Ternary composite antiviral nanocoating material for fabric and preparation method therefor

Abstract

Disclosed in the present invention are a ternary composite high-efficiency antiviral coating material for a surface of a textile and a preparation method therefor. The coating material is prepared by mixing a ternary composite high-efficiency antiviral aggregate powder with a coating slurry, wherein the composition of the ternary composite high-efficiency antiviral aggregate powder is a complex aggregate of small-sheet-diameter graphene oxide, organic antiviral molecules and superfine titania, and the aggregate has a size not larger than 5 micrometers and is a three-dimensional loose aggregate; the organic antiviral molecules are grafted onto the surface of the small-sheet-diameter graphene oxide; and the coating slurry is a water-based coating finishing agent.

Description

A ternary composite antiviral fabric nanomaterial coating material and its preparation method Technical Field

[0001] The invention belongs to the field of antibacterial and antiviral fabric finishing materials, and specifically relates to a multi-element long-lasting washable antiviral fabric surface coating additive and a preparation method thereof. Background Art

[0002] Antibacterial and antiviral treatment of fabric surfaces has a significant effect on improving public health and inhibiting the spread of airborne infectious diseases. Currently, a variety of antibacterial and antiviral materials are used in synthetic fiber modification, fabric surface post-treatment, surface finishing agents, etc. to make various fabrics or surface finishing agents with comprehensive anti-viral properties. These methods include inorganic materials, organic materials, and nanomaterials to modify fibers or fabric finishing agents. Since the components of fabric yarns contain a variety of natural materials, synthetic materials, biomaterials, etc., the antibacterial and antiviral treatments suitable for organic fiber modification or surface treatment are not suitable for natural materials and biomaterials, and conventional fabrics must undergo printing, dyeing, finishing and other processes. The surface organic molecular layer will block the efficiency of inactivating microorganisms on the fiber surface, and it is necessary to add materials to inactivate microbial pathogens in the fabric surface coating or finishing agent.

[0003] Currently, the materials for inactivating microbial pathogens added to fabric surface coatings or finishing agents include metal nanoparticles (such as silver nanoparticles), photocatalytic nanoparticles (titanium oxide, zinc oxide, etc.), and organic molecules (chitosan, halamine, imidazole, etc.). Since silver nanoparticles have certain skin allergenicity, photocatalytic nanomaterials and organic molecules have the advantages of being colorless, non-toxic, and non-allergenic, and exhibit good antibacterial and antiviral efficiency. In order to achieve more efficient antiviral efficiency (short-term, weak light environment, inactivation of highly pathogenic pathogens such as the new coronavirus), the development of high-efficiency, washable, low-color universal antiviral materials has broad economic and social benefits.

[0004] Graphene, an atomically thin, two-dimensional nanomaterial, has recently been used to prepare antimicrobial fibers. Its high specific surface area allows for the formation of numerous atomically thin graphene flakes on the polymer surface when embedded in it, disrupting cell membranes adsorbed to the surface and resulting in a potent antibacterial effect. Nano-titanium oxide and zinc oxide generate reactive oxygen species upon exposure to light, which inactivate bacteria and viruses. Chitosan and its derivatives have demonstrated excellent antibacterial and antiviral properties and are used in textile modification and surface treatment. Halamine and its various derivatives have been used in textile surface treatment and coating additives, exhibiting excellent bacterial and viral inhibition. The blending of organic and biomolecules with polymers can lead to a decrease in antibacterial and antiviral efficacy after washing, while excessive addition can compromise the hydrophobicity and comfort of the fabric surface. Fabric-modifying functional materials can be formulated into microcapsules and mixed with a finishing polymer and then coated on the fabric surface, resulting in a sustained-release effect and preventing the polymer matrix from entrapping the functional molecules and impacting their antibacterial and antiviral efficacy. The size of traditional microcapsules is mostly several to tens of microns, which are quickly worn out and damaged during washing or consumption, and have low long-term water-washing resistance.

[0005] The present invention provides a method for preparing a high-efficiency antiviral fabric coating or finishing agent additive of a ternary aggregate of small-diameter graphene loaded with ultrafine titanium oxide nanoparticles, small-diameter graphene loaded with chitosan and its derivatives, or loaded with chitosan loaded with halamine and its derivatives. The coating or finishing agent additive has the advantages of being non-allergenic, washable and having a high-efficiency antiviral effect.

[0006] Summary of the Invention

[0007] Purpose of the invention: The present invention provides a preparation method of a ternary composite aggregate based on graphene oxide, ultrafine nanoparticles, and antibacterial and antiviral organic molecules, and a fabric surface coating or treatment agent is made based on the aggregate to form a functional fabric with antibacterial and antiviral properties.

[0008] Technical solution: A ternary composite high-efficiency antiviral textile surface coating material is prepared by mixing a ternary composite high-efficiency antiviral aggregate powder with a coating slurry; wherein the ternary composite high-efficiency antiviral aggregate powder is composed of complex agglomerates of small-diameter graphene oxide, organic antiviral molecules, and ultrafine titanium oxide, the agglomerate size is not greater than 5 microns, and it is a three-dimensional loose aggregate; the organic antiviral molecules are grafted onto the surface of small-diameter graphene oxide; and the coating slurry is a water-based coating finishing agent.

[0009] The small-diameter graphene flakes are single-layer graphene oxide, and the flake diameter is 50 to 200 nanometers.

[0010] The organic antiviral molecule is chitosan or halamine; when it is chitosan, it is grafted by carboxylamine reaction method, and when it is halamine, it is grafted by quaternization reaction or copolymerization.

[0011] The halamines are 3-bromopropyl-5,5-dimethylhydantoin and 1,3-dichloro-5,5-dimethylhydantoin.

[0012] The coating slurry is water-soluble polyurethane or polyacrylate.

[0013] The solid phase mass ratio of the ternary composite high-efficiency antiviral aggregate powder to the coating slurry is 1:10-50.

[0014] A method for preparing the ternary composite high-efficiency antiviral textile surface coating material,

[0015] Step 1: Preparation of graphene-supported photocatalytic titanium oxide ultrafine nanoparticles: heating a graphene oxide aqueous solution to obtain partially reduced graphene oxide, then mixing it with a butyl titanate sol precursor, and treating it with laser irradiation to obtain graphene oxide supported on ultrafine nano-titanium oxide; the butyl titanate sol precursor contains metal ions;

[0016] Step 2: preparing graphene oxide grafted with antiviral organic molecules: mixing carboxylated graphene and antiviral organic molecule solution, and obtaining graphene oxide grafted with antiviral organic molecules after reaction;

[0017] Step three, preparing a ternary composite antiviral aggregate powder: adding semi-hydrophobic titanium oxide nanoparticles to tributyl phosphate and dispersing them, mixing an aqueous solution of graphene oxide loaded with nano-titanium oxide and grafted with antiviral organic molecules, dissolving them in ascorbic acid, adjusting the pH value, and mixing them with an oil phase containing partially lipophilic nano-titanium oxide particles to form an emulsion, preparing hydrogel particles at 60°C, and drying them at low temperature to prepare a ternary composite antiviral aggregate powder;

[0018] Step 4, preparing the coating material: mechanically mixing the ternary composite antiviral aggregate powder and the coating slurry evenly, and finishing them on the chemical fiber fabric or blended fabric by padding or roller coating.

[0019] The metal ion is Pt + 、Zn 2+ 、Cu 2+ One of these materials has an average particle diameter of less than 3 nanometers and exhibits higher photocatalytic efficiency than p25 nanoparticles of the same mass. Ultrafine nano-titanium oxide is a monodisperse nanoparticle with an average diameter of less than 8 nanometers that exhibits photocatalytic activity. The nano-titanium oxide-loaded graphene has a heterojunction structure produced by an irradiation method and exhibits efficient photocatalytic performance in the ultraviolet and visible light ranges. Beneficial effects:

[0020] The antiviral material prepared by this method does not contain metal elements such as silver, has biosafety, and is suitable for applications requiring skin allergies, including infants and young children. The size of the multi-component composite graphene three-dimensional skeleton structure is controllable, the high specific surface area is not covered by film-forming polymers, and has high antiviral efficiency. It has high bonding strength with polymer composites, and is resistant to washing and wear. The coating formed by coating the ternary composite antiviral aggregates of the present invention and various textile coating materials on the surface of the fabric has the ability to inactivate viruses for a variety of virus particles attached to the fabric; the ternary composite antiviral aggregates are aqueous materials and can form stable dispersions in a variety of water-soluble polymer slurries; the coating containing the aggregates of the present invention (~0.5%wt) forms an inactivation efficiency for a variety of viruses (H1N1, Corvid-19, etc.) reaching more than 99% under indoor light for 2 hours, and more than 99% inactivation within 5 hours without light. Indoor light for virus inactivation refers to an illumination of not less than 400Lux, and no light refers to an illumination of not less than 50Lux. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1. Flow chart for the preparation of ternary composite antiviral fabric nanomaterial coating. DETAILED DESCRIPTION

[0022] The specific implementation method of the present invention is further described below.

[0023] The ternary composite aggregates described in the present invention include ultrafine titanium oxide nanoparticles loaded on the surface of graphene oxide, and antibacterial and antiviral organic molecules loaded on the surface of graphene oxide. Graphene, titanium oxide, and organic molecules synergistically form broad-spectrum antibacterial and antiviral functions. The aggregates are dispersed and filled in a polymer coating material solution and coated on the surfaces of various fabrics to form low-chroma, non-allergenic, washable, antibacterial, and antiviral fabrics.

[0024] Furthermore, the method for preparing the agglomerates is to mix a prefabricated aqueous solution of graphene oxide loaded with ultrafine titanium oxide nanoparticles and graphene oxide loaded with antibacterial and antiviral organic molecules with an oil phase dissolved with partially lipophilic P25 titanium oxide nanoparticles, and the emulsion droplets prepared by the Pickering emulsion method have a size of less than 50 microns. After vacuum drying, agglomerates with an aggregation size of less than 5 microns are prepared, and the graphene in the agglomerates forms a three-dimensional spatial structure.

[0025] Furthermore, the ultrafine nano-titanium oxide loaded graphene is a heterojunction structure prepared by an excitation irradiation method, and has high-efficiency photocatalytic performance in the ultraviolet and visible light ranges.

[0026] Furthermore, the graphene oxide loaded with antibacterial and antiviral organic molecules is graphene oxide prepared by the Hummer method. When the organic molecule is chitosan, carboxylated graphene and chitosan are catalytically coupled using EDC molecules to form graphene-loaded chitosan molecules. When the organic molecule is halamine, graphene oxide-complex halamine molecules are prepared by grafting or mixing methods.

[0027] Furthermore, the ternary aggregate is prepared by the Pickering emulsion method, wherein the prepared graphene-loaded nano-titanium oxide and graphene-loaded chitosan or halamine aqueous solution are mixed with ascorbic acid solution, and then added to the oil phase containing partially lipophilic P25 titanium oxide nanoparticles, stirred and emulsified, and kept warm at 60°C for a long time to prepare hydrogel micron particles, which are then freeze-dried and separated to obtain the ternary composite graphene aggregate particles.

[0028] Furthermore, the fabric coating or finishing agent is prepared by mixing the composite aggregate powder with a water-soluble polymer slurry to form a coating.

[0029] Example 1

[0030] Step 1: The method for preparing graphene-loaded photocatalytic titanium oxide ultrafine nanoparticles is similar to the invention patent (Carbon-based materials loaded with titanium oxide nanoparticles, preparation methods and applications thereof, CN114433046A). First, a 1% wt aqueous solution of graphene oxide prepared by the Hummer method with a single layer or less than 5 layers of flake diameter of 100 to 500 nm is heated at 60°C for 3 hours to obtain partially reduced graphene oxide.

[0031] At 4°C, 130 ml of butyl titanate was mixed with 25 ml of anhydrous ethanol, stirred evenly, and then slowly added dropwise to 340 ml of nitric acid aqueous solution, wherein the nitric acid aqueous solution contains zinc nitrate, and the amount of titanium is Zn 2+ The concentration was 3.5 mol%. The final mixed solution had a molar ratio of butyl titanate: nitric acid: ethanol: water of 0.38:0.11:0.43:18.61. The system pH was 3, resulting in a butyl titanate sol precursor.

[0032] At 4°C, a graphene oxide aqueous solution with an average flake diameter of 400 nm and a concentration of 0.01 wt% was mixed with the precursor in a volume ratio of 1:3;

[0033] The solution was irradiated with a carbon dioxide laser with a wavelength of 10.6 μm and a spot diameter of 0.2 mm (power density 5×10 6 W / m 2 ), repeat scanning 50×50×2mm 3 The scanning speed is set so that the irradiation time of each spot is 0.2 milliseconds, and the scanning is repeated 100 to 200 times. The irradiation dose of the spot is 5 to 10×10 4 J / m2 .

[0034] The laser-treated solution was filtered once with a filter membrane having a pore size of 50 nm, and the filtrate was graphene oxide loaded with ultrafine nano-titanium oxide.

[0035] Step 2: 100 ml of 0.1 g / ml graphene oxide with a sheet diameter of 200 nm (less than 5 layers) was mixed with 1 g of chloroacetic acid and 1.2 g of sodium hydroxide solution. After ultrasonic vibration for 3 h, the mixture was filtered through a filter membrane with a pore size of 50 nm and dispersed with ultrapure water. After repeating this three times, the mixture was freeze-dried at -20 ° C to obtain carboxylated graphene.

[0036] Carboxylated graphene at a concentration of 0.1 mg / ml was dissolved in 100 ml of deionized water, 5.4 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide (EDC) and 5.5 g of N-hydroxysuccinimide (NHS) were added, and 2 g of chitosan with a molecular weight of less than 10 KDa was added. After stirring at room temperature for 5 hours, the mixture was dispersed with ultrapure water using a filter membrane with a pore size of 50 nm. After repeating this process three times, the mixture was freeze-dried to obtain chitosan-loaded graphene.

[0037] Step 3: Add 2 g of P25 titanium oxide nanoparticles with an average diameter of 10 nm to a mixture of 30 ml and 10 ml of deionized water, adjust the pH to 4 with 1 mol / L hydrochloric acid, and ultrasonically disperse for 10 minutes. Add 0.34 ml of hexadecyltrimethylsilane, stir at 80°C for 6 hours, filter with a filter membrane with a pore size of 50 nm, and disperse with ultrapure water. Repeat this process three times, and freeze-dry at 20°C to obtain semi-hydrophobic P25 titanium oxide nanoparticles.

[0038] 0.5 g of semi-hydrophobic P25 titanium oxide nanoparticles was added to 100 ml of tributyl phosphate, and the mixture was evenly dispersed by ultrasonication for 5 minutes. Then, 0.25 g of graphene loaded with nano-titanium oxide and 0.25 g of graphene loaded with chitosan were added to 100 ml of deionized water, and evenly dispersed by ultrasonication for 10 minutes. After 2.4 g of ascorbic acid was added and fully dissolved, ammonia water was added to adjust the pH value to 10.5. The mixture was then added to the tributyl phosphate solution, stirred vigorously, heated to 60 ° C for 14 hours, dried at -30 ° C and 40 Pa vacuum for 1 hour, filtered with a 1 micron pore size filter membrane, washed once with water, and dried to obtain a ternary composite antiviral powder.

[0039] Step 4: The powder was mixed with a water-based polyurethane finishing agent at a concentration of 5% by weight, applied to the fabric surface, and dried to produce the antiviral fabric. The antiviral efficacy of the fabric was tested using the ISO 18184-2019 standard. Under indoor fluorescent light (illuminance > 500 Lux), the inactivation efficiency of the H1N1 or Coronavirus-19 virus was greater than 99% within 2 hours. Under no-light conditions (illuminance < 50 Lux), the inactivation efficiency of the H1N1 or Coronavirus-19 virus was greater than 99% within 5 hours.

[0040] Example 2

[0041] Step 1: Same as in Example 1;

[0042] Step 2: Dissolve 3.2 g of 5,5-dimethylhydantoin (DMH) in 120 ml of acetone, add 10 g of potassium carbonate, reflux at 70°C for one hour, add 2.8 ml of 1,3-dibromopropane, reflux for 12 hours, and purify to obtain 3-bromopropyl-5,5-dimethylhydantoin.

[0043] 0.2 g of graphene oxide was ultrasonically dissolved in 20 mL of deionized water, and then 0.27 g of potassium sulfate and 1.5 ml of 4-vinylpyridine were added. The mixture was stirred at 65 ° C under high-purity nitrogen protection for 2 hours. After filtering with a 50 nm pore size filter membrane, it was dissolved in deionized water and washed three times to obtain graphene oxide grafted with 4-vinylpyridine.

[0044] 0.2 g of graphene oxide grafted with 4-vinylpyridine was ultrasonically dissolved in 15 mL of deionized water, and 1 g of 3-bromopropyl-5,5-dimethylhydantoin was added. The mixture was refluxed at 90°C for 18 hours, filtered and washed once with deionized water, and freeze-dried to obtain graphene oxide loaded with 3-bromopropyl-5,5-dimethylhydantoin.

[0045] Step 3: Add 2 g of P25 titanium oxide nanoparticles with an average diameter of 10 nm to a mixture of 30 ml and 10 ml of deionized water, adjust the pH to 4 with 1 mol / L hydrochloric acid, and ultrasonically disperse for 10 minutes. Add 0.34 ml of hexadecyltrimethylsilane, stir at 80°C for 6 hours, filter with a filter membrane with a pore size of 50 nm, and disperse with ultrapure water. Repeat this process three times, and freeze-dry at 20°C to obtain semi-hydrophobic P25 titanium oxide nanoparticles.

[0046] 0.5 g of semi-hydrophobic P25 titanium oxide nanoparticles was added to 100 ml of tributyl phosphate, and the mixture was uniformly dispersed by ultrasonication for 5 minutes. Then, 0.25 g of graphene loaded with nano-titanium oxide and 0.25 g of graphene loaded with 3-bromopropyl-5,5-dimethylhydantoin were added to 100 ml of deionized water, and the mixture was uniformly dispersed by ultrasonication for 10 minutes. After 2.4 g of ascorbic acid was added to fully dissolve the mixture, ammonia water was added to adjust the pH value to 10.5, and the mixture was added to the tributyl phosphate solution. The mixture was stirred vigorously, heated to 60 ° C for 14 hours, dried at -30 ° C and 40 Pa vacuum for 1 hour, filtered with a 1 micron pore size filter membrane, washed with water once, and dried to obtain a ternary composite antiviral powder.

[0047] Step 4: Same as in Example 1.

[0048] Example 3

[0049] Step 1: Same as in Example 1;

[0050] Step 2: Add 2 g of P25 titanium oxide nanoparticles with an average diameter of 10 nm to a mixture of 30 ml and 10 ml of deionized water, adjust the pH to 4 with 1 mol / L hydrochloric acid, and ultrasonically disperse for 10 minutes. Add 0.34 ml of hexadecyltrimethylsilane, stir at 80°C for 6 hours, filter with a filter membrane with a pore size of 50 nm, and disperse with ultrapure water. Repeat this process three times, and freeze-dry at 20°C to obtain semi-hydrophobic P25 titanium oxide nanoparticles.

[0051] 0.5 g of semi-hydrophobic P25 titanium oxide nanoparticles was added to 100 ml of tributyl phosphate, and the mixture was uniformly dispersed by ultrasonication for 5 minutes. Then, 0.25 g of graphene loaded with nano-titanium oxide, 0.15 g of 1,3-dichloro-5,5-dimethylhydantoin and 0.05 g of graphene oxide were added to 100 ml of deionized water, and the mixture was uniformly dispersed by ultrasonication for 10 minutes. After 2.4 g of ascorbic acid was added and fully dissolved, ammonia water was added to adjust the pH value to 10.5. The mixture was then added to the tributyl phosphate solution, stirred vigorously, heated to 60 ° C for 14 hours, dried at -30 ° C and 40 Pa vacuum for 1 hour, filtered with a 1 micron pore size filter membrane, washed once with water, and dried to obtain a ternary composite antiviral powder.

[0052] Step 3 is the same as step 4 in embodiment 1.

Claims

1. A ternary composite highly efficient antiviral textile surface coating material, characterized in that: It is prepared by mixing a ternary composite high-efficiency antiviral aggregate powder with a coating slurry; wherein the ternary composite high-efficiency antiviral aggregate powder is composed of a complex agglomerate of small-diameter graphene oxide, organic antiviral molecules, and ultrafine titanium oxide, the agglomerate size is not more than 5 microns, and it is a three-dimensional loose aggregate; the organic antiviral molecules are grafted onto the surface of small-diameter graphene oxide; and the coating slurry is a water-based coating finishing agent.

2. The ternary composite highly efficient antiviral textile surface coating material according to claim 1, characterized in that: The small-diameter graphene flakes are single-layer graphene oxide, and the flake diameter is 50 to 200 nanometers.

3. The ternary composite highly efficient antiviral textile surface coating material according to claim 1, characterized in that: The organic antiviral molecule is chitosan or halamine; when it is chitosan, it is grafted by carboxylamine reaction method, and when it is halamine, it is grafted or copolymerized by quaternization reaction.

4. The ternary composite highly efficient antiviral textile surface coating material according to claim 3, characterized in that: The halamines are 3-bromopropyl-5,5-dimethylhydantoin and 1,3-dichloro-5,5-dimethylhydantoin.

5. The ternary composite high-efficiency antiviral textile surface coating material according to claim 1, characterized in that: The coating slurry is water-soluble polyurethane or polyacrylate.

6. The ternary composite high-efficiency antiviral textile surface coating material according to claim 1, wherein: The solid phase mass ratio of the ternary composite high-efficiency antiviral aggregate powder to the coating slurry is 1:10-50.

7. A method for preparing the ternary composite high-efficiency antiviral textile surface coating material according to any one of claims 1 to 6, characterized in that: Step 1, preparing graphene-loaded photocatalytic titanium oxide ultrafine nanoparticles: heating a graphene oxide aqueous solution to obtain partially reduced graphene oxide, then mixing it with a butyl titanate sol precursor, and treating it with a laser irradiation method to obtain graphene oxide loaded with ultrafine nano titanium oxide; the butyl titanate sol precursor contains metal ions; Step 2, preparing graphene oxide grafted with antiviral organic molecules: mixing carboxylated graphene and antiviral organic molecule solution, and obtaining graphene oxide grafted with antiviral organic molecules after reaction; Step 3, preparing a ternary composite antiviral aggregate powder: adding semi-hydrophobic titanium oxide nanoparticles to tributyl phosphate for dispersion, mixing an aqueous solution of graphene oxide loaded with nano-titanium oxide and grafted with antiviral organic molecules, dissolving in ascorbic acid, adjusting the pH value, and mixing with an oil phase containing partially lipophilic nano-titanium oxide particles to form an emulsion, preparing hydrogel particles at 60°C, and preparing a ternary composite antiviral aggregate powder after low-temperature drying; Step 4, preparing the coating material: mechanically mixing the ternary composite antiviral aggregate powder and the coating slurry evenly, and finishing them on the chemical fiber fabric or blended fabric by padding or roller coating.

8. The method for preparing the ternary composite highly efficient antiviral textile surface coating material according to claim 7, characterized in that: The metal ion described is Pt + , Zn 2+ , Cu 2+ One of them, with an average particle diameter less than 3 nanometers and a photocatalytic efficiency higher than that of p25 nanoparticles of the same mass. The ultrafine nano-titanium oxide is a monodisperse nanoparticle with a photocatalytic activity and an average diameter less than 8 nanometers.

9. The method for preparing the ternary composite highly efficient antiviral textile surface coating material according to claim 7, characterized in that: The nano-titanium oxide-loaded graphene is a heterojunction structure prepared by an excitation irradiation method and has high-efficiency photocatalytic performance in the ultraviolet and visible light ranges.

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