackets and other cold-proof and thermal clothing.

[0008] One object of the present invention is to provide a graphene-based skin-friendly and warm fabric, wherein the raw materials of the graphene-based skin-friendly and warm fabric include fabric and sizing agent, and the sizing agent comprises the following components in parts by weight: 30-60 parts of organic resin 1-10 parts of modified graphene 1-5 parts of amino-modified titanium dioxide 2-10 parts chitosan Crosslinking agent 0.2-2 parts 0.1-2 parts of additives Solvent 50-100 parts; in, The modified graphene is a product of the reaction between polyethyleneimine and graphene oxide.

[0009] Furthermore, the fabric is selected from one or more of natural fibers, regenerated fibers, and synthetic fibers.

[0010] Furthermore, the organic resin is selected from one or more of polyurethane resin and polyacrylic acid resin.

[0011] Furthermore, the additive is selected from one or more of the following: dispersant, wetting agent, defoamer, foaming agent, softener, thickener, and antibacterial agent.

[0012] Another object of the present invention is to provide a method for preparing the above-mentioned graphene skin-friendly and warm fabric, wherein the method for preparing the graphene skin-friendly and warm fabric includes the following steps: S1. Graphene oxide and polyethyleneimine are mixed and heated to react, resulting in modified graphene. S2. Mix titanium dioxide and silane coupling agent and heat to react to obtain amino-modified titanium dioxide; S3. The modified graphene, amino-modified titanium dioxide and chitosan are added to a solvent, then a crosslinking agent is added, the mixture is stirred and reacted, and then aged and freeze-dried to obtain graphene aerogel. S4. The graphene aerogel, organic resin, additives and solvent are mixed to obtain a slurry, which is then coated on the surface of the fabric to obtain a graphene skin-friendly and warm fabric.

[0013] Further, in step S1, the mass ratio of graphene oxide to polyethyleneimine is 1:(0.5-5).

[0014] Furthermore, in step S1, the heating reaction is carried out at a temperature of 60-100°C for 4-10 hours.

[0015] Further, in step S2, the mass ratio of the titanium dioxide to the silane coupling agent is 1:(0.1-2).

[0016] Furthermore, in step S2, the heating reaction is carried out at a temperature of 50-100°C for 1-12 hours.

[0017] Furthermore, in step S3, the aging time is 2-24 hours.

[0018] Furthermore, the silane coupling agent is APTES (γ-aminopropyltriethoxysilane).

[0019] Furthermore, the crosslinking agent is glutaraldehyde.

[0020] The present invention has the following beneficial effects: This invention discloses a graphene-based skin-friendly and warm fabric. It utilizes polyethyleneimine-modified graphene, APTES-modified titanium dioxide, and natural chitosan as raw materials, and glutaraldehyde as a crosslinking agent to prepare graphene aerogel. The resulting product possesses a porous aerogel structure, combining the thermal properties of both graphene and titanium dioxide, exhibiting excellent heat retention. The introduction of the polyethyleneimine component effectively enhances the crosslinking density of the product, allowing numerous active groups to fully crosslink through chemical and hydrogen bonds, thus improving its affinity with waterborne polyurethane resin. This not only improves the stability and strength of the aerogel but also enhances its adsorption and adhesion to the fabric. Simultaneously, the modified graphene and titanium dioxide can crosslink with chitosan to form an integrated thermal insulation network structure, preventing the aggregation of single substances and generating heat through photothermal properties, further improving the warmth retention function. Furthermore, the chitosan, graphene, and titanium dioxide of this invention all possess antibacterial properties, thus achieving a synergistic antibacterial effect through a combination of electrostatic adsorption, physical cutting, penetration, and photocatalysis, thereby endowing the fabric with excellent antibacterial properties. Detailed Implementation

[0021] To more clearly illustrate the technical solution of the present invention, the following embodiments are provided. Unless otherwise stated, the raw materials, reactions, and post-processing methods appearing in the embodiments are all commercially available raw materials and technical methods well known to those skilled in the art.

[0022] The terms "preferred," "more preferably," and "more suitable" used in this invention refer to embodiments of the invention that provide certain beneficial effects under certain circumstances. However, other embodiments may also be preferred under the same or other circumstances. Furthermore, the description of one or more preferred embodiments does not imply that other embodiments are unavailable, nor is it intended to exclude other embodiments from the scope of this invention.

[0023] It should be understood that, except in any operational instance or otherwise indicated, all figures representing the amounts of ingredients used, for example, in the specification and claims, should be understood to be modified in all cases by the term "about". Therefore, unless otherwise stated, the numerical parameters set forth in the following specification and appended claims are approximations varying with the desired performance to be obtained according to the invention.

[0024] It is worth mentioning that the product of this invention has been tested and meets the Class C requirements of the "National Basic Safety Technical Specifications for Textile Products" (GB18401-2010), and no substances harmful to the human body have been detected.

[0025] The fabric in this embodiment of the invention is 16×12 / 108×56, 270 g / m². 2 Twill cotton.

[0026] The organic resin used in this embodiment of the invention is waterborne polyurethane, Shenzhen Yoshida F0402.

[0027] The graphene oxide used in this embodiment of the invention is self-made, and the preparation method refers to the method in "2.1.2 Preparation of graphene oxide (GO)" in "Wang Hao. Preparation of carboxylated graphene oxide and its application in modified polylactic acid [D]. Zhengzhou University".

[0028] The titanium dioxide in this embodiment of the invention is P25 nano titanium dioxide.

[0029] The polyethyleneimine used in this embodiment of the invention was purchased from Maclean's, E808880.

[0030] The chitosan used in this embodiment of the invention was purchased from Maclean's, C766420.

[0031] The auxiliary agent in the embodiments of the present invention is wetting and dispersing agent PE-100.

[0032] The solvent used in this embodiment of the invention is distilled water.

[0033] In the embodiments of this invention, "parts" refers to parts by mass. Example 1

[0034] A graphene-based skin-friendly and warm fabric, wherein the raw materials of the graphene-based skin-friendly and warm fabric include fabric and sizing agent, and the sizing agent comprises the following components in parts by weight: 40 parts organic resin 4 parts of modified graphene 1 part amino-modified titanium dioxide 6 parts chitosan 0.5 parts glutaraldehyde 0.5 parts of additives 50 parts solvent; The preparation method of the above-mentioned graphene skin-friendly and warm fabric includes the following steps: S1. Mix graphene oxide and water at a mass ratio of 1:100, disperse ultrasonically for 30 min, then add polyethyleneimine (the mass ratio of polyethyleneimine to graphene oxide is 2:1), stir and react at 80℃ for 8 h, and obtain modified graphene after filtration, washing and drying. S2. Ethanol and water were mixed in a volume ratio of 9:1 to obtain a mixture. Titanium dioxide was added to the mixture at a mass ratio of 1:100 and ultrasonically dispersed for 30 min. Then, APTES (the mass ratio of titanium dioxide to APTES was 1:0.8) was added. After heating to 70℃, 2 mol / L hydrochloric acid was added to adjust the pH to 6.0. The reaction was continued at 70℃ for 6 h. After centrifugation, washing, and drying, amino-modified titanium dioxide was obtained. S3. According to the above mass proportions, add modified graphene, amino-modified titanium dioxide and chitosan to 200 parts of 2wt% acetic acid aqueous solution, sonicate for 30 min, then add glutaraldehyde, stir for 10 min, age at room temperature for 24 h, then soak and wash with water several times until the pH is neutral, and then freeze dry at -50℃ for 24 h to obtain graphene aerogel. S4. After pulverizing the graphene aerogel and passing it through a 200-mesh sieve, mix it with organic resin, additives, and solvent in the above-mentioned mass proportions and stir evenly to obtain a slurry, at a concentration of 40 g / m³. 2 The graphene coating is applied to the fabric surface, pre-baked at 90℃ for 3 minutes, and then baked at 150℃ for 5 minutes to obtain a skin-friendly and warm fabric. Example 2

[0035] A graphene-based skin-friendly and warm fabric, wherein the raw materials of the graphene-based skin-friendly and warm fabric include fabric and sizing agent, and the sizing agent comprises the following components in parts by weight: 50 parts organic resin 5 parts of modified graphene 1.3 parts of amino-modified titanium dioxide 7 parts chitosan 0.6 parts glutaraldehyde 0.6 parts of additives 60 parts solvent; The preparation method of the above-mentioned graphene skin-friendly and warm fabric includes the following steps: S1. Mix graphene oxide and water at a mass ratio of 1:100, disperse ultrasonically for 30 min, then add polyethyleneimine (the mass ratio of polyethyleneimine to graphene oxide is 2:1), stir and react at 80℃ for 8 h, and obtain modified graphene after filtration, washing and drying. S2. Ethanol and water were mixed in a volume ratio of 9:1 to obtain a mixture. Titanium dioxide was added to the mixture at a mass ratio of 1:100 and ultrasonically dispersed for 30 min. Then, APTES (the mass ratio of titanium dioxide to APTES was 1:0.8) was added. After heating to 70℃, 2 mol / L hydrochloric acid was added to adjust the pH to 6.0. The reaction was continued at 70℃ for 6 h. After centrifugation, washing, and drying, amino-modified titanium dioxide was obtained. S3. According to the above mass proportions, add modified graphene, amino-modified titanium dioxide and chitosan to 220 parts of 2wt% acetic acid aqueous solution, sonicate for 30 min, then add glutaraldehyde, stir for 10 min, age at room temperature for 24 h, then soak and wash several times with water until the pH is neutral, and then freeze dry at -50℃ for 24 h to obtain graphene aerogel. S4. After pulverizing the graphene aerogel and passing it through a 200-mesh sieve, mix it with organic resin, additives, and solvent in the above-mentioned mass proportions and stir evenly to obtain a slurry, at a concentration of 40 g / m³. 2 The graphene coating is applied to the fabric surface, pre-baked at 90℃ for 3 minutes, and then baked at 150℃ for 5 minutes to obtain a skin-friendly and warm fabric. Example 3

[0036] A graphene-based skin-friendly and warm fabric, wherein the raw materials of the graphene-based skin-friendly and warm fabric include fabric and sizing agent, and the sizing agent comprises the following components in parts by weight: 60 parts organic resin 6 parts of modified graphene 1.6 parts of amino-modified titanium dioxide 9 parts chitosan 0.7 parts glutaraldehyde 0.7 parts of additives 70 parts solvent; The preparation method of the above-mentioned graphene skin-friendly and warm fabric includes the following steps: S1. Mix graphene oxide and water at a mass ratio of 1:100, disperse ultrasonically for 30 min, then add polyethyleneimine (the mass ratio of polyethyleneimine to graphene oxide is 2:1), stir and react at 80℃ for 8 h, and obtain modified graphene after filtration, washing and drying. S2. Ethanol and water were mixed in a volume ratio of 9:1 to obtain a mixture. Titanium dioxide was added to the mixture at a mass ratio of 1:100 and ultrasonically dispersed for 30 min. Then, APTES (the mass ratio of titanium dioxide to APTES was 1:0.8) was added. After heating to 70℃, 2 mol / L hydrochloric acid was added to adjust the pH to 6.0. The reaction was continued at 70℃ for 6 h. After centrifugation, washing, and drying, amino-modified titanium dioxide was obtained. S3. According to the above mass proportions, add modified graphene, amino-modified titanium dioxide and chitosan to 250 parts of 2wt% acetic acid aqueous solution, sonicate for 30 min, then add glutaraldehyde, stir for 10 min, age at room temperature for 24 h, then soak and wash with water several times until the pH is neutral, and then freeze dry at -50℃ for 24 h to obtain graphene aerogel. S4. After pulverizing the graphene aerogel and passing it through a 200-mesh sieve, mix it with organic resin, additives, and solvent in the above-mentioned mass proportions and stir evenly to obtain a slurry, at a concentration of 40 g / m³. 2 The graphene coating is applied to the fabric surface, pre-baked at 90℃ for 3 minutes, and then baked at 150℃ for 5 minutes to obtain a skin-friendly and warm fabric.

[0037] Comparative Example 1 The difference between this comparative example and Example 1 is that steps S3-S4 are modified as follows: According to the above-mentioned mass proportions, the modified graphene, amino-modified titanium dioxide, chitosan, organic resin, additives, and solvent are mixed and stirred evenly to obtain a slurry, at a concentration of 40 g / m³. 2 The coating is applied to the surface of the fabric, pre-baked at 90°C for 3 minutes, and then baked at 150°C for 5 minutes to obtain a graphene-based skin-friendly and warm fabric; other components and preparation methods are the same as in Example 1.

[0038] Comparative Example 2 The difference between this comparative example and Example 1 is that step S1 is modified as follows: Ethanol and water were mixed in a volume ratio of 9:1 to obtain a mixture. Graphene oxide was added to the mixture at a mass ratio of 1:100 and ultrasonically dispersed for 30 min. Then, APTES (the mass ratio of graphene oxide to APTES was 1:0.8) was added. The mixture was heated to 70°C, and 2 mol / L hydrochloric acid was added to adjust the pH to 6.0. The reaction was continued at 70°C for 6 h. After centrifugation, washing, and drying, modified graphene oxide was obtained. Other components and preparation methods were the same as in Example 1.

[0039] Test case The samples prepared in the examples and comparative examples were subjected to performance tests.

[0040] Test method: Thermal insulation: The thermal insulation rate was determined using a fabric thermal insulation performance tester (YG(B)606EC) in accordance with GB / T 11048-1989.

[0041] Antibacterial properties: The antibacterial rate against Staphylococcus aureus and Escherichia coli was tested according to GB / T 20944.3 "Evaluation of antibacterial properties of textiles - Part 3: Shaking method".

[0042] The test results are shown in Table 1.

[0043] Table 1 Performance Test Results

[0044] As shown in Table 1, the fabric prepared in the embodiments of the present invention possesses excellent thermal insulation properties through the aerogel formed by cross-linking modified graphene, amino-modified titanium dioxide, and chitosan, achieving a thermal insulation rate of up to 57.2%. Simultaneously, the multiple components synergistically exhibit antibacterial properties, with an inhibition rate of up to 99.7% against Escherichia coli. In contrast, Comparative Example 1 directly mixed modified graphene, amino-modified titanium dioxide, and chitosan with resin and other components without preparing an aerogel, resulting in a significant decrease in thermal insulation. Because the components could not cross-link to form a porous network structure, they were prone to stacking and accumulating, reducing the active sites and area in contact with microorganisms, and significantly decreasing antibacterial activity. Comparative Example 2 replaced the polyethyleneimine-modified graphene, resulting in a decrease in the cross-linking and binding degree of the components in the aerogel, and varying degrees of decline in both thermal insulation and antibacterial activity.

[0045] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.

[0046] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A graphene-based skin-friendly and warm fabric, characterized in that, The raw materials for the graphene-based skin-friendly and warm fabric include fabric and sizing agent, wherein the sizing agent comprises the following components in parts by weight: 30-60 parts of organic resin 1-10 parts of modified graphene 1-5 parts of amino-modified titanium dioxide 2-10 parts chitosan Crosslinking agent 0.2-2 parts 0.1-2 parts of additives Solvent 50-100 parts; The modified graphene is a product of the reaction between polyethyleneimine and graphene oxide.

2. The graphene-based skin-friendly and warm fabric according to claim 1, characterized in that, The fabric is selected from one or more of natural fibers, regenerated fibers, and synthetic fibers.

3. The graphene-based skin-friendly and warm fabric according to claim 1, characterized in that, The organic resin is selected from one or more of polyurethane resin and polyacrylic acid resin.

4. The graphene-based skin-friendly and warm fabric according to claim 1, characterized in that, The additives are selected from one or more of the following: dispersants, wetting agents, defoamers, foaming agents, softeners, thickeners, and antibacterial agents.

5. The method for preparing the graphene skin-friendly and warm fabric according to any one of claims 1-4, characterized in that, The preparation method of the graphene skin-friendly and warm fabric includes the following steps: S1. Graphene oxide and polyethyleneimine are mixed and heated to react, resulting in modified graphene. S2. Mix titanium dioxide and silane coupling agent and heat to react to obtain amino-modified titanium dioxide; S3. The modified graphene, amino-modified titanium dioxide and chitosan are added to a solvent, then a crosslinking agent is added, the mixture is stirred and reacted, and then aged and freeze-dried to obtain graphene aerogel. S4. The graphene aerogel, organic resin, additives and solvent are mixed to obtain a slurry, which is then coated on the surface of the fabric to obtain a graphene skin-friendly and warm fabric.

6. The method for preparing the graphene-based skin-friendly and warm fabric according to claim 5, characterized in that, In step S1, the mass ratio of graphene oxide to polyethyleneimine is 1:(0.5-5).

7. The method for preparing the graphene-based skin-friendly and warm fabric according to claim 5, characterized in that, In step S1, the heating reaction is carried out at a temperature of 60-100℃ for 4-10 hours.

8. The method for preparing the graphene skin-friendly and warm fabric according to claim 5, characterized in that, In step S2, the mass ratio of titanium dioxide to silane coupling agent is 1:(0.1-2).

9. The method for preparing the graphene-based skin-friendly and warm fabric according to claim 5, characterized in that, In step S2, the heating reaction is carried out at a temperature of 50-100℃ for 1-12 hours.

10. The method for preparing the graphene-based skin-friendly and warm fabric according to claim 5, characterized in that, In step S3, the aging time is 2-24 hours.

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