Preparation method of an antibacterial and flame-retardant fabric

Abstract

The present invention relates to the field of multifunctional textiles, and particularly to a preparation method of an antibacterial and flame-retardant fabric. The characteristics of the present invention are that cuprous oxide is adsorbed on the active sites on the fabric surface by means of carboxyl groups, and based on the principle of electrostatic adsorption, cuprous oxide is loaded onto antimony trioxide. At the same time, copper atoms partially replace antimony atoms, and a Cu-O-Sb bonding bond is formed through electron transfer, endowing the fabric with antibacterial and flame-retardant properties. The antibacterial and flame-retardant fabric prepared by the method of the present invention has a stable structure and excellent antibacterial performance. After testing, the antibacterial rates against Escherichia coli and Staphylococcus aureus are both > 99%, and the flame-retardant effect is remarkable, with the limiting oxygen index of combustion increased by ~25%. At the same time, the raw materials and preparation process are simple, with low cost, safety and environmental protection, and it is easy to carry out large-scale industrial production, having a broad market prospect.

Description

Technical Field

[0001] The present invention relates to the field of multifunctional textiles, and particularly to a preparation method of an antibacterial and flame-retardant fabric. Background Art

[0002] Cotton fabrics are widely used in the fields of clothing, home decoration, etc. due to their characteristics such as being renewable, water-absorbent, having strong air permeability and soft handfeel. However, their good water absorbency makes them prone to bacterial growth during use, endangering human health. At the same time, the limiting oxygen index of cotton fabrics is relatively low, all < 19%, belonging to flammable fabrics. Once on fire, it will threaten human life and property safety. Therefore, developing multifunctional fabrics with antibacterial and flame-retardant properties has important research significance and potential commercial value.

[0003] Currently, in order to endow fabrics with dual antibacterial and flame-retardant functions, it is mainly achieved by mixing a variety of single-functional materials. However, the mixed use of functional materials will greatly reduce their own protection effect and cannot provide long-term effective protection for fabrics. At the same time, the above methods have disadvantages such as cumbersome processes, poor wash resistance, large consumption of chemical reagents and being non-environmental friendly. Research shows that modifying monomer materials with different functions on fabrics to endow fabrics with multiple functions is an effective way to solve the above problems.

[0004] Antimony trioxide is an additive flame retardant, which has characteristics such as small particle size, large surface activity and strong heat absorption ability. When burning, the nano powder covers the surface of the polymer condensed phase, which can well promote the formation of a carbonized layer and form a flame-retardant barrier between the combustion source and the material, thus playing a flame-retardant role. Copper oxide, as a new type of green antibacterial material, can activate water and oxygen in the air under light conditions and generate very active strongly oxidizing hydroxyl radicals ·OH and reactive oxygen ions O 2- ., directly or indirectly damage the structure and function of the cell membrane, resulting in the rupture of the cell membrane and the leakage of contents, and finally playing an antibacterial effect. Therefore, modifying the above two functional materials on fabrics to endow fabrics with dual antibacterial and flame-retardant functions has an important promoting effect on the development of multifunctional fabrics. However, in the prior art, there is no report or disclosure on this antibacterial and flame-retardant fabric and its preparation method. Summary of the Invention

[0005] Based on the above, the present invention provides a preparation method of an antibacterial and flame-retardant fabric. The antibacterial and flame-retardant fabric prepared by the method of the present invention has a stable structure, excellent antibacterial performance and remarkable flame-retardant effect. At the same time, the raw materials and preparation process are simple, the cost is low, it is safe and environmental friendly, and it is easy to be mass-produced industrially, with broad market prospects. The specific technical solutions are as follows:

[0006] A preparation method of an antibacterial and flame-retardant fabric, comprising the following steps:

[0007] (1) Prepare a phosphate buffer solution, and then dissolve TEMPO (tetramethylpiperidine oxide) in the phosphate buffer solution to obtain solution A;

[0008] (2) Add the fabric, NaClO 2 and the NaClO solution to solution A, stir well, then take out the fabric and wash it;

[0009] (3) Add copper acetate powder to deionized water, and immerse the washed fabric in this solution, stir constantly at a constant temperature to obtain solution B;

[0010] (4) Add a certain amount of sodium hydroxide to solution B and react fully;

[0011] (5) Add ascorbic acid to the solution after the reaction in step (4), keep the reaction temperature constant, after reacting fully, take out the fabric and wash it;

[0012] (6) Add dry antimony glycolate powder to an anhydrous ethanol solution, disperse it by ultrasonic wave to obtain solution C;

[0013] (7) Add the fabric washed in step (5) to solution C, stir well, then add pure water, and adjust the pH of the solution to weakly alkaline with an acidic or alkaline medium, and react fully;

[0014] (8) Transfer all the solution obtained in step (7) to a high-pressure reactor for reaction;

[0015] (9) After the reaction is completed, take out the fabric, wash it, and dry it to obtain an antibacterial and flame-retardant fabric.

[0016] Further, in step (1), the phosphate buffer solution is prepared from NaH 2 PO 4 solution and Na 2 HPO 4 solution, and the concentration of the phosphate buffer solution is 0.03 - 0.1 mol / L; the mass ratio of TEMPO to the fabric is M TEMPO : M 织物 = 1:40 - 60, preferably 1:50 - 55.

[0017] Further, in step (2), the mass ratio of NaClO 2 to the fabric is M NaClO2 : M 织物 = 1:15 - 25; the mass fraction of the NaClO solution is 12%, and the mass ratio of the NaClO solution to the fabric is M NaClO溶液 : M 织物 = 1.5 - 4:1, preferably 2 - 3:1; the stirring time is 2 - 3 h.

[0018] Further, in step (3), the stirring time is 1 - 2 h; the temperature is 40 - 60 °C.

[0019] Further, in step (4), the molar ratio of sodium hydroxide to copper acetate is: n 氢氧化钠 : n 乙酸铜 = 5 - 10:1, preferably 6 - 8:1; the reaction temperature is 60 - 80 °C; the reaction time is 20 - 30 min.

[0020] Further, in step (5), the molar ratio of ascorbic acid to copper acetate is: n 抗坏血酸 : n 乙酸铜 = 1:2 - 6, preferably 1:3 - 4; the reaction temperature is 60 - 80 °C; the reaction time is 40 - 60 min.

[0021] Further, in step (6), the molar ratio of antimony glycolate powder to copper acetate is: n 乙二醇锑 : n 乙酸铜 = 1:3 - 50, preferably 1:5 - 10; the mass ratio of antimony glycolate powder to absolute ethanol added is: m 乙二醇锑 : m 无水乙醇 = 1:4 - 10, preferably 1:5 - 7.

[0022] Further, in step (7), the volume ratio of pure water to absolute ethanol is V 水 : V 无水乙醇 = 1 - 2:1; the acidic medium is selected from one or more of phosphoric acid, sulfuric acid, hydrochloric acid, and acetic acid; the basic medium is selected from one or more of sodium hydroxide, potassium hydroxide, and ammonia water; the weak basicity is pH = 8 - 9; the reaction time is 1 - 2 h.

[0023] Further, in step (8), the reaction temperature is 120 - 140 °C; the reaction time is 10 - 12 h.

[0024] Further, in step (9), the washing is carried out 2 - 5 times; the drying temperature is 60 - 80 °C.

[0025] The characteristics of the present invention are as follows: cuprous oxide is adsorbed on the active sites of the fabric by means of carboxyl groups grafted on the fabric, and based on the principle of electrostatic adsorption, cuprous oxide is loaded onto antimony trioxide. At the same time, copper atoms partially replace antimony atoms, and a Cu-O-Sb bonding is formed through electron transfer, effectively loading the inorganic functional material onto the organic material and endowing the fabric with antibacterial and flame-retardant properties. The mechanism for the excellent antibacterial effect of the present invention is mainly due to the synergistic effect of cuprous oxide and antimony trioxide: on the one hand, in the antibacterial and flame-retardant fabric prepared by the method of the present invention, cuprous oxide and antimony trioxide nanomaterials form a Cu-O-Sb bonding through electron transfer. Since the band gap of cuprous oxide is 2.14 eV and the band gap of antimony trioxide is 3.00 eV, the conduction band energy level and valence band energy level of cuprous oxide are both lower than those of antimony trioxide. Electrons on the conduction band of antimony trioxide are easily transferred to the conduction band of cuprous oxide, and holes on the valence band of cuprous oxide are easily transferred to the valence band of antimony trioxide, thus preventing the recombination of free electrons and holes. The un-recombined electrons and holes react with oxygen molecules and water molecules in water to generate strongly oxidizing free radicals, which react with bacteria and thus kill the bacteria; on the other hand, Cu and Sb ions released from cuprous oxide and antimony trioxide nanomaterials can bind to the membranes and proteins of bacteria, destroying the structure of the bacteria and thus killing the bacteria. In addition, the mechanism for the excellent flame-retardant effect of the present invention is mainly that the particle size of the cuprous oxide / antimony trioxide composite material is small, at the nanoscale (particle size 80-120 nm). Nanoscale cuprous oxide can catalyze dehydroxylation and decarbonylation, increase the char yield, reduce the generation of combustible organic small molecules, and at the same time synergize with the flame-retardant effect of antimony trioxide, thus effectively improving the flame-retardant performance of the material.

[0026] Based on the above, compared with the prior art, the beneficial effects of the present invention are as follows:

[0027] 1. The antibacterial and flame-retardant fabric of the present invention has excellent antibacterial and flame-retardant properties. After testing, the antibacterial rates against Escherichia coli and Staphylococcus aureus are both >99%, and the flame-retardant effect is remarkable. The limiting oxygen index of the antibacterial and flame-retardant fabric has increased by ~25%, avoiding the problem of functional decline caused by the mixed use of single functional materials.

[0028] 2. The antibacterial and flame-retardant fabric of the present invention adsorbs copper ions by means of carboxyl groups grafted on the fabric to form cuprous oxide, effectively improving the compatibility between the organic material and the inorganic material. At the same time, the particle size of cuprous oxide is small, evenly dispersed on the surface of the fabric, and does not affect the basic properties of the fabric.

[0029] 3. Since the surface of antimony trioxide is negatively charged and the surface of cuprous oxide is positively charged, based on the principle of electrostatic adsorption, cuprous oxide is successfully loaded onto the surface of antimony trioxide. At the same time, copper atoms partially replace antimony atoms, and through electron transfer, a Cu-O-Sb bonding is formed, improving the stability of the modified various functional materials.

[0030] 4. The raw materials and preparation process are simple, with low cost, safe, environmentally friendly, and easy for large-scale industrial production, having broad market prospects. Description of the Drawings

[0031] Figure 1 It is the XRD pattern of the original fabric and the antibacterial and flame-retardant fabric prepared in Example 1.

[0032] Figure 2 It is the SEM morphology diagram of the original fabric and the antibacterial and flame-retardant fabric prepared in Example 1.

[0033] Figure 3 It is the EDS element distribution map of the antibacterial and flame-retardant fabric prepared in Example 1.

[0034] Figure 4 It is the digital camera picture of the antibacterial effect of the antibacterial and flame-retardant fabric prepared in Example 1. Detailed Description of the Invention

[0035] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0036] Example 1

[0037] The antibacterial and flame-retardant fabric of this example is prepared according to the following steps:

[0038] (1) Take 39 ml of a solution with a concentration of 0.05 mol / L NaH 2 PO 4 solution and 61 ml of a solution with a concentration of 0.05 mol / L Na 2 HPO 4 solution, mix them to prepare 100 ml of a phosphate buffer solution with a concentration of 0.05 mol / L. Subsequently, dissolve 20 mg of TEMPO in 50 ml of the buffer solution to obtain solution A;

[0039] (2) Respectively add 1 g of fabric, 50 mg of NaClO 2 powder and 2.2 g of 12% NaClO solution into solution A, stir well for 3 h, then take out the fabric and wash it 2 - 3 times with deionized water;

[0040] (3) Add 0.003 mol of copper acetate powder into 50 ml of deionized water, and immerse the washed fabric into this solution, stir well in a water bath at 60 °C for 2 h to obtain solution B;

[0041] (4) Add 0.024 mol of sodium hydroxide to Solution B and react fully in a water bath at 70 °C for 30 min;

[0042] (5) Add 0.001 mol of ascorbic acid to the solution after the reaction in step (4), react fully for 60 min, keep the reaction temperature constant at 80 °C, take out the fabric after full reaction and wash it 2 - 3 times with deionized water;

[0043] (6) Add 0.015 mol of dry antimony glycolate powder to 50 ml of anhydrous ethanol solution and ultrasonically disperse it for 20 min to obtain Solution C;

[0044] (7) Add the fabric washed in step (5) to Solution C, stir well, then add 50 ml of pure water, and adjust the pH of the solution to 8 using a hydrochloric acid medium, and react fully for 1 h;

[0045] (8) Transfer all the solution obtained in step (7) to a high-pressure reactor and react at 120 °C for 12 h;

[0046] (9) After the reaction is completed, take out the fabric and wash it 4 times with deionized water, and dry it at 70 °C to finally obtain the antibacterial and flame-retardant fabric.

[0047] For the antibacterial and flame-retardant fabric prepared by the above method, use testing methods such as SEM, EDS, XRD, and agar plate counting to detect the surface morphology, element distribution, phase composition, and antibacterial performance of the antibacterial and flame-retardant fabric prepared in this example (see specifically Figures 1-4 ).

[0048] From Figure 1 the results, it can be seen that the prepared antibacterial and flame-retardant fabric is mainly composed of three substances: cellulose, cuprous oxide, and antimony trioxide, and there are no other impurity substances. According to Figure 2 it can be known that the surface of the prepared antibacterial and flame-retardant fabric is relatively rough and is loaded with many fine particles, indicating that cuprous oxide and antimony trioxide are successfully modified on the fabric surface. From Figure 3 the results, it can be known that each element (C, Cu, Sb, and O) of the prepared antibacterial and flame-retardant fabric is evenly distributed on the surface of the sample, indicating that the prepared antibacterial and flame-retardant fabric has good uniformity. From Figure 4 the results, it can be known that the prepared antibacterial and flame-retardant fabric has excellent antibacterial effects, and the antibacterial rates against Escherichia coli and Staphylococcus aureus are both > 99%.

[0049] Example 2

[0050] The antibacterial and flame-retardant fabric of this example is prepared according to the following steps:

[0051] (1) Take 39 ml of a solution with a concentration of 0.1 mol / L NaH 2 PO 4The solution is mixed with 61 ml of a solution of 0.1 mol / L Na 2 HPO 4 to prepare 100 ml of a phosphate buffer solution with a concentration of 0.1 mol / L. Subsequently, 20 mg of TEMPO is dissolved in 50 ml of the buffer solution to obtain Solution A;

[0052] (2) 1 g of fabric, 50 mg of NaClO 2 powder and 4 g of 12% NaClO solution are respectively added to Solution A. After stirring well for 3 h, the fabric is taken out and washed 2 - 3 times with deionized water;

[0053] (3) 0.003 mol of copper acetate powder is added to 50 ml of deionized water, and the washed fabric is immersed in this solution. It is stirred well in a water bath at 60 °C for 2 h to obtain Solution B;

[0054] (4) 0.024 mol of sodium hydroxide is added to Solution B, and it reacts fully in a water bath at 70 °C for 30 min;

[0055] (5) 0.001 mol of ascorbic acid is added to the solution after the reaction in step (4), and it reacts fully for 50 min. The reaction temperature is kept constant at 70 °C. After the reaction, the fabric is taken out and washed 2 - 3 times with deionized water;

[0056] (6) 0.015 mol of dry antimony glycolate powder is added to 50 ml of anhydrous ethanol solution, and it is ultrasonically dispersed for 20 min to obtain Solution C;

[0057] (7) The fabric washed in step (5) is added to Solution C, stirred well, then 50 ml of pure water is added, and the pH of the solution is adjusted to 9 using a hydrochloric acid medium, and it reacts fully for 1 h;

[0058] (8) All the solution obtained in step (7) is transferred to a high - pressure reaction kettle and reacted at 130 °C for 12 h;

[0059] (9) After the reaction, the fabric is taken out and washed 4 times with deionized water and dried at 70 °C to finally obtain the antibacterial and flame - retardant fabric.

[0060] Example 3

[0061] The antibacterial and flame - retardant fabric of this example is prepared according to the following steps:

[0062] (1) Take 39 ml of a solution of 0.05 mol / L NaH 2 PO 4 solution and mix it with 61 ml of a solution of 0.05 mol / L Na 2 HPO 4The solution was mixed and formulated into 100 ml of phosphate buffer with a concentration of 0.05 mol / L. Subsequently, 30 mg of TEMPO was dissolved in 50 ml of the buffer to obtain Solution A;

[0063] (2) 1.2 g of fabric, 80 mg of NaClO 2 powder and 3.5 g of 12% NaClO solution were added to Solution A. After stirring well for 3 h, the fabric was taken out and washed 2 - 3 times with deionized water;

[0064] (3) 0.003 mol of copper acetate powder was added to 50 ml of deionized water, and the washed fabric was immersed in this solution. It was stirred well in a water bath at 40 °C for 2 h to obtain Solution B;

[0065] (4) 0.024 mol of sodium hydroxide was added to Solution B, and it was reacted well in a water bath at 60 °C for 30 min;

[0066] (5) 0.001 mol of ascorbic acid was added to the solution after the reaction in step (4), and it was reacted well for 60 min. The reaction temperature was kept constant at 60 °C. After the reaction, the fabric was taken out and washed 2 - 3 times with deionized water;

[0067] (6) 0.015 mol of dry antimony glycolate powder was added to 50 ml of anhydrous ethanol solution, and it was ultrasonically dispersed for 20 min to obtain Solution C;

[0068] (7) The fabric washed in step (5) was added to Solution C, stirred well, then 50 ml of pure water was added, and the pH of the solution was adjusted to 8 with a hydrochloric acid medium, and it was reacted well for 1 h;

[0069] (8) All the solution obtained in step (7) was transferred to a high-pressure reactor and reacted at 120 °C for 12 h;

[0070] (9) After the reaction, the fabric was taken out and washed 4 times with deionized water and dried at 70 °C to finally obtain the antibacterial and flame-retardant fabric.

[0071] Comparative Example 1

[0072] The difference between Comparative Example 1 and Example 1 is that copper acetate powder was not added in step (3) of the preparation process of Comparative Example 1, and the prepared antibacterial and flame-retardant fabric does not contain cuprous oxide, and the others are the same.

[0073] Comparative Example 2

[0074] The difference between Comparative Example 2 and Example 1 is that antimony glycolate powder was not added in step (6) of the preparation process of Comparative Example 2, and the prepared antibacterial and flame-retardant fabric does not contain antimony trioxide, and the others are the same.

[0075] Comparative Example 3

[0076] Comparative Example 3 was prepared by physically mixing cuprous oxide particles and antimony trioxide particles and then modifying the surface of the fabric to obtain an antibacterial and flame-retardant fabric.

[0077] To further prove the effectiveness of the present invention, the following test methods were provided

[0078] 1. The antibacterial performance of the antibacterial and flame-retardant fabric was tested in accordance with Appendix A of the national standard GB / T 21510-2008. The test results are shown in Table 1.

[0079] Table 1. Antibacterial test results of the antibacterial and flame-retardant fabric

[0080] Escherichia coli Staphylococcus aureus Example 1 ＞99％ ＞99％ Example 2 ＞99％ ＞99％ Example 3 ＞99％ ＞99％ Comparative Example 1 18.6％ 13.2 Comparative Example 2 ＞99％ ＞99％ Comparative Example 3 26.5％ 20.8％

[0081] 2. The flame-retardant performance of the antibacterial and flame-retardant fabric was tested in accordance with the national standard GB / T 5454-1997. The test results are shown in Table 2.

[0082] Table 2. Flame-retardant test results of the antibacterial and flame-retardant fabric

[0083] Limiting oxygen index (LOI) / % Original fabric 18.0 Example 1 22.7 Example 2 22.5 Example 3 22.6 Comparative Example 1 22.0 Comparative Example 2 19.2 Comparative Example 3 18.9

[0084] From the antibacterial and flame-retardant tests in Table 1 and Table 2, it can be seen that the antibacterial and flame-retardant effects of the antibacterial and flame-retardant fabric prepared by the method of the present invention are higher than those of the fabric modified with a single component, and also higher than those of the fabric modified with physically mixed components. Through the method of the present invention, a synergistic enhancement is formed between cuprous oxide and antimony trioxide, strengthening their antibacterial and flame-retardant effects. The antibacterial rates against Escherichia coli and Staphylococcus aureus are both > 99%, and the limiting oxygen index of combustion has increased by ~25% compared with the original fabric, indicating that the antibacterial and flame-retardant fabric prepared by the present invention can endow the fabric with dual antibacterial and flame-retardant effects, and has great economic value and social value.

[0085] The above has described the preferred embodiments of this patent in detail. However, this patent is not limited to the above embodiments. Within the scope of knowledge possessed by those of ordinary skill in the art, various changes can be made without departing from the gist of this patent.

Claims

1. A preparation method of an antibacterial and flame-retardant fabric, characterized in that: It includes the following steps: (1) Prepare a phosphate buffer solution, and then dissolve TEMPO (tetramethylpiperidine oxide) in the phosphate buffer solution to obtain solution A; (2) Add the fabric, NaClO 2 and the NaClO solution to Solution A, take out the fabric after thorough stirring and wash it; (3) Add copper acetate powder to deionized water, and immerse the washed fabric in this solution, stir constantly at a constant temperature to obtain solution B; (4) Add a certain amount of sodium hydroxide to solution B and react fully; (5) Add ascorbic acid to the solution after the reaction in step (4), keep the reaction temperature constant, take out the fabric after sufficient reaction and wash it; wherein, the molar ratio of ascorbic acid to copper acetate is: n 抗坏血酸 : n 乙酸铜 = 1: 2 - 6, the reaction temperature is 60 - 80 °C; the reaction time is 40 - 60 min; (6) Add dry ethylene glycol antimonide powder to an anhydrous ethanol solution, disperse it by ultrasonic wave to obtain solution C; (7) Add the fabric washed in step (5) to solution C, stir fully, then add pure water, and adjust the pH of the solution to weakly alkaline with an acidic or alkaline medium and react fully; wherein, the weak alkalinity is pH = 8 - 9; the reaction time is 1 - 2 h; (8) Transfer all the solution obtained in step (7) to a high-pressure reactor for reaction; wherein, the reaction temperature is 120 - 140 °C; the reaction time is 10 - 12 h; (9) After the reaction is completed, take out the fabric, wash it, and dry it to obtain the antibacterial and flame-retardant fabric.

2. The preparation method according to claim 1, characterized in that: In step (1), the phosphate buffer solution is composed of NaH 2 PO 4 solution and Na 2 HPO 4 solution, and the concentration of the phosphate buffer solution is 0.03 - 0.1 mol / L; the mass ratio of TEMPO to the mass of the fabric is M TEMPO :M 织物 = 1:40 - 60.

3. The preparation method according to claim 2, characterized in that: In step (1), the mass ratio of TEMPO to the fabric is M TEMPO : M 织物 = 1:50 - 55.

4. The preparation method according to claim 1, characterized in that: In step (2), the mass ratio of NaClO 2 to the mass of the fabric is M NaClO2 :M 织物 = 1:15 - 25; the mass fraction of the NaClO solution is 12%, and the mass ratio of the NaClO solution to the mass of the fabric is M NaClO溶液 :M 织物 = 1.5 - 4:1; the stirring time is 2 - 3 h.

5. The preparation method according to claim 4, characterized in that: In step (2), the mass ratio of the NaClO solution to the fabric is M NaClO溶液 : M 织物 = 2 - 3:1 6. The preparation method according to claim 1, characterized in that: In step (3), the stirring time is 1 - 2 h; the temperature is 40 - 60 °C.

7. The preparation method according to claim 1, characterized in that: In step (4), the molar ratio of sodium hydroxide to copper acetate is: n 氢氧化钠 : n 乙酸铜 = 5 - 10:1; the reaction temperature is 60 - 80 °C; the reaction time is 20 - 30 min.

8. The preparation method according to claim 7, characterized in that: In step (4), the molar ratio of sodium hydroxide to copper acetate is: n 氢氧化钠 : n 乙酸铜 = 6 - 8:

1.

9. The preparation method according to claim 1, characterized in that: In step (5), the molar ratio of ascorbic acid to copper acetate is: n 抗坏血酸 : n 乙酸铜 = 1: 3 - 4.

10. The preparation method according to claim 1, characterized in that: In step (6), the molar ratio of antimony glycolate powder to copper acetate is: n 乙二醇锑 : n 乙酸铜 = 1: 3 - 50; the mass ratio of antimony glycolate powder to absolute ethanol added is: m 乙二醇锑 : m 无水乙醇 = 1: 4 - 10.

11. The preparation method according to claim 10, characterized in that: In step (6), the molar ratio of antimony glycolate powder to copper acetate is: n 乙二醇锑 : n 乙酸铜 = 1: 5 - 10; the mass ratio of antimony glycolate powder to absolute ethanol added is: m 乙二醇锑 : m 无水乙醇 = 1: 5 - 7.

12. The preparation method according to claim 1, characterized in that: In step (7), the volume ratio of pure water to absolute ethanol is V 水 :V 无水乙醇 = 1 - 2:1; the acidic medium is selected from one or more of phosphoric acid, sulfuric acid, hydrochloric acid, and acetic acid; the basic medium is selected from one or more of sodium hydroxide, potassium hydroxide, and ammonia water.

13. The preparation method according to claim 1, characterized in that: In step (9), the washing is carried out 2 - 5 times; the drying temperature is 60 - 80 °C.

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