An antibacterial composite fabric and its preparation method

Abstract

The present invention belongs to the field of textile and clothing, and discloses an antibacterial composite fabric and a preparation method thereof. The method includes: ① adding cucurbituril, gallnut extract, and silver nitrate into water, fully mixing, performing a hydrothermal reaction, slowly adding ether after the reaction, vigorously shaking, centrifuging, washing the precipitate with water, and drying to obtain a dendritic pseudo-rotaxane silver complex; ② adding the dendritic pseudo-rotaxane silver complex, polyurethane, and a dispersant into a mixed solvent of dimethylformamide and tetrahydrofuran, and electrospinning to obtain an antibacterial nanofiber membrane; ③ thermally pressing the antibacterial nanofiber membrane with the fabric to finally obtain the antibacterial composite fabric. The antibacterial composite fabric prepared by the present invention has a strong antibacterial effect and is acid and alkali resistant.

Description

Technical Field

[0001] The present invention belongs to the field of textile and clothing, and particularly relates to an antibacterial composite fabric and a preparation method thereof. Background Art

[0002] Textile fabrics composed of fibers, due to their porous object shape and the chemical structure of high molecular polymers being conducive to microbial attachment, become good hosts for the survival and reproduction of microorganisms. In addition to the harm to the human body, the host will also contaminate the fibers. Therefore, the main purpose of antibacterial fabrics is to eliminate these adverse effects. There are two mainstream treatment methods in the market: one is the built-in silver ion antibacterial fabric, which uses spinning-grade antibacterial technology to directly incorporate the antibacterial agent into the chemical fiber; the other is the post-treatment technology, that is, adding it through the subsequent shaping process of the fabric. The post-treatment process is relatively simple and the cost is easy to control according to the specific requirements of customers, and it is the most widely used one in the market.

[0003] Regardless of which one, the silver ion antibacterial agent is very sensitive to acids and alkalis. During the processes of soaping, dyeing, and rinsing, acids and alkalis will destroy the antibacterial effect of silver ions, resulting in a significant decline in the antibacterial effect. Summary of the Invention

[0004] In view of this, the purpose of the present invention is to provide an antibacterial composite fabric and a preparation method thereof. The antibacterial composite fabric has a strong antibacterial effect and is acid and alkali resistant.

[0005] In order to solve the above technical problems, the present invention provides a preparation method of an antibacterial composite fabric, including the following steps:

[0006] ① Add cucurbituril, gallnut extract, and silver nitrate into water, mix well. After hydrothermal reaction, slowly add ether, shake vigorously, then centrifuge, wash the precipitate with water, and dry to obtain dendritic pseudo-rotaxane silver complex;

[0007] ② Add the dendritic pseudo-rotaxane silver complex, polyurethane, and dispersant into a mixed solvent with an equal volume ratio of dimethylformamide and tetrahydrofuran, and electrospin to obtain an antibacterial nanofiber membrane;

[0008] ③ Hot press the antibacterial nanofiber membrane with the fabric to finally obtain the antibacterial composite fabric.

[0009] Preferably, in step ①, the feeding ratio of cucurbituril, gallnut extract, silver nitrate, water, and ether is (0.6 - 1.2) g : (3.4 - 6.8) g : (10.2 - 15.3) g : 100 ml : (8 - 10) ml.

[0010] Preferably, in step ①, the cucurbituril is one of cucurbit[5]uril, cucurbit[6]uril, and cucurbit[8]uril.

[0011] Preferably, in step ①, the temperature of the hydrothermal reaction is 105 - 120 °C, and the time is 2 - 6 h.

[0012] Preferably, in step ②, the feeding ratio of the dendritic pseudorotaxane silver complex, polyurethane, dispersant and mixed solvent is (1.20 - 1.44) g : (15 - 18) g : (0.06 - 0.08) ml : 100 ml.

[0013] Preferably, in step ②, the dispersant is one of the polymer polyol dispersants BDF - 3, BDF - 4 and BDF - 5A.

[0014] Preferably, in step ②, the electrospinning conditions are a voltage of 15 - 20 kV, a receiving distance of 15 - 20 cm, and a spinning solution flow rate of 0.5 - 1.2 ml / h.

[0015] Preferably, in step ③, the hot pressing conditions are 70 - 80 °C, a pressure of 0.2 - 0.3 MPa, and a time of 90 - 120 s.

[0016] Preferably, in step ③, the fabric is one of pure cotton fabric, cotton - polyester blended fabric and cotton - ammonia blended fabric.

[0017] The present invention also provides an antibacterial composite fabric prepared by the above - mentioned preparation method.

[0018] Compared with the prior art, the present invention has the following beneficial effects:

[0019] The present invention utilizes the stability, acid - alkali resistance and cavity of cucurbituril to achieve host - guest bonding. Tannic acid, the main component in the gallnut extract, is unstable to acids and alkalis due to its rich ester bonds. By encapsulating the ester - benzene ring structure with cucurbituril to form a dendritic pseudorotaxane structure, the acid - alkali stability of tannic acid is improved. At the port formed by the polar carbonyl groups of cucurbituril, it just forms a multidentate complex with the phenolic hydroxyl group of tannic acid and Ag + to form a complex. Ag + can form complexes in the forms of linear, T - shaped, tetrahedral, trigonal bipyramidal, etc. with a coordination number of 2 - 6. In addition, there are often weak bond interactions such as Ag - Ag, A - C, A - π in the formed complexes, which further enriches the forms of silver complexes. Finally, silver ion clusters are formed at the port of cucurbituril, showing strong antibacterial effects. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 It is a schematic diagram of the dendritic pseudorotaxane structure of tannic acid and cucurbituril in the gallnut extract;

[0021] Figure 2 It is a schematic diagram of the structure of silver ion clusters at the port of cucurbituril. DETAILED DESCRIPTION OF THE INVENTION

[0022] To further understand the present invention, the preferred embodiments of the present invention will be described below in conjunction with examples. However, it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention, rather than limiting the claims of the present invention.

[0023] The present invention provides a method for preparing an antibacterial composite fabric, comprising the following steps:

[0024] ① Add cucurbituril, gallnut extract (the main component is tannic acid), and silver nitrate into water, mix well, after hydrothermal reaction, slowly add ether, shake vigorously, centrifuge, wash the precipitate with water, and dry to obtain a dendritic pseudo-rotaxane silver complex; the ester bond-benzene ring structure of tannic acid is included by cucurbituril to form a dendritic pseudo-rotaxane structure, as shown in Figure 1 shown. This dendritic pseudo-rotaxane structure improves the acid-base stability of tannic acid. At the port formed by the polar carbonyl groups of cucurbituril, it just forms a multidentate complex with the phenolic hydroxyl groups of tannic acid and Ag + Ag + can form complexes in the forms of linear, T-shaped, tetrahedral, trigonal bipyramidal, etc. with a coordination number of 2-6. In addition, weak bond interactions such as Ag-Ag, A-C, and A-π often exist in the formed complexes, which further enriches the forms of silver complexes. Finally, silver ion clusters are formed at the ports of cucurbituril, as shown in Figure 2 shown, showing strong antibacterial effects.

[0025] Preferably, in step ①, the feeding ratio of cucurbituril, gallnut extract, silver nitrate, water, and ether is (0.6-1.2) g: (3.4-6.8) g: (10.2-15.3) g: 100 ml: (8-10) ml.

[0026] Preferably, in step ①, the cucurbituril is one of cucurbit[5]uril, cucurbit[6]uril, and cucurbit[8]uril.

[0027] Preferably, in step ①, the temperature of the hydrothermal reaction is 105-120 °C, and the time is 2-6 h.

[0028] ② Add the dendritic pseudo-rotaxane silver complex, polyurethane, and dispersant into a mixed solvent with an equal volume ratio of dimethylformamide and tetrahydrofuran, and electrospin to obtain an antibacterial nanofiber membrane;

[0029] Preferably, in step ②, the feeding ratio of the dendritic pseudo-rotaxane silver complex, polyurethane, dispersant, and mixed solvent is (1.20-1.44) g: (15-18) g: (0.06-0.08) ml: 100 ml.

[0030] Preferably, in step ②, the dispersant is one of polymer polyol dispersants BDF-3, BDF-4, and BDF-5A.

[0031] Preferably, in step ②, the electrospinning conditions are a voltage of 15 - 20 kV, a receiving distance of 15 - 20 cm, and a spinning solution flow rate of 0.5 - 1.2 ml / h.

[0032] ③Thermally press the antibacterial nanofiber membrane and the fabric to finally obtain the antibacterial composite fabric.

[0033] Preferably, in step ③, the thermal pressing conditions are 70 - 80 °C, a pressure of 0.2 - 0.3 MPa, and a time of 90 - 120 s.

[0034] Preferably, in step ③, the fabric is one of pure cotton fabric, cotton - polyester blended fabric, and cotton - ammonia blended fabric.

[0035] Example 1

[0036] 1. Add 1.1 g of cucurbit[6]uril, 5.8 g of Chinese gall extract, and 12.8 g of silver nitrate to 100 ml of water, mix well, after hydrothermal reaction at 110 °C for 4.5 h, slowly add 9 ml of ether, shake vigorously, then centrifuge, wash the precipitate with water, and dry to obtain the dendritic pseudorotaxane silver complex;

[0037] 2. Add 1.32 g of the dendritic pseudorotaxane silver complex prepared in step 1, 16.7 g of polyurethane, and 0.07 ml of polymer polyol dispersant BDF-4 to 100 ml of a mixed solvent with an equal volume ratio of dimethylformamide and tetrahydrofuran, and electrospin to obtain the antibacterial nanofiber membrane at a voltage of 18 kV, a receiving distance of 16 cm, and a spinning solution flow rate of 0.9 ml / h;

[0038] 3. Thermally press the antibacterial nanofiber membrane prepared in step 2 and the cotton - ammonia blended fabric at 76 °C and a pressure of 0.28 MPa for 100 s to finally obtain the antibacterial composite fabric.

[0039] Example 2

[0040] 1. Add 0.6 g of cucurbit[5]uril, 3.4 g of Chinese gall extract, and 10.2 g of silver nitrate to 100 ml of water, mix well, after hydrothermal reaction at 105 °C for 6 h, slowly add 8 ml of ether, shake vigorously, then centrifuge, wash the precipitate with water, and dry to obtain the dendritic pseudorotaxane silver complex;

[0041] 2. Add 1.2 g of the dendritic pseudorotaxane silver complex prepared in step 1, 15 g of polyurethane, and 0.06 ml of polymer polyol dispersant BDF-5A to a mixed solvent of 100 ml of dimethylformamide and tetrahydrofuran in an equal volume ratio, and electrospin at a voltage of 15 kV, a receiving distance of 15 cm, and a spinning solution flow rate of 0.5 ml / h to obtain an antibacterial nanofiber membrane;

[0042] 3. Hot press the antibacterial nanofiber membrane prepared in step 2 with a pure cotton fabric at 70 °C and a pressure of 0.3 MPa for 90 s to finally obtain an antibacterial composite fabric.

[0043] Example 3

[0044] 1. Add 1.2 g of cucurbit[8]uril, 6.8 g of gallnut extract, and 15.3 g of silver nitrate to 100 ml of water, mix well, after hydrothermal reaction at 120 °C for 2 h, slowly add 10 ml of diethyl ether, shake vigorously, centrifuge, wash the precipitate with water, and dry to obtain a dendritic pseudorotaxane silver complex;

[0045] 2. Add 1.44 g of the dendritic pseudorotaxane silver complex prepared in step 1, 18 g of polyurethane, and 0.08 ml of polymer polyol dispersant BDF-3 to a mixed solvent of 100 ml of dimethylformamide and tetrahydrofuran in an equal volume ratio, and electrospin at a voltage of 20 kV, a receiving distance of 20 cm, and a spinning solution flow rate of 1.2 ml / h to obtain an antibacterial nanofiber membrane;

[0046] 3. Hot press the antibacterial nanofiber membrane prepared in step 2 with a cotton-polyester blended fabric at 80 °C and a pressure of 0.2 MPa for 120 s to finally obtain an antibacterial composite fabric.

[0047] Comparative Example 1 (without cucurbituril)

[0048] 1. Add 5.8 g of gallnut extract and 12.8 g of silver nitrate to 100 ml of water, mix well, after hydrothermal reaction at 110 °C for 4.5 h, slowly add 9 ml of diethyl ether, shake vigorously, centrifuge, wash the precipitate with water, and dry to obtain a gallnut silver complex;

[0049] 2. Add 1.32 g of the gallnut silver complex prepared in step 1, 16.7 g of polyurethane, and 0.07 ml of polymer polyol dispersant BDF-4 to a mixed solvent of 100 ml of dimethylformamide and tetrahydrofuran in an equal volume ratio, and electrospin at a voltage of 18 kV, a receiving distance of 16 cm, and a spinning solution flow rate of 0.9 ml / h to obtain an antibacterial nanofiber membrane;

[0050] 3. Hot press the antibacterial nanofiber membrane prepared in step 2 with a cotton-polyamide blended fabric at 76 °C and a pressure of 0.28 MPa for 100 s to finally obtain an antibacterial composite fabric.

[0051] Comparative Example 2 (without hydrothermal reaction)

[0052] 1. Add 1.1 g of cucurbit[6]uril, 5.8 g of gallnut extract, and 12.8 g of silver nitrate into 100 ml of water, mix well, slowly add 9 ml of ether, shake vigorously, then centrifuge, wash the precipitate with water, and dry to obtain gallnut silver complex;

[0053] 2. Add 1.32 g of the gallnut silver complex prepared in step 1, 16.7 g of polyurethane, and 0.07 ml of polymer polyol dispersant BDF-4 into a mixed solvent with an equal volume ratio of 100 ml of dimethylformamide and tetrahydrofuran, electrospin at a voltage of 18 kV, a receiving distance of 16 cm, and a spinning solution flow rate of 0.9 ml / h to obtain an antibacterial nanofiber membrane;

[0054] 3. Hot press the antibacterial nanofiber membrane prepared in step 2 and the cotton-ammonia blended fabric at 76 °C and a pressure of 0.28 MPa for 100 s to finally obtain an antibacterial composite fabric.

[0055] Comparative Example 3 (using copper sulfate instead of silver nitrate)

[0056] 1. Add 1.1 g of cucurbit[6]uril, 5.8 g of gallnut extract, and 12.8 g of copper sulfate into 100 ml of water, mix well, carry out hydrothermal reaction at 110 °C for 4.5 h, then slowly add 9 ml of ether, shake vigorously, then centrifuge, wash the precipitate with water, and dry to obtain dendritic pseudorotaxane copper complex;

[0057] 2. Add 1.32 g of the dendritic pseudorotaxane copper complex prepared in step 1, 16.7 g of polyurethane, and 0.07 ml of polymer polyol dispersant BDF-4 into a mixed solvent with an equal volume ratio of 100 ml of dimethylformamide and tetrahydrofuran, electrospin at a voltage of 18 kV, a receiving distance of 16 cm, and a spinning solution flow rate of 0.9 ml / h to obtain an antibacterial nanofiber membrane;

[0058] 3. Hot press the antibacterial nanofiber membrane prepared in step 2 and the cotton-ammonia blended fabric at 76 °C and a pressure of 0.28 MPa for 100 s to finally obtain an antibacterial composite fabric.

[0059] Antibacterial performance test

[0060] The fabrics of Examples 1-3 and Comparative Examples 1-3 were subjected to antibacterial tests using the shaking method, and the results are shown in Table 1.

[0061] Table 1

[0062]

[0063]

[0064] As can be seen from Table 1, the fabric prepared in the example has strong antibacterial effects and still shows good antibacterial effects after 10 times of acid washing or 10 times of alkali washing. For the antibacterial composite fabrics prepared in Comparative Example 1 and Comparative Example 2, since the dendritic pseudo-rotaxane silver complex cannot be formed, the tannic acid structure cannot resist acid-base hydrolysis, resulting in the dissociation of supramolecules and the washing away of silver complexes, and the antibacterial effects are significantly reduced, indicating that the antibacterial effects of the fabrics are not acid-base resistant. Although a dendritic pseudo-rotaxane copper complex is formed in Comparative Example 3, the Cu 2+ ion has a relatively small radius, only half of that of Ag + , and cannot form copper clusters like Ag + , and both the antibacterial effect and the duration of the continuous action will be significantly reduced.

[0065] The present invention provides an idea and method for an antibacterial composite fabric and a preparation method thereof. There are many specific methods and ways to implement this technical solution. The above description is only a preferred embodiment of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be regarded as the protection scope of the present invention. Each component not clearly defined in this example can be realized by the prior art.

Claims

1. A preparation method of an antibacterial composite fabric, characterized in that, It includes the following steps: S1. Cucurbituril, gallnut extract, and silver nitrate are added to water and mixed thoroughly. After hydrothermal reaction, diethyl ether is slowly added. After vigorous oscillation, centrifugation is carried out, and the precipitate is washed with water and dried to obtain a dendritic pseudorotaxane silver complex; the feeding ratio of cucurbituril, gallnut extract, silver nitrate, water, and diethyl ether is (0.6 - 1.2) g : (3.4 - 6.8) g : (10.2 - 15.3) g : 100 ml : (8 - 10) ml; the cucurbituril is one of cucurbit[5]uril, cucurbit[6]uril, and cucurbit[8]uril; S2. The dendritic pseudorotaxane silver complex, polyurethane, and dispersant are added to a mixed solvent with an equal volume ratio of dimethylformamide and tetrahydrofuran, and an antibacterial nanofiber membrane is prepared by electrospinning; S3. The antibacterial nanofiber membrane is hot-pressed with the fabric to finally obtain an antibacterial composite fabric.

2. The preparation method according to claim 1, characterized in that, In step S1, the temperature of the hydrothermal reaction is 105 - 120 °C, and the time is 2 - 6 h.

3. The preparation method according to claim 1, characterized in that, In step S2, the feeding ratio of the dendritic pseudorotaxane silver complex, polyurethane, dispersant, and mixed solvent is (1.20 - 1.44) g : (15 - 18) g : (0.06 - 0.08) ml : 100 ml.

4. The preparation method according to claim 1, characterized in that, In step S2, the dispersant is one of polymer polyol dispersants BDF-3, BDF-4, and BDF-5A.

5. The preparation method according to claim 1, characterized in that, In step S2, the electrospinning conditions are a voltage of 15 - 20 kV, a receiving distance of 15 - 20 cm, and a spinning solution flow rate of 0.5 - 1.2 ml / h.

6. The preparation method according to claim 1, characterized in that, In step S3, the hot-pressing conditions are 70 - 80 °C, a pressure of 0.2 - 0.3 MPa, and a time of 90 - 120 s.

7. The preparation method according to claim 1, characterized in that, In step S3, the fabric is one of pure cotton fabric, cotton-polyester blended fabric, and cotton-ammonia blended fabric.

8. An antibacterial composite fabric prepared by the preparation method according to any one of claims 1 to 7.

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