阅读说明：本技术 抗菌抗病毒防护材料及其制备方法 (Antibacterial and antiviral protective material and preparation method thereof ) 是由 夏良君 周思婕 付专 张春华 宫钧耀 朱娜 刘欣 徐卫林 于 2021-07-05 设计创作，主要内容包括：本发明提供了一种抗菌抗病毒防护材料及其制备方法。该抗菌抗病毒防护材料的制备方法,首先对织物进行前处理,然后将织物依次浸渍铜源溶液、碱性溶液和还原溶液；最后再将织物置于溶剂中进行原位反应生成纳米氧化亚铜,反应温度为100℃～300℃,反应时间为5s～1800s。通过上述方式,在高温环境下进行原位合成反应,使得织物上的溶剂在原位合成的溶剂中气化,产生瞬时高压,几秒内即可完成纳米氧化亚铜的合成,降温时,得到的纳米氧化亚铜颗粒固定在前处理形成在纤维表面的凹槽中,显著提高了纳米氧化亚铜颗粒与织物的结合牢度,保证了织物的长效抗菌抗病毒性能。(The invention provides an antibacterial and antiviral protective material and a preparation method thereof. The preparation method of the antibacterial and antiviral protective material comprises the steps of firstly pretreating a fabric, and then sequentially dipping the fabric into a copper source solution, an alkaline solution and a reducing solution; finally, the fabric is placed in a solvent to carry out in-situ reaction to generate the nano cuprous oxide, the reaction temperature is 100-300 ℃, and the reaction time is 5-1800 s. By the mode, the in-situ synthesis reaction is carried out in a high-temperature environment, so that the solvent on the fabric is gasified in the solvent of the in-situ synthesis to generate instantaneous high pressure, the synthesis of the nano cuprous oxide can be completed within a few seconds, and the obtained nano cuprous oxide particles are fixed in the grooves formed on the surface of the fiber in the pretreatment process during cooling, so that the bonding fastness of the nano cuprous oxide particles and the fabric is remarkably improved, and the long-acting antibacterial and antiviral performance of the fabric is ensured.)

1. The preparation method of the antibacterial and antiviral protective material is characterized by comprising the following steps:

s1, fabric pretreatment

Placing the fabric in a pretreatment solution for padding; wherein the pretreatment solution is a sodium hydroxide solution, a potassium hydroxide solution, a mixed solution of sodium hydroxide and urea, a biological enzyme solution, an N-methylmorpholine-N-oxide solution, a chitosan solution or a plasma solution;

s2, pre-treatment fabric dipping precursor solution

Sequentially dipping the pretreated fabric into an alkaline solution, a copper source solution and a reducing solution for 5-360 s, wherein the liquid carrying rate of the padded fabric is 10-160%; wherein the mass fraction of solute in the copper source solution is 0.1-20%; the mass fraction of solute in the alkaline solution is 0.1-20%; the mass fraction of solute in the reduction solution is 0.1-20%;

s3, in-situ synthesis of cuprous oxide by using fabric

Placing the fabric impregnated with the precursor solution in a solvent for reaction to generate cuprous oxide in situ, wherein the reaction temperature is 100-300 ℃, and the reaction time is 5-1800 s;

the solvent is glycol, glycerol, ethyl acetate, toluene, xylene, N-dimethylformamide, N-dimethylacetamide, silicone oil, vegetable oil and animal oil.

2. The method for preparing the antibacterial and antiviral protective material according to claim 1, wherein the method comprises the following steps: in step S2, the copper source solution is a copper acetate solution, a copper nitrate solution, a copper sulfate solution, or a copper chloride solution; the alkaline solution is a sodium hydroxide solution, a potassium hydroxide solution, an ammonium carbonate solution or an ammonia water solution; the reducing solution is a solution of ascorbic acid, glucose, diethylene glycol or glycerol.

3. The method for preparing the antibacterial and antiviral protective material according to claim 1, wherein the method comprises the following steps: the silicone oil is methyl silicone oil, ethyl hydrogen-containing silicone oil, phenyl silicone oil, methyl chlorphenyl silicone oil, methyl ethoxy silicone oil, methyl trifluoro propyl silicone oil, methyl vinyl silicone oil or fluorine-containing silicone oil.

4. The method for preparing the antibacterial and antiviral protective material according to claim 1, wherein the method comprises the following steps: in step S1, the mass fraction of solute in the pretreatment solution is 0.1% to 20%; or in step S1, the dipping temperature is-12 to 80 ℃, the liquid carrying rate of the padded fabric is 10 to 160%, and the padding mode is one-dipping one-rolling or two-dipping two-rolling or three-dipping three-rolling.

5. The method for preparing the antibacterial and antiviral protective material according to claim 1, wherein the method comprises the following steps: in step S2, the padding mode is one-dip one-rolling, two-dip two-rolling, or three-dip three-rolling; the dipping temperature is 10-80 ℃.

6. An antibacterial and antiviral protective material is characterized in that: the antibacterial and antiviral protective material is prepared by the preparation method of the antibacterial and antiviral protective material according to any one of claims 1 to 5, wherein the antibacterial and antiviral protective material is a fabric modified by nano cuprous oxide; the nano cuprous oxide is generated by the in-situ reaction of a precursor solution and is uniformly distributed inside and outside the fiber of the antibacterial and antiviral protective material, and the particle size of the nano cuprous oxide is 50-600 nm.

7. The method for preparing the antibacterial and antiviral protective material according to claim 6, wherein the method comprises the following steps: the fabric is a natural fiber fabric or a chemical fiber fabric; the natural fiber fabric is a cotton fiber fabric or a wool fiber fabric in a hemp fiber fabric; the chemical fiber fabric is a polypropylene fiber fabric, a polyester fiber fabric, a viscose fiber fabric, a spandex fiber fabric or an aramid fiber fabric.

8. The antibacterial and antiviral protective material according to claim 7, wherein: the crystal form of the nano cuprous oxide is one or more of a cubic form, an octahedral form, a rhombohedral form, a decaoctahedral form and a hexahedral form.

9. The antibacterial and antiviral protective material according to claim 8, wherein: the fabric has bactericidal and virucidal properties.

10. The antibacterial and antiviral protective material according to claim 8, wherein: the antibacterial and antiviral protective material is applied to preparing masks, gas masks, protective clothing, air purifiers or air filter elements.

Technical Field

The invention relates to the technical field of antibacterial and antiviral materials, in particular to an antibacterial and antiviral protective material for in-situ synthesis of nano cuprous oxide on a fabric and a preparation method thereof.

Background

The fiber of the common textile does not have antibacterial capacity, and can provide living and breeding environment for bacteria under certain conditions, thus threatening the health of human beings. The ecological environment such as extreme environment, environmental pollution and the like in the current society is seriously worsened, and special living micro-environments such as closed space and the like cause urgent needs of people for functional protection textiles. In the prior art, the main method for solving the antibacterial problem of the fiber is to prepare the modified fiber with the antibacterial effect by carrying out composite modification on the nano particles with the antibacterial effect and the polymer matrix, and the antibacterial component is gradually released in the use process of the fiber to achieve the antibacterial aim.

Compared with the nano silver antibacterial agent, the copper antibacterial material has the advantage of lower raw material cost. In the prior art, the method for synthesizing cuprous oxide on the surface of a fabric generally adopts modification or grafting of active functional groups, and then synthesizes functional nanoparticles on the surface. However, the prior art has the defects of low loading capacity, long reaction time, high production cost, poor bonding fastness of the functional nanoparticles and the fabric, poor washing fastness and the like, and is difficult to meet the wide requirements of the current market.

Patent publication No. CN 103167798A provides an antimicrobial and antiviral composition. The antimicrobial and antiviral composition has a BET specific surface area of 5 to 100m²Cuprous oxide particles and a saccharide having an aldehyde group, wherein the content of the saccharide having an aldehyde group is 0.5 to 10 parts by mass based on 100 parts by mass of the cuprous oxide particles. The composition maintains good antimicrobial and antiviral properties by adding an appropriate amount of a saccharide having an aldehyde group to inhibit cuprous oxide oxidation.

The patent with publication number CN 105311668A provides a bacterial cellulose composite cuprous oxide antibacterial dressing and a preparation method thereof, wherein the bacterial cellulose composite cuprous oxide antibacterial dressing is formed by attaching cuprous oxide particles in a three-dimensional porous network structure of a bacterial cellulose hydrogel film; the cuprous oxide particles are in an octahedral crystal form, and the antibacterial dressing is obtained by soaking a bacterial cellulose hydrogel film containing a glucose solution in a mixed solution of an NaOH aqueous solution and a copper ion aqueous solution, and heating and pressurizing for reaction.

However, the cuprous oxide particles are loaded on the fabric/fiber to endow the fabric with antibacterial performance, so that the problems of limited loading capacity and poor binding fastness exist; the method for synthesizing the functional particles on the surface of the fabric has the problems of long reaction time, complex reaction process and high production cost.

In view of the above, there is a need to design an improved antibacterial and antiviral protective material containing nano cuprous oxide and a preparation method thereof, so as to solve the above problems.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide the preparation method of the antibacterial and antiviral protective material, which is simple in synthesis method and can quickly synthesize the nano cuprous oxide on the fabric in situ, and the obtained antibacterial and antiviral protective material has the advantages of high binding fastness of the nano cuprous oxide and the fabric, good washability, long-acting antibacterial and antiviral performance and capability of meeting the wide market demands.

In order to realize the aim, the invention provides a preparation method of an antibacterial and antiviral protective material, which comprises the following steps:

s1, fabric pretreatment

Placing the fabric in a pretreatment solution for padding; wherein the pretreatment solution is a sodium hydroxide solution, a potassium hydroxide solution, a mixed solution of sodium hydroxide and urea, a biological enzyme solution, an N-methylmorpholine-N-oxide solution, a chitosan solution or a plasma solution;

s2, pre-treatment fabric dipping precursor solution

Sequentially dipping the pretreated fabric into an alkaline solution, a copper source solution and a reducing solution for 5-360 seconds; wherein the mass fraction of solute in the copper source solution is 0.1-20%; the mass fraction of solute in the alkaline solution is 0.1-20%; the mass fraction of solute in the reduction solution is 0.1-20%;

s3, in-situ synthesis of cuprous oxide by using fabric

Placing the fabric impregnated with the precursor solution in a solvent for reaction to generate cuprous oxide in situ, wherein the reaction temperature is 100-300 ℃, and the reaction time is 5-1800 s;

the solvent is glycol, glycerol, ethyl acetate, toluene, xylene, N-dimethylformamide, N-dimethylacetamide, silicone oil, vegetable oil and animal oil.

As a further improvement of the present invention, in step S2, the copper source solution is a copper acetate solution, a copper nitrate solution, a copper sulfate solution, or a copper chloride solution; the alkaline solution is a sodium hydroxide solution, a potassium hydroxide solution, an ammonium carbonate solution or an ammonia water solution; the reducing solution is a solution of ascorbic acid, glucose, diethylene glycol or glycerol.

As a further improvement of the invention, the silicone oil is methyl silicone oil, ethyl hydrogen-containing silicone oil, phenyl silicone oil, methyl chlorphenyl silicone oil, methyl ethoxy silicone oil, methyl trifluoro propyl silicone oil, methyl vinyl silicone oil or fluorine-containing silicone oil.

As a further improvement of the present invention, in step S1, the mass fraction of the solute in the pretreatment solution is 0.1% to 20%; or in step S1, the dipping temperature is-12 to 80 ℃, the liquid carrying rate of the padded fabric is 10 to 160%, and the padding mode is one-dipping one-rolling or two-dipping two-rolling or three-dipping three-rolling.

As a further improvement of the present invention, in step S2, the padding mode is one-dip one-rolling, two-dip two-rolling or three-dip three-rolling; the dipping temperature is 10-80 ℃, and the liquid carrying rate of the fabric after padding is 10-160%.

As a further improvement of the present invention, the method further comprises a post-treatment step of washing the fabric obtained in step S3 to remove the solvent.

In order to realize the aim, the invention also provides an antibacterial and antiviral protective material, which is a fabric modified by the nano cuprous oxide; the nano cuprous oxide is generated by in-situ reaction of a precursor solution and is uniformly distributed inside and outside the fiber of the antibacterial and antiviral protective material, and the particle size of the nano cuprous oxide is 50-600 nm.

As a further improvement of the invention, the crystal form of the nano cuprous oxide is one or more of a cubic form, an octahedral form, a rhombohedral form, a decaoctahedral form and a hexahedral form.

As a further improvement of the present invention, the fabric has bactericidal and virucidal properties; the antibacterial and antiviral protective material is applied to preparing masks, gas masks, protective clothing, air purifiers or air filter elements.

The invention has the beneficial effects that:

(1) according to the invention, a proper pretreatment solution is selected to perform slightly-dissolving pretreatment on the fabric, so that grooves are formed on the surface of the fiber, and a plurality of reaction spaces are provided for the subsequent in-situ synthesis reaction; namely, providing a growth position for the subsequent nano cuprous oxide particles; then sequentially dipping the fabric into a copper source solution, an alkaline solution and a reducing solution; then placing the fabric in a solvent for reaction to generate cuprous oxide, wherein the reaction temperature is 100-300 ℃, and the reaction time is 5-1800 s; in the in-situ synthesis process, the liquid carrying rate of the fabric after padding is controlled to be 10% -160% based on the previous padding step, so that the fabric is provided with a solvent, the solvent on the fabric is gasified in the solvent synthesized in situ to generate instantaneous high pressure during the in-situ synthesis reaction in a high-temperature environment (100 ℃ -300 ℃), the synthesis of the nano cuprous oxide can be completed within a few seconds, the obtained nano cuprous oxide particles are fixed in grooves formed on the surface of the fiber in a pretreatment manner during cooling, the bonding firmness of the nano cuprous oxide particles and the fabric is remarkably improved, and the long-acting antibacterial and antiviral performance of the fabric is ensured.

(2) The antibacterial and antiviral protective material prepared by the invention has excellent antibacterial performance: the killing rate to bacteria and virus is as high as 99%, and the antibacterial material can be used in the fields of masks, protective clothing, face masks, air purification and other antibacterial materials.

(3) The preparation method of the antibacterial and antiviral protective material comprises the steps of firstly forming a reaction space on the surface of the fiber through pretreatment, then dipping the reaction material on the fabric, and then carrying out in-situ synthesis reaction in a high-temperature solvent to quickly and simply synthesize cuprous oxide nanoparticles, wherein the fastness of the nanoparticles is fixed on the fiber during cooling.

(4) The preparation method can synthesize cuprous oxide nanoparticles with different crystal forms on the fabric by regulating and controlling the temperature so as to meet different requirements, and has wide application range.

Drawings

FIG. 1 is an electron microscope image of the antibacterial and antiviral protective material prepared in example 1 of the present invention, with a scale of 10 um.

Fig. 2 is an electron microscope image of the antibacterial and antiviral protective material prepared in example 1 of the present invention, with a scale of 1 um.

Fig. 3 is an electron microscope image of the antibacterial and antiviral protective material prepared in example 1 of the present invention, with a scale of 1 um.

FIG. 4 is a spectrum analysis chart of the antibacterial and antiviral protective material prepared in example 1 of the present invention.

FIG. 5 is an element distribution diagram of the antibacterial and antiviral protective material prepared in example 1 of the present invention.

FIG. 6 is a graph showing the result of the antibacterial test of the antibacterial and antiviral protective material prepared in example 1 of the present invention.

FIG. 7 is an electron micrograph of the antibacterial and antiviral protective material prepared in example 13 of the present invention, with a scale of 1 um.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to the accompanying drawings and specific embodiments.

It should be noted that, in order to avoid obscuring the present invention with unnecessary details, only the structures and/or processing steps closely related to the aspects of the present invention are shown in the drawings, and other details not closely related to the present invention are omitted.

In addition, it is also to be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.

The invention provides a preparation method of an antibacterial and antiviral protective material, which comprises the following steps:

s1, fabric pretreatment

Placing the fabric in a pretreatment solution for padding; wherein the pretreatment solution is a sodium hydroxide solution, a potassium hydroxide solution, a mixed solution of sodium hydroxide and urea, a biological enzyme solution, an N-methylmorpholine-N-oxide solution, a chitosan solution or a plasma solution;

s2, pre-treatment fabric dipping precursor solution

Sequentially dipping the pretreated fabric into an alkaline solution, a copper source solution and a reducing solution for 5-360 seconds; wherein the mass fraction of solute in the copper source solution is 0.1-20%; the mass fraction of solute in the alkaline solution is 0.1-20%; the mass fraction of solute in the reduction solution is 0.1-20%;

s3, in-situ synthesis of cuprous oxide by using fabric

Placing the fabric impregnated with the precursor solution in a solvent for reaction to generate cuprous oxide in situ, wherein the reaction temperature is 100-300 ℃, and the reaction time is 5-1800 s;

the solvent is glycol, glycerol, ethyl acetate, toluene, xylene, N-dimethylformamide, N-dimethylacetamide, silicone oil, vegetable oil and animal oil. The silicone oil is methyl silicone oil, ethyl hydrogen-containing silicone oil, phenyl silicone oil, methyl chlorphenyl silicone oil, methyl ethoxy silicone oil, methyl trifluoro propyl silicone oil, methyl vinyl silicone oil or fluorine-containing silicone oil.

In step S1, the mass fraction of solute in the pretreatment solution is 0.1% to 20%; the dipping temperature is-12-80 ℃, the liquid carrying rate of the fabric after padding is 10-160%, and the padding mode is one-dipping one-rolling or two-dipping two-rolling or three-dipping three-rolling.

In step S2, the copper source solution is a copper acetate solution, a copper nitrate solution, a copper sulfate solution, or a copper chloride solution; the alkaline solution is a sodium hydroxide solution, a potassium hydroxide solution, an ammonium carbonate solution or an ammonia water solution; the reducing solution is a solution of ascorbic acid, glucose, diethylene glycol or glycerol.

The padding mode is one-dipping one-rolling or two-dipping two-rolling or three-dipping three-rolling; the dipping temperature is 10-80 ℃, and the liquid carrying rate of the fabric after padding is 10-160%.

It should be understood that the preparation method may further include a post-treatment step of washing the fabric obtained in step S3 to remove the solvent.

The fabric is a woven fabric, a knitted fabric or a non-woven fabric; the fabric is woven by one or more of natural fibers or synthetic fibers; the natural fiber is cotton fiber, hemp fiber, silk fiber, wool fiber, kapok fiber or rush fiber; the synthetic fiber is polyester fiber, polyamide fiber, acrylic fiber, vinylon fiber, polypropylene fiber or polyvinyl chloride fiber.

The weaving mode comprises spinning, weaving, knitting, melt blowing or needling.

The following will explain the preparation method of the antibacterial and antiviral protective material provided by the present invention with reference to the examples and comparative examples.

Example 1

The embodiment provides a preparation method of an antibacterial and antiviral protective material, which comprises the following steps:

s1, fabric pretreatment

Placing the polypropylene fiber fabric in a sodium hydroxide solution with the mass fraction of 7% for padding; wherein the dipping time is 5s, the dipping temperature is 25 ℃, the liquid carrying rate of the fabric after padding is 120 percent, and the padding is one-dipping one-rolling or two-dipping two-rolling or three-dipping three-rolling;

s2, pre-treatment fabric dipping precursor solution

Sequentially dipping the pretreated polypropylene fabric into 7% by mass of sodium hydroxide alkaline solution for 60s, 4% by mass of copper sulfate solution for 30s and 4% by mass of glucose reduction solution for 300 s;

s3, in-situ synthesis of cuprous oxide by using fabric

Placing the fabric soaked with the precursor solution into a dimethyl silicone oil solvent with the temperature of 150 ℃ for reaction to generate cuprous oxide in situ, wherein the reaction time is 15 s; namely, the antibacterial and antiviral protective material containing the nano cuprous oxide particles is obtained.

Scanning electron microscope characterization is carried out on the antibacterial and antiviral protective material prepared in example 1, and the results are shown in fig. 1-3. As can be seen from FIGS. 1 to 3, a large number of nanoparticles are uniformly loaded on the surface of the fiber, which indicates that the preparation method provided by the invention can synthesize the nanoparticles in situ and uniformly load the nanoparticles on the surface of the fiber.

EDS (electron-dispersive spectroscopy) analysis of the antibacterial and antiviral protective material prepared in example 1 shows that the antibacterial and antiviral protective material contains 16 wt% of oxygen atoms and 11.6 wt% of copper atoms, which indicates that the surface of the polypropylene fabric has been successfully synthesized with Cu in situ₂And O. FIG. 5 is a distribution diagram of the elements, showing that the distribution of Cu element is uniform, further illustrating Cu₂The distribution of O is very uniform.

After the antibacterial and antiviral protective material is washed for 30 times by referring to GN/T20944-.

Examples 2 to 4 and comparative example 1

Examples 2 to 4 respectively provide a method for preparing an antibacterial and antiviral protective material, which is different from example 1 in that the liquid carrying rate of the fabric subjected to padding treatment in step S1 is changed, and the preparation parameters corresponding to the examples are shown in table 1. The remaining steps of examples 2-4 and comparative example 1 are substantially the same as example 1, and are not repeated herein.

TABLE 1 test results of liquid carrying rate of padded fabrics of examples 2 to 4 and step S1 of comparative example 1 and antibacterial and antiviral protective material prepared therefrom

As can be seen from comparison of examples 1 to 4, as the liquid carrying rate of the fabric after padding treatment increases, the amount of nano-cuprous oxide loaded tends to increase first and then decrease, and when the liquid carrying rate is 120%, the amount of nano-cuprous oxide loaded is the greatest.

Experiments show that when the liquid carrying rate of the fabric after padding treatment is less than 10%, the load of the reaction solution is not facilitated, and therefore the generation load of cuprous oxide is small.

When the liquid carrying rate of the fabric after padding treatment is more than 120%, the growth of cuprous oxide is not facilitated due to the overlarge reaction solution.

Examples 5 to 8

Examples 5 to 8 each provide a method for producing an antibacterial and antiviral protective material, which is different from example 1 in that the mass fraction of the solute in the pretreatment solution in step S1 is changed, and the mass fractions of the solute in the pretreatment solutions corresponding to the examples are shown in table 2. The remaining steps of examples 5 to 8 are substantially the same as those of example 1, and are not described herein again.

TABLE 2 test results of the process parameters and the antibacterial and antiviral protective materials prepared in examples 5 to 8

Experiments show that when the mass fraction of the solute in the current treatment solution is less than 0.1%, the alkaline solution carried on the fabric is too little, and the subsequent reaction is not enough to form obvious antibacterial and antiviral effects on the fabric.

When the mass fraction of the solute in the solution to be treated is more than 20%, the surface layer of the fabric has too large load after the reaction of the copper sulfate solution, the load reaction precipitate is easy to fall off from the surface layer of the fabric, and the obvious antibacterial and antiviral effects cannot be formed on the fabric after the subsequent reaction.

Examples 9 to 12

Examples 9 to 12 respectively provide a method for preparing an antibacterial and antiviral protective material, which is different from example 1 in that the reaction temperature of the in-situ synthesis reaction in step S3 and the mass fractions of the copper source solution, the alkaline solution and the reducing solution in step S2 are changed, as shown in table 3. The remaining steps of examples 9 to 12 are substantially the same as those of example 1, and are not described herein again.

TABLE 2 Process parameters for examples 9-12

Experiments show that the higher the concentration of the reaction solution, the higher the temperature, the more the shape of the generated cuprous oxide nanoparticles is close to spherical.

The solvent may be ethylene glycol, glycerol, ethyl acetate, toluene, xylene, N-dimethylformamide, N-dimethylacetamide, silicone oil, vegetable oil, or animal oil. The silicone oil is methyl silicone oil, ethyl hydrogen-containing silicone oil, phenyl silicone oil, methyl chlorphenyl silicone oil, methyl ethoxy silicone oil, methyl trifluoro propyl silicone oil, methyl vinyl silicone oil or fluorine-containing silicone oil.

The copper source solution is a copper acetate solution, a copper nitrate solution, a copper sulfate solution or a copper chloride solution; the alkaline solution is a sodium hydroxide solution, a potassium hydroxide solution, an ammonium carbonate solution or an ammonia water solution; the reducing solution is a solution of ascorbic acid, glucose, diethylene glycol or glycerol.

Example 13

The embodiment provides a preparation method of an antibacterial and antiviral protective material, which comprises the following steps:

s1, fabric pretreatment

Soaking the cotton fabric in a mixed solution of 7% of sodium hydroxide and 12% of urea by mass percent, and then padding; wherein the dipping time is 2 hours, the padding time is 15 seconds, the dipping temperature is-12 ℃, the padding temperature is 25 ℃, the liquid carrying rate of the padded fabric is 150 percent, and the padding is one-dipping one-rolling or two-dipping two-rolling or three-dipping three-rolling;

s2, pre-treatment fabric dipping precursor solution

Sequentially dipping the pretreated cotton fabric in 7% by mass of sodium hydroxide alkaline solution for 5s, 4% by mass of copper sulfate copper source solution for 15s and 6% by mass of glucose reduction solution for 300 s;

s3, in-situ synthesis of cuprous oxide by using fabric

Placing the fabric soaked with the precursor solution into a dimethyl silicone oil solvent at the temperature of 200 ℃ for reaction to generate cuprous oxide in situ, wherein the reaction time is 20 s; namely, the antibacterial and antiviral protective material containing the nano cuprous oxide particles is obtained.

Scanning electron microscope characterization was performed on the antibacterial and antiviral protective material prepared in example 13, and the results are shown in fig. 7. As can be seen from FIG. 7, a large number of nanoparticles are uniformly loaded on the surface of the fiber, which indicates that the preparation method provided by the invention can rapidly synthesize the nanoparticles in situ and uniformly load the nanoparticles on the surface of the fiber.

In conclusion, according to the preparation method of the antibacterial and antiviral protective material provided by the invention, the fabric is subjected to slightly-dissolving pretreatment by selecting a proper pretreatment solution, so that grooves are formed on the surface of the fiber, and a plurality of reaction spaces are provided for the subsequent in-situ synthesis reaction; namely, providing a growth position for the subsequent nano cuprous oxide particles; then sequentially dipping the fabric into a copper source solution, an alkaline solution and a reducing solution; then placing the fabric in a solvent for reaction to generate nano cuprous oxide, wherein the reaction temperature is 100-300 ℃, and the reaction time is 5-1800 s; in the in-situ synthesis process, the liquor carrying rate of the fabric after padding is controlled to be 10% -160% based on the previous padding step, so that the fabric is provided with the solvent, the solvent on the fabric is gasified in the solvent synthesized in situ to generate instantaneous high pressure during the in-situ synthesis reaction in a high-temperature environment (100 ℃ -300 ℃), the synthesis of the nano cuprous oxide can be completed within a few seconds, the obtained nano cuprous oxide particles are fixed in grooves formed on the surface of the fiber in a pretreatment manner during cooling, the bonding firmness of the nano cuprous oxide particles and the fabric is obviously improved, the long-acting antibacterial and antiviral performance of the fabric is ensured, the preparation method is simple to operate, the application range is wide, the production cost is reduced, and the application value is high.

The antibacterial and antiviral protective material can be used in the fields of antibacterial materials such as masks, protective clothing, masks, air purification and the like.

Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the spirit and scope of the present invention.