Preparation method of straw-based copper-zinc long-acting antibacterial agent and application of straw-based copper-zinc long-acting antibacterial agent in textile fibers

Abstract

The invention discloses a preparation method of a straw-based copper-zinc long-acting antibacterial agent and application of the straw-based copper-zinc long-acting antibacterial agent in textile fibers. The method comprises the following steps: preparing nano copper oxide by taking corn straw with a honeycomb structure as a reducing agent and a fixing agent, and then loading a metal organic framework ZIF-8 with a topological structure, so as to prepare the ZIF-8 / nano copper oxide / corn straw composite material with light-chemical synergistic lasting antibacterial property. And carrying out melt spinning with polyester to obtain the textile fiber with a lasting antibacterial effect. The obtained textile fiber has broad-spectrum antibacterial performance. An antibacterial experiment result shows that the antibacterial effect of the antibacterial textile fiber on staphylococcus aureus and escherichia coli reaches 95% or above. When the textile fiber is applied to textiles, the textile fiber has a long-acting antibacterial effect and plays an important role in guaranteeing the health and safety of a human body.

Description

Technical Field

[0001] The invention relates to the field of textile fibers, and in particular to a preparation method and application of a straw-based copper-zinc long-acting antibacterial textile fiber. Background Art

[0002] Ordinary textiles do not have antibacterial effects. Bacteria not only cause textiles to mold, but also affect human health and cause skin diseases. The development of textile antibacterial fibers can effectively cut off the transmission pathways of germs and protect human health. At present, some textile antibacterial fiber products are available on the market, such as direct finishing or blending with impregnation or addition of Zn 2+ , Cu 2 + Antimicrobial agents impart antimicrobial activity to textile fibers. However, these products suffer from a large loss of antimicrobial agents during the printing, dyeing, washing and other processing processes, resulting in problems such as short product life, unstable antimicrobial effects, insufficient durability, and low safety.

[0003] Corn stalks are a kind of porous structure material with three-dimensional honeycomb. The three-dimensional porous pipe structure is a natural "honeycomb" that loads and fixes nanoparticles or other substances. It can reduce the loss of antibacterial components and continuously release antibacterial components to achieve a long-lasting antibacterial effect. In particular, the main components of corn stalks are cellulose, hemicellulose and lignin, all of which have reducing ability and can reduce metal ions to nanometals. Therefore, the reduction and fixation ability of corn stalks can be used to study and develop corn stalk-based composite antibacterial agents with stable and long-lasting antibacterial and sterilization functions, and their application in the antibacterial finishing of textiles has important practical significance, and also has an important role in promoting the high-value utilization of corn stalks, and has attractive application prospects and a broad market. Summary of the invention

[0004] In order to overcome the deficiencies of the prior art, the purpose of the present invention is to provide a straw-based copper-zinc long-acting antibacterial textile fiber and a preparation method and application thereof.

[0005] The purpose of the present invention is to address the deficiencies of the prior art and provide a textile antibacterial fiber, specifically a textile fiber containing a straw-based copper-zinc antibacterial agent with long-lasting antibacterial properties.

[0006] The present invention also aims to provide a straw-based copper-zinc long-lasting antibacterial textile fiber and its preparation method and application. The preparation method uses corn straw with a honeycomb structure as a reducing agent and a fixing agent to prepare nano copper oxide, and then loads a metal organic framework ZIF-8 with a topological structure to prepare a corn straw / nano copper oxide / ZIF-8 composite material with photo-chemical synergistic antibacterial and long-lasting effect. Then, the composite material is melt-spun with polyester to obtain a textile fiber with a long-lasting antibacterial effect.

[0007] The purpose of the present invention is achieved by at least one of the following technical solutions.

[0008] The invention uses corn stalks with a honeycomb structure to prepare a long-acting antibacterial agent, and prepares textile fibers with a long-lasting antibacterial effect by melt spinning.

[0009] The straw-based copper-zinc long-acting antibacterial textile fiber and the preparation method thereof provided by the present invention use corn straw with a honeycomb structure as a reducing agent and a fixing agent to prepare nano copper oxide, and load a metal organic framework ZIF-8 with a topological structure to prepare a corn straw / nano copper oxide / ZIF-8 composite material with photo-chemical synergistic antibacterial and long-lasting effect. Then, the composite material is melt-spun with polyester to obtain a textile fiber with a long-lasting antibacterial effect.

[0010] A method for preparing a straw-based copper-zinc long-acting antibacterial agent comprises the following steps:

[0011] (1) washing, drying, and crushing corn stalks to obtain block corn stalks with a honeycomb structure;

[0012] (2) soaking the block corn stalks with a honeycomb structure obtained in step (1) in a copper ion adsorption solution to adsorb copper ions; adding a sodium hydroxide solution to adjust the pH in a water bath to reduce the copper ions to nano copper oxide, washing with deionized water, and drying to obtain block nano copper oxide / corn stalks;

[0013] (3) dispersing the blocky nano copper oxide / corn stalks obtained in step (2) in a zinc nitrate methanol solution, adsorbing zinc ions in the zinc nitrate methanol solution, adding 2-methylimidazole methanol solution after the nano copper oxide / corn stalks are saturated with adsorption, and forming a metal organic framework ZIF-8 with a topological structure through self-assembly of zinc ions and 2-methylimidazole molecules, and obtaining a ZIF-8 / nano copper oxide / corn stalk long-acting antibacterial agent after drying, that is, a straw-based copper-zinc long-acting antibacterial agent.

[0014] Furthermore, in step (1), the particle size of the corn stalk block is 0.5-1.0 cm; and the pulverization time is 0.5-1.0 h.

[0015] Furthermore, the mass fraction of sodium hydroxide in step (2) is 2-7%, and the mass fraction of copper nitrate is 0.1%-0.5%; in the corn stalk solution in step (1), the concentration of corn stalk is 0.1-5 g / L; the reaction temperature of the water bath is 80° C.-85° C., and the adjusted pH value is 9-11.

[0016] Furthermore, in step (3), the mass fraction of the zinc nitrate is 1%-5%; the mass fraction of the 2-methylimidazole is 1%-5%.

[0017] Furthermore, the drying temperatures in step (1), step (2) and step (3) are all 30-60°C.

[0018] The straw-based copper-zinc long-acting antibacterial agent is applied to textile fibers, specifically: the straw-based copper-zinc long-acting antibacterial agent is crushed into powder, and then melt-spun with polyester fibers to obtain textile antibacterial fibers with lasting antibacterial properties; the antibacterial rates of the textile antibacterial fibers against Escherichia coli and Staphylococcus aureus are both greater than 95%.

[0019] Furthermore, the mesh size of the straw-based copper-zinc long-acting antibacterial agent is 400-500 meshes, and the ZIF-8 / nano-copper oxide / corn straw long-acting antibacterial agent is used to develop antibacterial textiles with photo-chemical synergistic and long-lasting antibacterial properties to address the problems of insufficient antibacterial properties and short-term antibacterial effects of textiles; the mass fraction of the straw-based copper-zinc long-acting antibacterial agent in the textile antibacterial fiber is 1%-2%, and the melting temperature is 100-200°C.

[0020] The present invention provides a straw-based copper-zinc long-acting antibacterial textile fiber prepared by the above-mentioned preparation method, and the antibacterial effect on Escherichia coli and Staphylococcus aureus is greater than 95%.

[0021] The application of the straw-based copper-zinc long-acting antibacterial agent provided by the present invention in textile fibers can meet the requirements of antibacterial textile fibers.

[0022] Compared with the prior art, the present invention has the following advantages:

[0023] (1) The agricultural waste corn stalks used in the present invention are widely available, low in cost, safe, non-toxic, and biodegradable;

[0024] (2) The present invention uses corn stalks with a honeycomb structure as a reducing agent and a fixing agent to prepare nano copper oxide, and loads a metal organic framework ZIF-8 with a topological structure to prepare a corn stalk / nano copper oxide / ZIF-8 composite material with photo-chemical synergistic antibacterial and long-lasting effect. Then, the composite material is melt-spun with polyester to obtain a textile fiber with a long-lasting antibacterial effect.

[0025] (3) The preparation method of the present invention is simple and easy to operate, has low energy consumption, and is conducive to large-scale industrial production;

[0026] (4) The straw-based copper-zinc long-acting antibacterial agent of the present invention is used in textile fibers, and the antibacterial effect of the antibacterial textile fibers on Staphylococcus aureus and Escherichia coli reaches more than 95%. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 Example 2 is an electron microscope image of nano copper oxide / corn straw reduced and fixed with corn straw of honeycomb structure and the prepared ZIF-8 / nano copper oxide / corn straw;

[0028] Figure 2 The antibacterial effect diagram of the straw-based copper-zinc antibacterial agent prepared in Example 2 and Example 3 on Escherichia coli, the composite material obtained in Example 2, and the composite material obtained in Example 3;

[0029] Figure 3 The antibacterial effect diagram of the straw-based copper-zinc antibacterial agent prepared in Example 2 and Example 3 on Staphylococcus aureus is shown;

[0030] Figure 4 This is the antibacterial performance of the straw-based copper-zinc antibacterial agent prepared in Example 4 under light and heat. DETAILED DESCRIPTION

[0031] The specific implementation of the present invention is further described below in conjunction with the accompanying drawings and examples, but the implementation and protection of the present invention are not limited thereto. It should be noted that if there are processes that are not particularly described in detail below, they can be implemented or understood by those skilled in the art with reference to the prior art. If the manufacturer of the reagents or instruments used is not indicated, they are deemed to be conventional products that can be purchased commercially.

[0032] Example 1

[0033] A method for preparing straw-based copper-zinc long-acting antibacterial textile fiber comprises the following steps:

[0034] (1) crushing the collected corn stalks for 0.5 h to make corn stalk blocks with a honeycomb structure (the particle size of the block stalks is 0.5-1.0 cm);

[0035] (2) The above 5 g block corn stalks were added to 50 mL of 0.1% copper nitrate solution at room temperature. After sufficient adsorption for 30 min, the solution was heated to 80°C under alkaline conditions of pH 9 to reduce the copper ions to nano-copper oxide, thereby constructing corn stalk@nano-copper oxide structural fibers with photocatalytic properties.

[0036] (3) 5 g of the blocky nano copper oxide / corn stalks was added to 50 mL of methanol containing 1% zinc nitrate and fully adsorbed for 30 min. 0.5 g of 2-methylimidazole was added at room temperature to form a metal organic framework (ZIF-8) with a topological structure through self-assembly of zinc ions and 2-methylimidazole molecules, thereby obtaining ZIF-8 / nano copper oxide / corn stalks.

[0037] (4) The prepared ZIF-8 / nano copper oxide / corn straw long-lasting antibacterial agent was crushed and ball-milled into corn straw powder (powder particle size was 400-500 mesh), and then melt-spun with polyester fiber (melting temperature was 150 degrees) to obtain a textile antibacterial fiber with long-lasting antibacterial properties.

[0038] Example 2

[0039] A method for preparing straw-based copper-zinc long-acting antibacterial textile fiber comprises the following steps:

[0040] (1) crushing the collected corn stalks for 0.5 h to make corn stalk blocks with a honeycomb structure (the particle size of the block stalks is 0.5-1.0 cm);

[0041] (2) The above 5 g of corn stalk block was added to 50 mL of 0.2% copper nitrate solution at room temperature. After sufficient adsorption for 40 minutes, it was heated to 80°C under alkaline conditions of pH 9 to reduce the copper ions to nano-copper oxide, thereby constructing nano-copper oxide / corn stalk structural fibers with photocatalytic properties.

[0042] (3) 5 g of the blocky nano copper oxide / corn stalks was added to 50 mL of methanol containing 2% zinc nitrate and fully adsorbed for 30 min. A 2.0% 2-methylimidazole solution was added at room temperature to form a metal organic framework (ZIF-8) with a topological structure through self-assembly of zinc ions and 2-methylimidazole molecules, thereby obtaining ZIF-8 / nano copper oxide / corn stalks.

[0043] (4) The prepared ZIF-8 / nano copper oxide / corn straw long-lasting antibacterial agent was crushed and ball-milled into corn straw powder (powder particle size was 400-500 mesh), and then melt-spun with polyester fiber (melting temperature was 160 degrees) to obtain a textile antibacterial fiber with long-lasting antibacterial properties.

[0044] Figure 1 Example 2 is an electron microscope image of nano copper oxide / corn stalks reduced and fixed by corn stalks with a honeycomb structure and the prepared ZIF-8 / nano copper oxide / corn stalks; wherein a is corn stalks with a honeycomb structure; b is ZIF-8 / nano copper oxide / corn stalks;

[0045] The experimental diagram of the prepared ZIF-8 / nano copper oxide / corn straw long-lasting antibacterial textile fiber against Staphylococcus aureus and Escherichia coli, as shown in Figure 2 The composite material obtained in Example 2 is shown in FIG. Figure 2 It can be seen that the prepared ZIF-8 / nano copper oxide / corn straw long-lasting antibacterial textile fiber has good antibacterial effect against Staphylococcus aureus and Escherichia coli.

[0046] Example 3

[0047] A method for preparing straw-based copper-zinc long-acting antibacterial textile fiber comprises the following steps:

[0048] (1) crushing the collected corn stalks for 0.5 h to make corn stalk blocks with a honeycomb structure (the particle size of the block stalks is 0.5-1.0 cm);

[0049] (2) The above 5 g of corn stalk block was added to 50 mL of 0.3% copper nitrate solution at room temperature. After sufficient adsorption for 40 minutes, it was heated to 80°C under alkaline conditions of pH 10 to reduce the copper ions to nano-copper oxide, thereby constructing nano-copper oxide / corn stalk structural fibers with photocatalytic properties.

[0050] (3) 5 g of the blocky nano copper oxide / corn stalks was added to 50 mL of methanol containing 3% zinc nitrate and fully adsorbed for 30 min. 3.0% 2-methylimidazole was added at room temperature to form a metal organic framework (ZIF-8) with a topological structure through self-assembly of zinc ions and 2-methylimidazole molecules, thereby obtaining ZIF-8 / nano copper oxide / corn stalks.

[0051] (4) The prepared ZIF-8 / nano copper oxide / corn straw long-lasting antibacterial agent was crushed and ball-milled into corn straw powder (powder particle size was 400-500 mesh), and then melt-spun with polyester fiber (melting temperature was 160 degrees) to obtain a textile antibacterial fiber with long-lasting antibacterial properties.

[0052] The experimental diagram of the prepared ZIF-8 / nano copper oxide / corn straw long-lasting antibacterial textile fiber against Staphylococcus aureus and Escherichia coli, as shown in Figure 3 The composite material obtained in Example 3 is shown in FIG. Figure 3 It can be seen that the prepared ZIF-8 / nano copper oxide / corn straw long-lasting antibacterial textile fiber has good antibacterial effect against Staphylococcus aureus and Escherichia coli.

[0053] Example 4

[0054] A method for preparing straw-based copper-zinc long-acting antibacterial textile fiber comprises the following steps:

[0055] (1) crushing the collected corn stalks for 0.5 h to make corn stalk blocks with a honeycomb structure (the particle size of the block stalks is 0.5-1.0 cm);

[0056] (2) The above 5 g of corn stalk block was added to 50 mL of 0.4% copper nitrate solution at room temperature. After sufficient adsorption for 40 minutes, it was heated to 80°C under alkaline conditions of pH 11 to reduce the copper ions to nano-copper oxide, thereby constructing nano-copper oxide / corn stalk structural fibers with photocatalytic properties.

[0057] (3) 5 g of the blocky nano copper oxide / corn stalks was added to 50 mL of methanol containing 4% zinc nitrate and fully adsorbed for 30 min. 4.0% 2-methylimidazole was added at room temperature to form a metal organic framework (ZIF-8) with a topological structure through self-assembly of zinc ions and 2-methylimidazole molecules, thereby obtaining ZIF-8 / nano copper oxide / corn stalks.

[0058] (4) The prepared ZIF-8 / nano copper oxide / corn straw long-lasting antibacterial agent was crushed and ball-milled into corn straw powder (powder particle size was 400-500 mesh), and then melt-spun with polyester fiber (melting temperature was 160 degrees) to obtain a textile antibacterial fiber with long-lasting antibacterial properties. Figure 4 As shown, the straw-based copper-zinc antibacterial agent prepared in Example 4 has good antibacterial properties under light and heat.

[0059] Example 5

[0060] A method for preparing straw-based copper-zinc long-acting antibacterial textile fiber comprises the following steps:

[0061] (1) crushing the collected corn stalks for 0.5 h to make corn stalk blocks with a honeycomb structure (the particle size of the block stalks is 0.5-1.0 cm);

[0062] (2) The above 5 g of corn stalk block was added to 50 mL of 0.5% copper nitrate solution at room temperature. After sufficient adsorption for 40 minutes, it was heated to 80°C under alkaline conditions of pH 11 to reduce the copper ions to nano-copper oxide, thereby constructing nano-copper oxide / corn stalk structural fibers with photocatalytic properties.

[0063] (3) 5 g of the blocky nano copper oxide / corn stalks was added to 50 mL of methanol containing 5% zinc nitrate and fully adsorbed for 30 min. Then, 5.0% 2-methylimidazole was added at room temperature to form a metal organic framework (ZIF-8) with a topological structure through self-assembly of zinc ions and 2-methylimidazole molecules, thereby obtaining ZIF-8 / nano copper oxide / corn stalks.

[0064] (4) The prepared ZIF-8 / nano copper oxide / corn straw long-lasting antibacterial agent was crushed and ball-milled into corn straw powder (powder particle size was 400-500 mesh), and then melt-spun with polyester fiber (melting temperature was 160 degrees) to obtain a textile antibacterial fiber with long-lasting antibacterial properties.

[0065] The above embodiments are only preferred implementation modes of the present invention and are only used to explain the present invention rather than to limit the present invention. Any changes, substitutions, modifications, etc. made by those skilled in the art without departing from the spirit of the present invention should fall within the scope of protection of the present invention.

Claims

1. A method for preparing a straw-based copper-zinc long-acting antibacterial agent, characterized in that: The steps include: (1) washing, drying, and crushing corn stalks to obtain block corn stalks with a honeycomb structure; (2) soaking the block corn stalks with a honeycomb structure obtained in step (1) in a copper ion adsorption solution to adsorb copper ions; adding a sodium hydroxide solution to adjust the pH in a water bath to reduce the copper ions to nano copper oxide, washing with deionized water, and drying to obtain block nano copper oxide / corn stalks; (3) dispersing the blocky nano copper oxide / corn stalks obtained in step (2) in a zinc nitrate methanol solution, adsorbing zinc ions in the zinc nitrate methanol solution, adding 2-methylimidazole methanol solution after the nano copper oxide / corn stalks are saturated with adsorption, and forming a metal organic framework ZIF-8 with a topological structure through self-assembly of zinc ions and 2-methylimidazole molecules, and obtaining a ZIF-8 / nano copper oxide / corn stalk long-acting antibacterial agent after drying, that is, a straw-based copper-zinc long-acting antibacterial agent.

2. The method for preparing a straw-based copper-zinc long-acting antibacterial agent according to claim 1, characterized in that: In step (1), the particle size of the corn stalk block is 0.5-1.0 cm; and the pulverization time is 0.5-1.0 h.

3. The method for preparing a straw-based copper-zinc long-acting antibacterial agent according to claim 1, characterized in that: In step (2), the reaction temperature of the water bath is 80° C.-85° C., the mass fraction of sodium hydroxide is 2-7%, and the adjusted pH value is 9-11.

4. The method for preparing a straw-based copper-zinc long-acting antibacterial agent according to claim 1, characterized in that: In step (2), the copper ion solution is a copper nitrate solution, the mass fraction of the copper ion solution is 0.1%-0.5%, and the concentration of the block corn stalks with a honeycomb structure in the copper ion solution is 0.1-5g / L.

5. The method for preparing a straw-based copper-zinc long-acting antibacterial agent according to claim 1, characterized in that: In step (3), the mass fraction of the zinc nitrate is 1%-5%; the mass fraction of the 2-methylimidazole is 1%-5%.

6. The preparation method of the straw-based copper-zinc long-acting antibacterial agent and its application in textile fibers according to claim 1, characterized in that: The drying temperatures in step (1), step (2) and step (3) are all 30-60°C.

7. The straw-based copper-zinc long-acting antibacterial agent prepared by the preparation method according to any one of claims 1 to 6.

8. The straw-based copper-zinc long-acting antibacterial agent according to claim 7 is applied to textile fibers, characterized in that: The straw-based copper-zinc long-acting antibacterial agent is crushed into powder and then melt-spun with polyester fiber to obtain a textile antibacterial fiber with lasting antibacterial performance; the antibacterial rate of the textile antibacterial fiber against Escherichia coli and Staphylococcus aureus is greater than 95%.

9. The use according to claim 1, characterized in that: The straw-based copper-zinc long-acting antibacterial agent has a mesh size of 400-500 meshes.

10. The use according to claim 1, characterized in that: The mass fraction of the straw-based copper-zinc long-acting antibacterial agent in the textile antibacterial fiber is 1%-2%, and the melting temperature is 100-200°C.

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