Active antibacterial self-cleaning fabric and preparation method thereof

Abstract

The present invention belongs to the field of textiles, and in particular to a kind of active antibacterial self-cleaning fabric and preparation method thereof. The preparation method includes: first, melamine, genipin, copper sulfate and ammonium chloride are dissolved in water together, ethanol is added to prepare a prepolymer finishing agent, and then cotton fabric is immersed in it. After microwave reaction, the cotton fabric is further immersed in a DMF solution containing a tetravalent vanadium salt and meso-tetrakis (3-carboxyphenyl) porphine, and then hydrothermal reaction is carried out, followed by washing and drying to obtain an active antibacterial self-cleaning fabric. The fabric can achieve antibacterial properties by generating superoxide anions, hydroxyl radicals and singlet oxygen, and can also achieve surface self-cleaning by oxidative degradation of oil stains and blood stains on the surface of the fabric.

Description

Technical Field

[0001] The invention belongs to the field of textiles, and in particular relates to an active antibacterial self-cleaning fabric and a preparation method thereof. Background Art

[0002] Bacteria, the most widespread microorganisms in the human environment, are not only ubiquitous but also diverse, highly adaptable, and rapidly reproducing. Harmful pathogens, in particular, pose a serious threat to human health. They can not only aggravate wound infections and worsen illnesses through direct contact, but can also invade the human body and cause illness by contaminating the surrounding environment, such as water, food, air, and clothing.

[0003] Textiles, as essential functional items for human life, are highly susceptible to microbial contamination due to their inherent microporous structure. Furthermore, the human body's favorable temperature and humidity, as well as secretions of oil and sweat, create favorable conditions for microbial reproduction and growth under certain circumstances. Therefore, it is crucial to quickly and effectively kill pathogens and hinder their metabolism and growth in textiles to address bacterial contamination and disease. Furthermore, the rapid development of modern textile science and technology and the increasing demand for textile functionality and comfort have led to a surge in consumer demand for textiles with specialized functions.

[0004] In recent years, numerous experts and scholars have attempted to exploit various methods and approaches to achieve new breakthroughs in the antimicrobial functionalization of textiles. Metal-organic framework-based photodynamic therapy and catalytic antimicrobial materials, such as transition metal nanozymes, have become the most prominent antimicrobial agents in current research due to their high oxidative activity and stability, as well as their non-toxicity, odorlessness, and lack of secondary pollution. These agents, when applied to textiles for antimicrobial finishing, can impart multiple functions, such as antimicrobial deodorization and self-cleaning. Compared to traditional textiles, these textiles often offer higher added value while improving people's lives, undoubtedly driving the textile industry to create greater social and economic benefits. Summary of the Invention

[0005] In view of this, the purpose of the present invention is to provide an active antibacterial self-cleaning fabric and a preparation method thereof, which can not only achieve antibacterial properties by generating superoxide anions, hydroxyl radicals and singlet oxygen, but also oxidize and degrade oil stains and blood stains on the surface of the fabric to achieve surface self-cleaning.

[0006] In order to solve the above technical problems, the present invention provides an active antibacterial self-cleaning fabric and a preparation method thereof, comprising the following steps:

[0007] S1. Melamine, copper sulfate, and ammonium chloride were added to water, ethanol was added, the pH was adjusted to 3.0-4.5, the temperature was raised to 60-70 ° C, genipin was added, and the mixture was stirred thoroughly to obtain a prepolymer finishing agent;

[0008] S2. Wash and dry the cotton fabric base cloth, immerse it in the prepolymer finishing agent prepared in step S1, dip it in two pads, perform a microwave reaction, then wash it and dry it;

[0009] S3. Immerse the cotton fabric treated in step S2 in an N,N-dimethylformamide solution containing a tetravalent vanadium salt and meso-tetrakis(3-carboxyphenyl)porphine, place it in a hydrothermal reactor, perform a hydrothermal reaction, then wash with water, and dry to obtain an active antibacterial self-cleaning fabric.

[0010] Preferably, in step S1, the feed ratio of melamine, copper sulfate, ammonium chloride, water, ethanol and genipin is (2-3) g: (1.2-2.0) g: (0.5-1.0) g: 500 ml: (150-200) ml: (0.6-0.9) g.

[0011] Preferably, in step S2, the bath ratio of the cotton fabric base cloth to the prepolymer finishing agent is 1:30-50.

[0012] Preferably, in step S2, the rolling rate of the double dipping and double rolling is 85-95%.

[0013] Preferably, in step S2, the microwave reaction has a frequency of 3000-4000 Hz, a power of 1000-1200 W, and a time of 20-50 s.

[0014] Preferably, in step S3, the tetravalent vanadium salt is one of vanadyl oxalate, vanadium (IV) oxide diacetylacetonate, and vanadyl (IV) methyl maltol.

[0015] Preferably, in step S3, the concentrations of the tetravalent vanadium salt and meso-tetrakis(3-carboxyphenyl)porphine are 2.0-2.8 w / v % and 0.5-0.8 w / v %, respectively.

[0016] Preferably, in step S3, the bath ratio of the cotton fabric to the N,N-dimethylformamide solution containing the tetravalent vanadium salt and meso-tetrakis(3-carboxyphenyl)porphine is 1:10-20.

[0017] Preferably, in step S3, the hydrothermal reaction temperature is 120-140° C., and the reaction time is 30-50 min.

[0018] The present invention also provides an active antibacterial self-cleaning fabric prepared by the above preparation method.

[0019] Compared with the prior art, the present invention has the following beneficial effects:

[0020] 1) The present invention cross-links melamine to cellulose through microwave reaction and binds copper ions through the coordination of nitrogen atoms. A hydrothermal reaction then complexes the porphine-vanadium ions with the melamine-copper ions, forming an asymmetric copper-vanadium bimetallic catalytic active center in situ on the fiber surface. This active center, through the energy level transitions of the two transition metal electrons and electron transfer between the surrounding ligands, can convert oxygen into activated particles such as singlet oxygen, superoxide anions, and hydroxyl radicals, actively attacking bacteria and destroying their structure. Furthermore, these activated particles can oxidize and degrade organic contaminants such as oil and blood stains attached to fabric fibers, causing them to fade, achieving a self-cleaning effect.

[0021] 2) The in situ formed catalytic active center is triple-surrounded by fiber, melamine and porphine ring, which has better water resistance. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 The following are scanning electron microscope photos of the cotton fabric base cloth and the prepared active antibacterial self-cleaning fabric selected in Example 1;

[0023] Figure 2 Statistical chart of the antibacterial test results in Experimental Example 1;

[0024] Figure 3 This is a statistical chart of the oil stain and blood stain decomposition experimental results in Experimental Example 2. DETAILED DESCRIPTION

[0025] In order to further understand the present invention, preferred embodiments of the present invention are 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 for limiting the claims of the present invention.

[0026] Example 1

[0027] An active antibacterial self-cleaning fabric and a preparation method thereof, comprising the following steps:

[0028] 1. Add 2.7g melamine, 1.4g copper sulfate, and 0.8g ammonium chloride to 500ml water, add 170ml ethanol, adjust the pH to 3.9, raise the temperature to 65℃, add 0.81g genipin, and stir thoroughly to obtain a prepolymer finishing agent.

[0029] 2. Take the washed and dried cotton fabric base cloth, immerse it in the prepolymer finishing agent prepared in step 1 at a bath ratio of 1:40, double dip and double padding, with a padding rate of 90%, and perform microwave reaction at a frequency of 3500 Hz, a power of 1100 W, and a time of 30 s. Then wash it with water and dry it.

[0030] 3. The cotton fabric treated in step 2 was immersed in an N,N-dimethylformamide solution containing 2.5 w / v% vanadyl oxalate and 0.6 w / v% meso-tetrakis(3-carboxyphenyl)porphine at a bath ratio of 1:15, placed in a hydrothermal reactor, and subjected to a hydrothermal reaction at a reaction temperature of 130°C for 35 minutes. The fabric was then washed with water and dried to obtain an active antibacterial self-cleaning fabric. Figure 1 These are scanning electron microscope photos of the active antibacterial self-cleaning fabric before and after preparation. It can be observed that before preparation, the surface of the cotton fiber is slightly rough, but overall smooth. After preparation, the surface of the cotton fiber is covered with irregular nanoparticles with a particle size of 50-300nm. These particles are composite coordinated nanoparticles with copper-vanadium bimetallic as the structural center.

[0031] Example 2

[0032] An active antibacterial self-cleaning fabric and a preparation method thereof, comprising the following steps:

[0033] 1. Add 2g melamine, 1.2g copper sulfate, and 0.5g ammonium chloride to 500ml water, add 150ml ethanol, adjust the pH to 3, raise the temperature to 60℃, add 0.6g genipin, and stir thoroughly to obtain a prepolymer finishing agent.

[0034] 2. Take the washed and dried cotton fabric base cloth, immerse it in the prepolymer finishing agent prepared in step 1 at a bath ratio of 1:30, double dip and double padding, with a padding rate of 85%, and perform microwave reaction at a frequency of 3000 Hz, a power of 1000 W, and a time of 50 s. Then wash it with water and dry it.

[0035] 3. The cotton fabric treated in step 2 was immersed in an N,N-dimethylformamide solution containing 2 w / v% vanadium (IV) oxide diacetylacetonate and 0.5 w / v% meso-tetrakis (3-carboxyphenyl) porphine at a bath ratio of 1:10, placed in a hydrothermal reactor, and subjected to a hydrothermal reaction at a reaction temperature of 120 ° C for 50 min. The fabric was then washed with water and dried to obtain an active antibacterial self-cleaning fabric.

[0036] Example 3

[0037] An active antibacterial self-cleaning fabric and a preparation method thereof, comprising the following steps:

[0038] 1. Add 3g melamine, 2g copper sulfate, and 1g ammonium chloride to 500ml water, add 200ml ethanol, adjust the pH to 4.5, raise the temperature to 70℃, add 0.9g genipin, and stir thoroughly to obtain a prepolymer finishing agent.

[0039] 2. Take the washed and dried cotton fabric base cloth, immerse it in the prepolymer finishing agent prepared in step 1 at a bath ratio of 1:50, double dip and double padding, with a padding rate of 95%, and perform microwave reaction at a frequency of 4000 Hz, a power of 1200 W, and a time of 20 s. Then wash it with water and dry it.

[0040] 3. The cotton fabric treated in step 2 was immersed in an N,N-dimethylformamide solution containing 2.8w / v% methylmaltol oxyvanadium (IV) and 0.8w / v% meso-tetrakis(3-carboxyphenyl)porphine at a bath ratio of 1:20, placed in a hydrothermal reactor, and subjected to a hydrothermal reaction at a reaction temperature of 140°C for 30 minutes. The fabric was then washed with water and dried to obtain an active antibacterial self-cleaning fabric.

[0041] Comparative Example 1 (no copper)

[0042] A fabric and a preparation method thereof, comprising the following steps:

[0043] 1. Add 2.7g melamine and 0.8g ammonium chloride to 500ml water, add 170ml ethanol, adjust the pH to 3.9, raise the temperature to 65℃, add 0.81g genipin, and stir thoroughly to obtain a prepolymer finishing agent.

[0044] 2. Take the washed and dried cotton fabric base cloth, immerse it in the prepolymer finishing agent prepared in step 1 at a bath ratio of 1:40, double dip and double padding, with a padding rate of 90%, and perform microwave reaction at a frequency of 3500 Hz, a power of 1100 W, and a time of 30 s. Then wash it with water and dry it.

[0045] 3. The cotton fabric treated in step 2 was immersed in an N,N-dimethylformamide solution containing 2.5 w / v% vanadyl oxalate and 0.6 w / v% meso-tetrakis(3-carboxyphenyl)porphine at a bath ratio of 1:15, placed in a hydrothermal reactor, and subjected to a hydrothermal reaction at a reaction temperature of 130° C. for 35 min. The fabric was then washed with water and dried to obtain the fabric.

[0046] Comparative Example 2 (no vanadium)

[0047] A fabric and a preparation method thereof, comprising the following steps:

[0048] 1. Add 2.7g melamine, 1.4g copper sulfate, and 0.8g ammonium chloride to 500ml water, add 170ml ethanol, adjust the pH to 3.9, raise the temperature to 65℃, add 0.81g genipin, and stir thoroughly to obtain a prepolymer finishing agent.

[0049] 2. Take the washed and dried cotton fabric base cloth, immerse it in the prepolymer finishing agent prepared in step 1 at a bath ratio of 1:40, double dip and double padding, with a padding rate of 90%, and perform microwave reaction at a frequency of 3500 Hz, a power of 1100 W, and a time of 30 s. Then wash it with water and dry it.

[0050] 3. The cotton fabric treated in step 2 was immersed in an N,N-dimethylformamide solution containing 0.6 w / v% meso-tetrakis(3-carboxyphenyl)porphine at a bath ratio of 1:15, placed in a hydrothermal reactor, and subjected to a hydrothermal reaction at a reaction temperature of 130° C. for 35 min. The fabric was then washed with water and dried to obtain the fabric.

[0051] Comparative Example 3 (without melamine)

[0052] A fabric and a preparation method thereof, comprising the following steps:

[0053] 1. Add 1.4g copper sulfate and 0.8g ammonium chloride to 500ml water, add 170ml ethanol, adjust the pH to 3.9, raise the temperature to 65℃, add 0.81g genipin, stir thoroughly to obtain a prepolymer finishing agent.

[0054] 2. Take the washed and dried cotton fabric base cloth, immerse it in the prepolymer finishing agent prepared in step 1 at a bath ratio of 1:40, double dip and double padding, with a padding rate of 90%, and perform microwave reaction at a frequency of 3500 Hz, a power of 1100 W, and a time of 30 s. Then wash it with water and dry it.

[0055] 3. The cotton fabric treated in step 2 was immersed in an N,N-dimethylformamide solution containing 2.5 w / v% vanadyl oxalate and 0.6 w / v% meso-tetrakis(3-carboxyphenyl)porphine at a bath ratio of 1:15, placed in a hydrothermal reactor, and subjected to a hydrothermal reaction at a reaction temperature of 130° C. for 35 min. The fabric was then washed with water and dried to obtain the fabric.

[0056] Comparative Example 4 (without porphyrin)

[0057] A fabric and a preparation method thereof, comprising the following steps:

[0058] 1. Add 2.7g melamine, 1.4g copper sulfate, and 0.8g ammonium chloride to 500ml water, add 170ml ethanol, adjust the pH to 3.9, raise the temperature to 65℃, add 0.81g genipin, and stir thoroughly to obtain a prepolymer finishing agent.

[0059] 2. Take the washed and dried cotton fabric base cloth, immerse it in the prepolymer finishing agent prepared in step 1 at a bath ratio of 1:40, double dip and double padding, with a padding rate of 90%, and perform microwave reaction at a frequency of 3500 Hz, a power of 1100 W, and a time of 30 s. Then wash it with water and dry it.

[0060] 3. The cotton fabric treated in step 2 was immersed in an N,N-dimethylformamide solution containing 2.5 w / v% vanadyl oxalate at a bath ratio of 1:15, placed in a hydrothermal reactor, and subjected to a hydrothermal reaction at a reaction temperature of 130° C. for 35 min. The fabric was then washed with water and dried to obtain the fabric.

[0061] Experimental Example 1: Antibacterial Experiment

[0062] GBT 20944.3-2008 "Evaluation of antibacterial properties of textiles - Part 3 Oscillation method" was used to test the antibacterial ability of washed and dried cotton fabrics, the fabrics of Examples 1-3 and Comparative Examples 1-4 against Staphylococcus aureus, Escherichia coli and Candida albicans. The results are shown in the table. Figure 2 .

[0063] Depend on Figure 2 As can be seen, the fabrics prepared according to the examples of the present invention have excellent antibacterial properties. In comparison, the antibacterial properties of the fabric of Comparative Example 4 are relatively poor, followed by the fabrics of Comparative Examples 1 and 2. The fabrics of Comparative Example 3 have the worst antibacterial properties. This is because the fabric of Comparative Example 1 lacks copper sulfate during its preparation. Consequently, the Cu-V catalytic centers in the nanoparticles on the cotton fiber surface lack copper, effectively preventing the generation of activated particles such as singlet oxygen, leading to a significant decrease in bactericidal properties. The fabric of Comparative Example 2 does not contain a tetravalent vanadium salt. Similarly, the Cu-V catalytic centers in the nanoparticles on the cotton fiber surface lack vanadium, preventing the generation of activated particles such as singlet oxygen. However, the copper present in the system has some antibacterial properties. While its bactericidal properties are superior to those of the fabric of Comparative Example 1, they are still far inferior to those of the examples. The fabric of Comparative Example 3 does not contain melamine during its preparation, preventing the catalytically active nanoparticles and copper and vanadium ions from tightly binding to the cotton fibers, resulting in a lack of catalytic activity and the worst bactericidal properties. Comparative Example 4 does not add meso-tetrakis(3-carboxyphenyl)porphine, and cannot form porphine-oxyvanadium ions, nor can it form a complex coordination with melamine-copper ions. There is no highly active Cu-V catalytic center, and it will also affect the stability of the nanoparticles, resulting in a weakened bactericidal performance.

[0064] Experimental Example 2: Oil and blood stain decomposition experiment

[0065] The washed and dried cotton fabric base, the fabrics of Examples 1-3 and Comparative Examples 1-4 were placed in an aqueous solution containing oleic acid, and the oleic acid content in the solution was detected by gas chromatography by continuous stirring. The oleic acid degradation rate was calculated. The results are shown in FIG. Figure 3 .

[0066] The washed and dried cotton fabric base, the fabrics of Examples 1-3 and Comparative Examples 1-4 were placed in an aqueous solution containing anticoagulated healthy rabbit blood, and the changes in the hemoglobin content in the solution were detected by 540 nm absorbance through continuous stirring, and the decolorization rate was calculated. Figure 3 .

[0067] Depend on Figure 3 It can be seen that the fabrics prepared in the embodiments of the present invention have excellent grease degradation and blood stain decolorization capabilities. In comparison, the comparative example and base fabric have poor grease degradation and blood stain decolorization capabilities. The reason for this is that copper sulfate was not added during the preparation of the fabric in comparative example 1. As a result, the Cu-V catalytic centers in the nanoparticles on the cotton fiber surface lacked copper participation and could not effectively generate activated particles such as singlet oxygen. Therefore, the grease degradation and blood stain decolorization capabilities were relatively poor. The fabric in comparative example 2 did not add tetravalent vanadium salt. Similarly, the Cu-V catalytic centers in the nanoparticles on the cotton fiber surface lacked vanadium participation and could not effectively generate activated particles such as singlet oxygen. Its grease degradation and blood stain decolorization performance were similar to those of the fabric in comparative example 1. The fabric in comparative example 3 did not use melamine in its preparation, so the catalytically active nanoparticles and copper, vanadium ions were unable to tightly bind to the cotton fibers, resulting in no catalytic activity and no generation of activated particles such as singlet oxygen. The grease degradation and blood stain decolorization capabilities were the worst. Comparative Example 4 does not add meso-tetrakis(3-carboxyphenyl)porphine, and cannot form porphine-oxyvanadium ions, nor can it form a complex coordination with melamine-copper ions. It does not have a highly active Cu-V catalytic center, and it will affect the stability of the nanoparticles and cannot effectively produce activated particles such as singlet oxygen, resulting in a weakened ability to degrade oil and fat and decolorize blood stains.

[0068] The present invention provides a method and concept for an active antibacterial self-cleaning fabric and its preparation. There are many methods and approaches to implement this technical solution. The above is only a preferred embodiment of the present invention. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principles of the present invention, and such improvements and modifications should also be considered within the scope of protection of the present invention. Any components not specified in this embodiment may be implemented using existing technologies.

Claims

1. A method for preparing an active antibacterial self-cleaning fabric, characterized in that: The steps include: S1. Melamine, copper sulfate, and ammonium chloride were added to water, ethanol was added, the pH was adjusted to 3.0-4.5, the temperature was raised to 60-70 ° C, genipin was added, and the mixture was stirred thoroughly to obtain a prepolymer finishing agent; S2. Wash and dry the cotton fabric base cloth, immerse it in the prepolymer finishing agent prepared in step S1, dip it in two pads, perform a microwave reaction, then wash it and dry it; S3. Immerse the cotton fabric treated in step S2 in an N,N-dimethylformamide solution containing a tetravalent vanadium salt and meso-tetrakis(3-carboxyphenyl)porphine to undergo a hydrothermal reaction, and then wash and dry to obtain an active antibacterial self-cleaning fabric.

2. The preparation method according to claim 1, characterized in that In step S1, the feed ratio of melamine, copper sulfate, ammonium chloride, water, ethanol and genipin is (2-3) g: (1.2-2.0) g: (0.5-1.0) g: 500 ml: (150-200) ml: (0.6-0.9) g.

3. The preparation method according to claim 1, characterized in that In step S2, the bath ratio of the cotton fabric base cloth to the prepolymer finishing agent is 1:30-50.

4. The preparation method according to claim 1, characterized in that In step S2, the rolling rate of the double dipping and double rolling is 85-95%.

5. The preparation method according to claim 1, characterized in that In step S2, the microwave reaction has a frequency of 3000-4000 Hz, a power of 1000-1200 W, and a time of 20-50 s.

6. The preparation method according to claim 1, characterized in that In step S3, the tetravalent vanadium salt is one of vanadyl oxalate, vanadium diacetylacetonate oxide and vanadyl methyl maltol.

7. The preparation method according to claim 1, characterized in that In the N,N-dimethylformamide solution containing the tetravalent vanadium salt and meso-tetrakis(3-carboxyphenyl)porphine, the concentrations of the tetravalent vanadium salt and meso-tetrakis(3-carboxyphenyl)porphine are 2.0-2.8 w / v % and 0.5-0.8 w / v %, respectively.

8. The preparation method according to claim 1, characterized in that In step S3, the bath ratio of the cotton fabric to the N,N-dimethylformamide solution containing the tetravalent vanadium salt and meso-tetrakis(3-carboxyphenyl)porphine is 1:10-20.

9. The preparation method according to claim 1, characterized in that In step S3, the hydrothermal reaction temperature is 120-140° C., and the reaction time is 30-50 min.

10. Active antibacterial self-cleaning fabric prepared according to the preparation method according to any one of claims 1 to 9.

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