CN118581740A - A kind of UV-proof composite fabric filled with biological natural crystal powder and preparation method thereof - Google Patents

Abstract

The present invention relates to the technical field of new fabric materials, and in particular to an anti-ultraviolet composite fabric filled with biological natural crystal powder and a preparation method thereof. The method comprises the following steps: uniformly mixing nylon slices, natural crystal powder and spinning aids to obtain a mixture; adding the mixture to a melt spinning machine for spinning, and then cold-cutting the spun yarn bundle into shape; oiling the formed yarn bundle, and after the oiling is completed, sequentially drawing and winding to obtain nylon fiber; blending cotton fiber with nylon fiber to obtain blended yarn, weaving the blended yarn to obtain nylon/cotton blended fabric; adding graphene to an aqueous polyurethane solution, stirring and mixing uniformly to form a suspension, and then immersing the nylon/cotton blended fabric in the above suspension, and after the immersion is completed, placing the textile in an oven for drying treatment to obtain the fabric. The fabric prepared by the present invention has good infrared release performance and anti-ultraviolet performance, and improves people's quality of life.

Description

A kind of UV-proof composite fabric filled with biological natural crystal powder and preparation method thereof

Technical Field

The invention relates to the technical field of new fabric materials, and in particular to an anti-ultraviolet composite fabric filled with biological natural crystal powder and a preparation method thereof.

Background Art

As the core of the clothing industry, clothing fabrics are the key factors that determine the performance and appearance of clothing. With the advancement of science and technology and the diversification of consumer demand, the innovation of clothing fabrics has become an important driving force for the development of the industry. The current clothing fabric technology on the market is quite mature, but with the improvement of consumer requirements for clothing functionality, comfort, environmental protection, etc., the existing technology faces new challenges. The progress of materials science has provided unlimited possibilities for the innovation of clothing fabrics. The application of cutting-edge technologies such as nanotechnology, bioengineering technology, and smart materials has made fabrics more functional and intelligent.

Ultraviolet (UV) radiation is a part of sunlight and has certain harmfulness. It not only causes fabric aging and fading, but also may cause damage to human skin, such as sunburn, spots, and even induce skin cancer. Therefore, the development of fabrics with UV resistance has become an important research direction in the textile industry. Graphene, which is mainly composed of a layered structure formed by sp2 hybridization of carbon atoms, has good chemical stability and conductivity. In recent years, graphene and its derivatives (such as graphene) have shown great application potential in the field of UV-resistant fabrics due to their unique physical and chemical properties.

Chinese patent publication number CN110699945 discloses a sunscreen and anti-ultraviolet sports fabric and its preparation method, comprising the following steps: treating the fabric with a NaOH aqueous solution; immersing the treated fabric in a citric acid solution, adding graphene, stirring at high temperature to react, and after the reaction system cools to room temperature, taking out the fabric and drying it; immersing the fabric in a finishing agent composed of amino silicone oil, triethanolamine, sodium tripolyphosphate, polybutyl acrylate, lauryl methacrylate, carboxymethyl cellulose, sodium lauryl alcohol polyether sulfate, fatty alcohol polyoxyethylene ether, ethanol, and water, and washing and baking to obtain a sunscreen and anti-ultraviolet sports fabric. In this patented technical solution, the fabric is given anti-ultraviolet properties by immersing it in a liquid containing graphene, but graphene is prone to agglomeration, which affects the improvement of graphene on the anti-ultraviolet properties of the fabric.

Summary of the invention

In order to overcome the above problems of the prior art, the present invention provides an anti-ultraviolet composite fabric filled with biological natural crystal powder and a preparation method thereof.

In order to achieve the above-mentioned object of the invention, the present invention adopts the following technical solutions:

A method for preparing an anti-ultraviolet composite fabric filled with biological natural crystal powder comprises the following steps:

S1, mixing nylon chips, natural crystal powder and spinning aids uniformly to obtain a mixture;

S2, adding the mixed material into a melt spinning machine for spinning, and then cold-cutting the spun filament bundle into shape;

S3, applying oil to the formed tow, and then drawing and winding the tow in sequence to obtain nylon fiber;

S4, blending the cotton fiber with the nylon fiber to obtain a blended yarn, and weaving the blended yarn to obtain a nylon/cotton blended fabric;

S5, adding graphene to the aqueous polyurethane solution, stirring and mixing evenly to form a suspension, and then immersing the nylon/cotton blended fabric in the suspension. After the immersion is completed, the textile is placed in an oven for drying.

The nylon of the present invention is mixed with natural crystal powder, which produces a unique and stable frequency, can enhance the human immune system, promote the rapid discharge of toxins from the body and increase the oxygen level. Since this special frequency is at the same vibration frequency as that of humans, it has the functions of reducing muscle tension, slowing down the heartbeat, relaxing breathing, increasing the body's oxygen content, releasing pressure and improving sleep.

As a new type of two-dimensional carbon material, graphene has shown great application potential in the field of UV resistance due to its unique structure and properties. The present invention uses water-based polyurethane as an adhesive to coat the graphene adhesive on the surface of the fabric fiber to form an anti-ultraviolet coating on the surface of the fabric fiber, giving the fabric excellent anti-ultraviolet performance.

Preferably, in step S1, the mass ratio of nylon chips, natural crystal powder and spinning aid is 1:0.08:0.01.

Preferably, in step S1, the natural crystal powder is mixed with the following substances:

Fluorite powder, orange crystal calcite powder, graphite powder, bloodstone powder, gypsum powder, aragonite powder, tourmaline powder, white crystal powder, rose crystal powder, aventurine powder, red jasper powder, serpentine powder.

The present invention blends natural crystal powder with nylon slices. Natural crystal powder is a natural energy medium. By interacting with the human energy field, it can regulate and balance the human energy, relieve mental stress and promote relaxation, improve the human energy level, and is beneficial to human health.

Preferably, in step S4, the blending ratio of cotton fiber to nylon fiber is 1:1-5.

Preferably, in step S5, the concentration of the aqueous polyurethane solution is 5-10 wt %.

Preferably, in step S5, the graphene is subjected to modification treatment, the steps being as follows:

S51, adding graphene to a sulfuric acid solution, cooling to below 0°C, adding potassium permanganate, stirring evenly and heating, then adding an aqueous hydrogen peroxide solution for oxidation reaction, filtering and separating the graphene, washing with water and drying to obtain graphene oxide;

S52, adding _TiCl4 to ammonia water, stirring to react, obtaining a white precipitate, adding oxalic acid to the white precipitate, stirring to dissolve, obtaining a titanium oxalate solution; adding graphene oxide, ammonium acetate and citric acid to the titanium oxalate solution, heating and stirring to react, standing for aging, and calcining at high temperature to obtain a titanium dioxide-graphene oxide composite;

S53, adding sodium carboxymethyl cellulose into water, stirring and dissolving, preparing a sodium carboxymethyl cellulose aqueous solution with a mass concentration of 0.5%, adding an acid catalyst into the sodium carboxymethyl cellulose solution, stirring and mixing evenly, then adding titanium dioxide-graphene oxide composite, heating to 80°C, keeping warm for reaction, and after the reaction is completed, filtering, washing and drying in sequence to obtain the product.

The present invention finds that the graphene agglomerates when adding graphene to an aqueous polyurethane solution. A large amount of agglomerated graphene exists in a part of the surface of the fabric fiber, while the number of graphene in another part is scarce, which seriously affects the improvement of the anti-ultraviolet performance of the fabric fiber by graphene. The dispersion effect of the graphene by using a general dispersant is not obvious. Therefore, the present invention modifies the graphene, firstly prepares the graphene oxide under the oxidation of potassium permanganate and hydrogen peroxide, and makes the graphene surface load active functional groups such as epoxy groups and hydroxyl groups. Under the action of an acidic catalyst, the reaction activity of the epoxy group is used to react with the hydroxyl groups on the sodium carboxymethyl cellulose molecules to generate a ring-opening reaction, so that the carboxymethyl cellulose is loaded on the graphene surface, and the sodium carboxymethyl cellulose grafted on the graphene surface will ionize -COO ^- in the polyurethane aqueous solution, so that the graphene surface is negatively charged, and under the action of electrostatic repulsion, the graphenes repel each other, thereby solving the problem of agglomeration between the graphenes.

Further research during the experiment found that: although the grafting of sodium carboxymethyl cellulose on the graphene surface can improve the dispersion performance of graphene, carboxymethyl cellulose will cause a certain shielding effect on the anti-ultraviolet performance of graphene. To solve the above problems, the present invention uses _TiCl4 as a titanium source to deposit a certain amount of nano-titanium dioxide on the graphene surface. On the one hand, nano-titanium dioxide is combined with the graphene surface, reducing a certain amount of epoxy group binding sites on the graphene surface, thereby reducing the carboxymethyl cellulose grafted on the graphene surface. Avoid excessive carboxymethyl cellulose from causing a shielding effect on the anti-ultraviolet performance of graphene. On the other hand, nano-titanium dioxide reflects and scatters ultraviolet rays, further enhancing the anti-ultraviolet performance of the fabric.

Preferably, in step S51, the mass ratio of graphene to potassium permanganate is 1:3-8.

Preferably, in step S51, the concentration of the aqueous hydrogen peroxide solution is 10-20 wt %.

Preferably, in step S53, the insulation reaction time is controlled within a range of 120-152 minutes.

A UV-proof composite fabric filled with biological natural crystal powder is prepared by the above method.

The present invention has the following beneficial effects:

1) Natural crystal powder is mixed into nylon. Natural crystal powder produces a unique and stable frequency that can enhance the human immune system, promote the rapid discharge of toxins from the body and increase oxygen levels. Since this special frequency is at the same vibration frequency as humans, it has the functions of reducing muscle tension, slowing down heartbeat, relaxing breathing, increasing body oxygen content, releasing stress and improving sleep;

2) Using water-based polyurethane as adhesive, graphene adhesive is applied to the surface of fabric fibers to form an anti-ultraviolet coating on the surface of fabric fibers, giving the fabric excellent anti-ultraviolet properties;

3) The sodium carboxymethyl cellulose grafted on the graphene surface will ionize -COO ^- in the polyurethane aqueous solution, so that the graphene surface is negatively charged. Under the action of electrostatic repulsion, the graphenes repel each other, thus improving the dispersion performance of graphene;

4) Deposit a certain amount of nano-titanium dioxide on the graphene surface. On the one hand, nano-titanium dioxide is combined with the graphene surface, reducing a certain amount of epoxy group binding sites on the graphene surface, thereby reducing the carboxymethyl cellulose grafted on the graphene surface. Avoid excessive carboxymethyl cellulose from shielding the graphene's anti-ultraviolet performance; on the other hand, nano-titanium dioxide reflects and scatters ultraviolet rays, further enhancing the fabric's anti-ultraviolet performance.

DETAILED DESCRIPTION

The present invention is further described in detail below in conjunction with specific embodiments. Those of ordinary skill in the art will be able to implement the present invention based on these descriptions. In addition, the embodiments of the present invention involved in the following description are generally only embodiments of a part of the present invention, rather than all embodiments. Therefore, based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative work should fall within the scope of protection of the present invention.

Unless otherwise specified, the raw materials used in the examples of the present invention are all commercially available or available to those skilled in the art; unless otherwise specified, the methods used in the examples of the present invention are all methods known to those skilled in the art.

Example 1

A method for preparing an anti-ultraviolet composite fabric filled with biological natural crystal powder comprises the following steps:

S1, mixing nylon 6 slices, natural crystal powder and spinning aid calcium stearate evenly, wherein the mass ratio of nylon slices, natural crystal powder and spinning aid is 1:0.08:0.01, to obtain a mixture;

As mentioned above, the natural crystal powder is mixed by the following substances in equal quantities:

Fluorite powder, orange crystal calcite powder, shungite powder, bloodstone powder, gypsum powder, aragonite powder, tourmaline powder, white crystal powder, rose crystal powder, aventurine powder, red jasper powder, serpentine powder;

S2, adding the mixed material into a melt spinning machine for spinning, the spinning temperature is controlled at 220°C, and after the silk fibroin is ejected from the spinneret, it is cold cut into shape at room temperature;

S3, applying oil to the formed tow, and then drawing and winding the tow in sequence to obtain nylon fiber;

S4, blending the cotton fiber and the nylon fiber in a mass ratio of 1:4 to obtain a blended yarn, and weaving the blended yarn to obtain a nylon/cotton blended fabric;

S5, adding the modified graphene into an 8wt% aqueous polyurethane solution at a mass volume ratio of 1g/200mL, stirring and mixing evenly to form a suspension, and then immersing the nylon/cotton blended fabric in the above suspension. After the immersion is completed, the textile is placed in an oven at 60°C for drying to obtain.

Preparation method of modified graphene:

S51, adding graphene to a sulfuric acid solution at a mass volume ratio of 1g/80mL, cooling to below 0°C, adding potassium permanganate, the mass ratio of graphene to potassium permanganate is 1:7, stirring evenly and heating to 70°C, keeping warm for 50min, then adding a 18wt% aqueous hydrogen peroxide solution for oxidation reaction, the volume ratio of sulfuric acid solution to hydrogen peroxide solution is 1:0.8, filtering and separating the graphene, washing with water and drying to obtain graphene oxide;

S52, adding TiCl ₄ to ammonia water, the volume ratio of TiCl ₄ to ammonia water is 1:4, stirring to react, obtaining a white precipitate, adding the white precipitate to oxalic acid with a mass concentration of 10% at a mass volume ratio of 1 g/100 mL, stirring to dissolve, and obtaining a titanium oxalate solution; adding graphene oxide, ammonium acetate and citric acid to the titanium oxalate solution, the mass ratio of graphene oxide, ammonium acetate and citric acid is 10:2:1, the mass volume ratio of graphene oxide to the titanium oxalate solution is 1 g/80 mL, heating to 80°C, stirring to react for 2 h, standing to age for 10 h, separating, placing at 180°C for 20 min, and then calcining at 600°C for 3 h to obtain a titanium dioxide-graphene oxide composite;

S53, adding sodium carboxymethyl cellulose into water and stirring to dissolve to prepare a sodium carboxymethyl cellulose aqueous solution with a mass concentration of 0.5%, adding an acid catalyst to the sodium carboxymethyl cellulose solution, the acid catalyst added in an amount of 0.05wt% of the acid in the sodium carboxymethyl cellulose aqueous solution, the catalyst being a mixture of SnCl4 and 10wt% hydrochloric acid, the mass volume ratio of the two being 0.001:1, stirring to mix evenly, and then adding titanium dioxide-graphene oxide composite at a mass volume ratio of 1g/150mL, heating to 80°C, keeping the temperature for reaction for 150min, filtering, washing and drying in sequence after the reaction is completed to obtain the product.

Example 2

A method for preparing an anti-ultraviolet composite fabric filled with biological natural crystal powder comprises the following steps:

S1, mixing nylon 6 slices, natural crystal powder and spinning aid calcium stearate evenly, wherein the mass ratio of nylon slices, natural crystal powder and spinning aid is 1:0.08:0.01, to obtain a mixture;

As mentioned above, the natural crystal powder is mixed by the following substances in equal quantities:

Fluorite powder, orange crystal calcite powder, shungite powder, bloodstone powder, gypsum powder, aragonite powder, tourmaline powder, white crystal powder, rose crystal powder, aventurine powder, red jasper powder, serpentine powder;

S2, adding the mixed material into a melt spinning machine for spinning, the spinning temperature is controlled at 220°C, and after the silk fibroin is ejected from the spinneret, it is cold cut into shape at room temperature;

S3, applying oil to the formed tow, and then drawing and winding the tow in sequence to obtain nylon fiber;

S4, blending the cotton fiber and the nylon fiber in a mass ratio of 1:2 to obtain a blended yarn, and weaving the blended yarn to obtain a nylon/cotton blended fabric;

S5. Add the modified graphene to a 6wt% aqueous polyurethane solution at a mass volume ratio of 1g/200mL, stir and mix evenly to form a suspension, and then immerse the nylon/cotton blended fabric in the suspension. After the immersion is completed, place the textile in an oven at 60°C for drying to obtain the product.

Preparation method of modified graphene:

S51, adding graphene to a sulfuric acid solution at a mass volume ratio of 1g/80mL, cooling to below 0°C, adding potassium permanganate, the mass ratio of graphene to potassium permanganate is 1:4, stirring evenly and heating to 70°C, keeping warm for 50min, then adding a 12wt% aqueous hydrogen peroxide solution for oxidation reaction, the volume ratio of sulfuric acid solution to hydrogen peroxide solution is 1:0.8, filtering and separating the graphene, washing with water and drying to obtain graphene oxide;

S52, adding TiCl ₄ to ammonia water, the volume ratio of TiCl ₄ to ammonia water is 1:4, stirring to react, obtaining a white precipitate, adding the white precipitate to oxalic acid with a mass concentration of 10% at a mass volume ratio of 1 g/100 mL, stirring to dissolve, and obtaining a titanium oxalate solution; adding graphene oxide, ammonium acetate and citric acid to the titanium oxalate solution, the mass ratio of graphene oxide, ammonium acetate and citric acid is 10:2:1, the mass volume ratio of graphene oxide to the titanium oxalate solution is 1 g/80 mL, heating to 80°C, stirring to react for 2 h, standing to age for 10 h, separating, placing at 180°C for 20 min, and then calcining at 600°C for 3 h to obtain a titanium dioxide-graphene oxide composite;

S53, adding sodium carboxymethyl cellulose into water and stirring to dissolve to prepare a sodium carboxymethyl cellulose aqueous solution with a mass concentration of 0.5%, adding an acid catalyst to the sodium carboxymethyl cellulose solution, the acid catalyst added in an amount of 0.05wt% of the acid in the sodium carboxymethyl cellulose aqueous solution, the catalyst being a mixture of SnCl4 and 10wt% hydrochloric acid, the mass volume ratio of the two being 0.001:1, stirring to mix evenly, and then adding titanium dioxide-graphene oxide composite at a mass volume ratio of 1g/150mL, heating to 80°C, keeping the temperature for reaction for 125min, filtering, washing and drying in sequence after the reaction is completed to obtain the product.

Example 3

A method for preparing an anti-ultraviolet composite fabric filled with biological natural crystal powder comprises the following steps:

S1, mixing nylon 6 slices, natural crystal powder and spinning aid calcium stearate evenly, wherein the mass ratio of nylon slices, natural crystal powder and spinning aid is 1:0.08:0.01, to obtain a mixture;

As mentioned above, the natural crystal powder is mixed by the following substances in equal quantities:

Fluorite powder, orange crystal calcite powder, shungite powder, bloodstone powder, gypsum powder, aragonite powder, tourmaline powder, white crystal powder, rose crystal powder, aventurine powder, red jasper powder, serpentine powder;

S2, adding the mixed material into a melt spinning machine for spinning, the spinning temperature is controlled at 220°C, and after the silk fibroin is ejected from the spinneret, it is cold cut into shape at room temperature;

S3, applying oil to the formed tow, and then drawing and winding the tow in sequence to obtain nylon fiber;

S4, blending the cotton fiber and the nylon fiber in a mass ratio of 1:3 to obtain a blended yarn, and weaving the blended yarn to obtain a nylon/cotton blended fabric;

S5. Add the modified graphene to a 7wt% aqueous polyurethane solution at a mass volume ratio of 1g/200mL, stir and mix evenly to form a suspension, and then immerse the nylon/cotton blended fabric in the suspension. After the immersion is completed, place the textile in an oven at 60°C for drying to obtain the product.

Preparation method of modified graphene:

S51, adding graphene to a sulfuric acid solution at a mass volume ratio of 1g/80mL, cooling to below 0°C, adding potassium permanganate, the mass ratio of graphene to potassium permanganate is 1:5, stirring evenly and heating to 70°C, keeping warm for 50min, then adding a 15wt% aqueous hydrogen peroxide solution for oxidation reaction, the volume ratio of sulfuric acid solution to hydrogen peroxide solution is 1:0.8, filtering and separating the graphene, washing with water and drying to obtain graphene oxide;

S52, adding TiCl ₄ to ammonia water, the volume ratio of TiCl ₄ to ammonia water is 1:4, stirring to react, obtaining a white precipitate, adding the white precipitate to oxalic acid with a mass concentration of 10% at a mass volume ratio of 1 g/100 mL, stirring to dissolve, and obtaining a titanium oxalate solution; adding graphene oxide, ammonium acetate and citric acid to the titanium oxalate solution, the mass ratio of graphene oxide, ammonium acetate and citric acid is 10:2:1, the mass volume ratio of graphene oxide to the titanium oxalate solution is 1 g/80 mL, heating to 80°C, stirring to react for 2 h, standing to age for 10 h, separating, placing at 180°C for 20 min, and then calcining at 600°C for 3 h to obtain a titanium dioxide-graphene oxide composite;

S53, adding sodium carboxymethyl cellulose into water, stirring and dissolving to prepare a sodium carboxymethyl cellulose aqueous solution with a mass concentration of 0.5%, adding an acid catalyst to the sodium carboxymethyl cellulose solution, the acid catalyst added in an amount of 0.05wt% of the acid in the sodium carboxymethyl cellulose aqueous solution, the catalyst being a mixture of SnCl4 and 10wt% hydrochloric acid, the mass volume ratio of the two being 0.001:1, stirring and mixing evenly, and then adding titanium dioxide-graphene oxide composite at a mass volume ratio of 1g/150mL, heating to 80°C, keeping the temperature for reaction for 135min, and filtering, washing and drying in sequence after the reaction is completed to obtain the product.

Example 4

A method for preparing an anti-ultraviolet composite fabric filled with biological natural crystal powder comprises the following steps:

S1, mixing nylon 6 slices, natural crystal powder and spinning aid calcium stearate evenly, wherein the mass ratio of nylon slices, natural crystal powder and spinning aid is 1:0.08:0.01, to obtain a mixture;

As mentioned above, the natural crystal powder is mixed by the following substances in equal quantities:

Fluorite powder, orange crystal calcite powder, shungite powder, bloodstone powder, gypsum powder, aragonite powder, tourmaline powder, white crystal powder, rose crystal powder, aventurine powder, red jasper powder, serpentine powder;

S2, adding the mixed material into a melt spinning machine for spinning, the spinning temperature is controlled at 220°C, and after the silk fibroin is ejected from the spinneret, it is cold cut into shape at room temperature;

S3, applying oil to the formed tow, and then drawing and winding the tow in sequence to obtain nylon fiber;

S4, blending the cotton fiber and the nylon fiber in a mass ratio of 1:5 to obtain a blended yarn, and weaving the blended yarn to obtain a nylon/cotton blended fabric;

S5. Add the modified graphene to a 10wt% aqueous polyurethane solution at a mass volume ratio of 1g/200mL, stir and mix evenly to form a suspension, and then immerse the nylon/cotton blended fabric in the suspension. After the immersion is completed, place the textile in an oven at 60°C for drying to obtain the product.

Preparation method of modified graphene:

S51, adding graphene to a sulfuric acid solution at a mass volume ratio of 1g/80mL, cooling to below 0°C, adding potassium permanganate, the mass ratio of graphene to potassium permanganate is 1:8, stirring evenly and heating to 70°C, keeping warm for 50min, then adding a 20wt% aqueous hydrogen peroxide solution for oxidation reaction, the volume ratio of sulfuric acid solution to hydrogen peroxide solution is 1:0.8, filtering and separating the graphene, washing with water and drying to obtain graphene oxide;

S52, adding TiCl ₄ to ammonia water, the volume ratio of TiCl ₄ to ammonia water is 1:4, stirring to react, obtaining a white precipitate, adding the white precipitate to oxalic acid with a mass concentration of 10% at a mass volume ratio of 1 g/100 mL, stirring to dissolve, and obtaining a titanium oxalate solution; adding graphene oxide, ammonium acetate and citric acid to the titanium oxalate solution, the mass ratio of graphene oxide, ammonium acetate and citric acid is 10:2:1, the mass volume ratio of graphene oxide to the titanium oxalate solution is 1 g/80 mL, heating to 80°C, stirring to react for 2 h, standing to age for 10 h, separating, placing at 180°C for 20 min, and then calcining at 600°C for 3 h to obtain a titanium dioxide-graphene oxide composite;

S53, adding sodium carboxymethyl cellulose into water, stirring and dissolving to prepare a sodium carboxymethyl cellulose aqueous solution with a mass concentration of 0.5%, adding an acid catalyst to the sodium carboxymethyl cellulose solution, the acid catalyst added in an amount of 0.05wt% of the acid in the sodium carboxymethyl cellulose aqueous solution, the catalyst being a mixture of SnCl4 and 10wt% hydrochloric acid, the mass volume ratio of the two being 0.001:1, stirring and mixing evenly, and then adding titanium dioxide-graphene oxide composite at a mass volume ratio of 1g/150mL, heating to 80°C, keeping the temperature for reaction for 152min, filtering, washing and drying in sequence after the reaction is completed.

Example 5

A method for preparing an anti-ultraviolet composite fabric filled with biological natural crystal powder comprises the following steps:

S1, mixing nylon 6 slices, natural crystal powder and spinning aid calcium stearate evenly, wherein the mass ratio of nylon slices, natural crystal powder and spinning aid is 1:0.08:0.01, to obtain a mixture;

As mentioned above, the natural crystal powder is mixed by the following substances in equal quantities:

Fluorite powder, orange crystal calcite powder, shungite powder, bloodstone powder, gypsum powder, aragonite powder, tourmaline powder, white crystal powder, rose crystal powder, aventurine powder, red jasper powder, serpentine powder;

S2, adding the mixed material into a melt spinning machine for spinning, the spinning temperature is controlled at 220°C, and after the silk fibroin is ejected from the spinneret, it is cold cut into shape at room temperature;

S3, applying oil to the formed tow, and then drawing and winding the tow in sequence to obtain nylon fiber;

S4, blending the cotton fiber and the nylon fiber in a mass ratio of 1:1 to obtain a blended yarn, and weaving the blended yarn to obtain a nylon/cotton blended fabric;

S5, adding the modified graphene into a 5wt% aqueous polyurethane solution at a mass volume ratio of 1g/200mL, stirring and mixing evenly to form a suspension, and then immersing the nylon/cotton blended fabric in the above suspension. After the immersion is completed, the textile is placed in an oven at 60°C for drying to obtain.

Preparation method of modified graphene:

S51, adding graphene to a sulfuric acid solution at a mass volume ratio of 1g/80mL, cooling to below 0°C, adding potassium permanganate, the mass ratio of graphene to potassium permanganate is 1:3, stirring evenly and heating to 70°C, keeping warm for 50min, then adding a 10wt% aqueous hydrogen peroxide solution for oxidation reaction, the volume ratio of sulfuric acid solution to hydrogen peroxide solution is 1:0.8, filtering and separating the graphene, washing with water and drying to obtain graphene oxide;

S52, adding TiCl ₄ to ammonia water, the volume ratio of TiCl ₄ to ammonia water is 1:4, stirring to react, obtaining a white precipitate, adding the white precipitate to oxalic acid with a mass concentration of 10% at a mass volume ratio of 1 g/100 mL, stirring to dissolve, and obtaining a titanium oxalate solution; adding graphene oxide, ammonium acetate and citric acid to the titanium oxalate solution, the mass ratio of graphene oxide, ammonium acetate and citric acid is 10:2:1, the mass volume ratio of graphene oxide to the titanium oxalate solution is 1 g/80 mL, heating to 80°C, stirring to react for 2 h, standing to age for 10 h, separating, placing at 180°C for 20 min, and then calcining at 600°C for 3 h to obtain a titanium dioxide-graphene oxide composite;

S53, adding sodium carboxymethyl cellulose into water and stirring to dissolve to prepare a sodium carboxymethyl cellulose aqueous solution with a mass concentration of 0.5%, adding an acid catalyst to the sodium carboxymethyl cellulose solution, the acid catalyst added in an amount of 0.05wt% of the acid in the sodium carboxymethyl cellulose aqueous solution, the catalyst being a mixture of SnCl4 and 10wt% hydrochloric acid, the mass volume ratio of the two being 0.001:1, stirring to mix evenly, and then adding titanium dioxide-graphene oxide composite at a mass volume ratio of 1g/150mL, heating to 80°C, keeping the temperature for reaction for 120min, filtering, washing and drying in sequence after the reaction is completed to obtain the product.

Comparative Example 1

The difference between Comparative Example 1 and Example 1 is:

In step S5, the modified graphene is replaced with ordinary graphene;

The remaining steps are the same as those in Example 1.

Comparative Example 2

The difference between Comparative Example 2 and Example 1 is:

Eliminate the S52 operation steps;

The remaining steps are the same as those in Example 1.

Comparative Example 3

The difference between Comparative Example 3 and Example 1 is that:

No natural crystal powder is added in step S1;

The remaining steps are the same as those in Example 1.

Performance Testing

1. Test of UV protection performance of fabrics: The UV protection index UPF of the fabrics of Examples 1-5 and Comparative Examples 1-2 was tested using a Labsphere UV-1000F fabric UV tester. Each fabric was tested 5 times and the average value was taken. The test results are shown in Table 1:

Table 1

2. The fabric materials prepared in Examples 1-5 were tested for wrinkle recovery angle using a YG541B fabric wrinkle elasticity tester according to the method specified in GB/T3819-1997, and the tensile breaking strength of the fabric was tested using a YG065 electronic fabric strength tester. The test results are shown in Table 2:

Table 2:

3. The far-infrared release performance of textile fabrics was tested using the GB/T30127-2013 method. The test results are shown in Table 3:

Table 3

The above are only preferred embodiments of the present invention. It should be noted that the above preferred embodiments should not be regarded as limiting the present invention, and the protection scope of the present invention should be based on the scope defined by the claims. For ordinary technicians in this technical field, several improvements and modifications can be made without departing from the spirit and scope of the present invention, and these improvements and modifications should also be regarded as the protection scope of the present invention.

Claims (10)

1. The preparation method of the ultraviolet-proof composite fabric filled with the biological natural crystal powder is characterized by comprising the following steps of:

S1, uniformly mixing nylon slices, natural crystal powder and spinning auxiliary agents to obtain a mixture;

S2, adding the mixture into a melt spinning machine for spinning, and then cold-cutting and molding a spinning beam obtained by spinning;

s3, oiling the formed tows, and drawing and winding the tows after oiling is finished to obtain nylon fibers;

s4, blending the cotton fibers and the nylon fibers to obtain blended yarns, and weaving the blended yarns to obtain nylon/cotton blended fabrics;

And S5, adding graphene into the aqueous polyurethane solution, stirring and mixing uniformly to form a suspension, then dipping nylon/cotton blended fabric into the suspension, and placing the textile in an oven for drying treatment after the dipping is completed, thus obtaining the polyurethane fabric.

2. The method for preparing the ultraviolet-resistant composite fabric filled with the biological natural crystal powder according to claim 1, wherein in the step S1, the mass ratio of the nylon chips, the natural crystal powder and the spinning auxiliary agent is 1:0.08:0.01.

3. The method for preparing the ultraviolet-proof composite fabric filled with the biological natural crystal powder according to claim 1, wherein in the step S1, the natural crystal powder is formed by mixing the following substances:

fluorite powder, orange calcite powder, hypographite powder, hematonite powder, gypsum powder, aragonite powder, tourmaline powder, white water crystal powder, rose crystal powder, placer powder, red jade powder and serpentine powder.

4. The method for preparing the ultraviolet-resistant composite fabric filled with the biological natural crystal powder according to claim 1, wherein in the step S4, the blending ratio of cotton fibers to nylon fibers is 1:1-5.

5. The method for preparing the ultraviolet-proof composite fabric filled with the biological natural crystal powder according to claim 1, wherein in the step S5, the concentration of the aqueous polyurethane solution is 5-10wt%.

6. The method for preparing the ultraviolet-proof composite fabric filled with the biological natural crystal powder according to claim 1, wherein in the step S5, graphene is modified, and the steps are as follows:

s51, adding graphene into sulfuric acid solution, cooling to below 0 ℃, adding potassium permanganate, uniformly stirring, heating, adding hydrogen peroxide aqueous solution for oxidation reaction, filtering to separate graphene, washing with water, and drying to obtain graphene oxide;

S52, adding TiCl ₄ into ammonia water, stirring for reaction to obtain white precipitate, adding oxalic acid into the white precipitate, and stirring for dissolution to obtain a titanyl oxalate solution; adding graphene oxide, ammonium acetate and citric acid into a titanyl oxalate solution, heating, stirring, reacting, standing, aging and calcining to obtain a titanium dioxide-graphene oxide compound;

And S53, adding sodium carboxymethyl cellulose into water, stirring and dissolving to prepare sodium carboxymethyl cellulose water solution with the mass concentration of 0.5%, adding an acid catalyst into the sodium carboxymethyl cellulose solution, stirring and mixing uniformly, then adding a titanium dioxide-graphene oxide compound, heating to 80 ℃, carrying out heat preservation reaction, and sequentially filtering, washing and drying after the reaction is completed, thus obtaining the catalyst.

7. The method for preparing the ultraviolet-proof composite fabric filled with the biological natural crystal powder according to claim 6, wherein in the step S51, the mass ratio of graphene to potassium permanganate is 1:3-8.

8. The method for preparing an ultraviolet-proof composite fabric filled with biological natural crystal powder according to claim 6, wherein in the step S51, the concentration of the hydrogen peroxide aqueous solution is 10-20wt%.

9. The method for preparing the ultraviolet-proof composite fabric filled with the biological natural crystal powder according to claim 6, wherein in the step S53, the heat preservation reaction time is controlled to be 120-152min.

10. An anti-ultraviolet composite fabric filled with biological natural crystal powder, which is characterized by being prepared by the method of any one of claims 1-9.