Active antibacterial self-cleaning fabric and preparation method thereof

Abstract

The invention belongs to the field of textiles, and particularly relates to an active antibacterial self-cleaning fabric and a preparation method thereof. The preparation method comprises the following steps: firstly, dissolving melamine, genipin, copper sulfate and ammonium chloride in water together, supplementing ethanol to prepare a prepolymer finishing agent, immersing the cotton fabric, carrying out microwave reaction, continuously immersing the cotton fabric in a DMF (Dimethyl Formamide) solution containing tetravalent vanadium salt and meso-tetra (3-carboxyphenyl) porphin, carrying out hydrothermal reaction, washing with water, and drying to obtain the antibacterial cotton fabric. And drying to obtain the active antibacterial self-cleaning fabric. The fabric not only can realize antibiosis by generating superoxide anions, hydroxyl radicals and singlet oxygen, but also can oxidize and degrade oil stains and bloodstains on the surface of the fabric to realize surface self-cleaning.

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, as the most widely distributed type of microorganisms in the human living environment, are not only ubiquitous, but also diverse, highly adaptable, and fast-growing. In particular, some harmful pathogenic bacteria seriously threaten human health. They can not only aggravate wound infection and disease progression through direct contact, but also invade the human body and cause illness by contaminating the surrounding environment, such as water, food, air, clothing, etc.

[0003] Textiles are essential functional products for human life. Due to their own microporous structure, they are very easy to absorb and contaminate microorganisms. In addition, the suitable temperature and humidity on the human body surface, the secretion of oil, sweat, etc., create favorable conditions for the reproduction and growth of microorganisms in certain special cases. How to quickly and effectively kill pathogens and hinder their metabolism and growth in textiles to solve bacterial pollution and diseases is particularly important. In addition, with the rapid development of modern textile science and technology and the improvement of people's demand for the functionality and comfort of textiles, textiles with special functions are often more likely to be favored by consumers.

[0004] In recent years, many experts and scholars have tried to use various methods to seek new breakthroughs in the antibacterial functionalization of textiles. Among them, photodynamic therapy based on metal organic framework materials and catalytic antibacterial materials represented by transition metal nanozymes have become the most prominent category in the current research on antibacterial agents due to their high oxidation activity and stability, non-toxicity, tastelessness, and no secondary pollution. They are applied to the antibacterial functional finishing of textiles, giving the fabrics multiple functions such as antibacterial deodorization and self-cleaning. Compared with traditional textiles, these textiles often have higher added value while improving people's lives, which will undoubtedly promote the textile industry to create greater social and economic benefits. Summary of the invention

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

[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. Add melamine, copper sulfate and ammonium chloride to water, add ethanol, adjust the pH to 3.0-4.5, raise the temperature to 60-70°C, add genipin, stir well, and obtain a prepolymer finishing agent;

[0008] S2. Take the washed and dried cotton fabric base cloth, immerse it in the prepolymer finishing agent prepared in step S1, and after two immersions and two rollings, perform microwave reaction, then wash and dry;

[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 N atoms, and then uses hydrothermal reaction to complex coordinate porphine-oxyvanadium ions with melamine-copper ions, forming an asymmetric copper-vanadium bimetallic catalytic active center in situ on the fiber surface. The active center can convert oxygen into activated particles such as singlet oxygen, superoxide anions and hydroxyl free radicals by means of the electron energy level transition of two transition metals and the electron transfer between the surrounding ligands, actively attacking bacteria and destroying bacterial structures. Moreover, these activated particles can also oxidize and degrade organic dirt such as oil stains and blood stains attached to fabric fibers, and make them fade, thereby achieving the purpose of self-cleaning.

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

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

[0023] Figure 2 It is a 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 test 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, but 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.

[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°C, add 0.81g genipin, stir well 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 immersion and double rolling, with a rolling rate of 90%, and carry out microwave reaction at a frequency of 3500 Hz, a power of 1100 W, and a time of 30 s, then wash and dry.

[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, and placed in a hydrothermal reactor for hydrothermal reaction at a reaction temperature of 130° C. for 35 min, followed by washing with water and drying to obtain an active antibacterial self-cleaning fabric. Figure 1 These are scanning electron microscope photos of active antibacterial self-cleaning fabrics 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 bimetal 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 into 500ml water, add 150ml ethanol, adjust the pH to 3, raise the temperature to 60℃, add 0.6g genipin, stir well 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 immersion and double rolling, with a rolling rate of 85%, and carry out microwave reaction at a frequency of 3000 Hz, a power of 1000 W, and a time of 50 s, then wash and dry.

[0035] 3. The cotton fabric treated in step 2 is immersed in an N,N-dimethylformamide solution containing 2 w / v% oxydiacetylacetonatovanadium (IV) and 0.5 w / v% meso-tetrakis(3-carboxyphenyl)porphine at a bath ratio of 1:10, and placed in a hydrothermal reactor for hydrothermal reaction at a reaction temperature of 120°C for 50 min, followed by washing with water and drying 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 into 500ml water, add 200ml ethanol, adjust the pH to 4.5, raise the temperature to 70℃, add 0.9g genipin, stir well 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 immersion and double rolling, with a rolling rate of 95%, and carry out microwave reaction at a frequency of 4000 Hz, a power of 1200 W, and a time of 20 s, then wash and dry.

[0040] 3. The cotton fabric treated in step 2 is immersed in an N,N-dimethylformamide solution containing 2.8w / v% methyl maltol oxyvanadium (IV) and 0.8w / v% meso-tetrakis(3-carboxyphenyl)porphine at a bath ratio of 1:20, and placed in a hydrothermal reactor for hydrothermal reaction at a reaction temperature of 140°C for 30 minutes. The fabric is 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°C, add 0.81g genipin, stir well, and 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 immersion and double rolling, with a rolling rate of 90%, and carry out microwave reaction at a frequency of 3500 Hz, a power of 1100 W, and a time of 30 s, then wash and dry.

[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, and placed in a hydrothermal reactor for hydrothermal reaction at a reaction temperature of 130° C. for a reaction time of 35 min, followed by washing with water and drying to obtain the fabric.

[0046] Comparative Example 2 (without 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°C, add 0.81g genipin, stir well 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 immersion and double rolling, with a rolling rate of 90%, and carry out microwave reaction at a frequency of 3500 Hz, a power of 1100 W, and a time of 30 s, then wash and dry.

[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, followed by washing with water and drying 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°C, add 0.81g genipin, stir well 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 immersion and double rolling, with a rolling rate of 90%, and carry out microwave reaction at a frequency of 3500 Hz, a power of 1100 W, and a time of 30 s, then wash and dry.

[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, and placed in a hydrothermal reactor for hydrothermal reaction at a reaction temperature of 130° C. for a reaction time of 35 min, followed by washing with water and drying 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°C, add 0.81g genipin, stir well 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 immersion and double rolling, with a rolling rate of 90%, and carry out microwave reaction at a frequency of 3500 Hz, a power of 1100 W, and a time of 30 s, then wash and dry.

[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, and placed in a hydrothermal reactor for hydrothermal reaction at a reaction temperature of 130° C. for 35 min, followed by washing with water and drying 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 Figure 2 .

[0063] Depend on Figure 2 It can be seen that the fabric prepared by the embodiment of the present invention has excellent antibacterial ability. In comparison, the antibacterial ability of the fabric of comparative example 4 is poor, followed by the fabrics of comparative examples 1 and 2. The fabrics with the worst antibacterial ability are the base fabric and the fabric of comparative example 3. The reason is that copper sulfate was not added during the preparation of the fabric of comparative example 1, and the Cu-V catalytic center in the nanoparticles on the surface of the cotton fiber lacked the participation of copper, and could not effectively produce activated particles such as singlet oxygen, so the bactericidal performance was significantly reduced. No tetravalent vanadium salt was added to the fabric of comparative example 2. Similarly, the Cu-V catalytic center in the nanoparticles on the surface of the cotton fiber lacked the participation of vanadium, and could not effectively produce activated particles such as singlet oxygen, but the copper present in the system itself has a certain antibacterial effect. Although its bactericidal ability is better than that of the fabric of comparative example 1, its bactericidal ability is far less than that of the fabric of the embodiment. Melamine was not used in the preparation of the fabric of comparative example 3, so that the nanoparticles with catalytic activity and copper, vanadium and other ions could not be closely combined with the cotton fiber, there was no catalytic activity, and the bactericidal performance was the worst. Comparative Example 4 does not add meso-tetrakis(3-carboxyphenyl)porphine, and cannot form porphine-oxyvanadium ions, and cannot form a complex coordination with melamine-copper ions. It has no highly active Cu-V catalytic center and 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 aqueous solutions containing oleic acid, respectively. The changes in the oleic acid content in the solutions were detected by gas chromatography through continuous stirring, and 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 using the absorbance at 540 nm by continuous stirring, and the decolorization rate was calculated. The results are shown in FIG. Figure 3 .

[0067] Depend on Figure 3 It can be seen that the fabric prepared by the embodiment of the present invention has excellent grease degradation ability and blood stain decolorization ability. In comparison, the grease degradation ability and blood stain decolorization ability of the comparative example and the base fabric are not good. The reason is that copper sulfate was not added during the preparation of the fabric of comparative example 1, and the Cu-V catalytic center in the nanoparticles on the surface of the cotton fiber lacked the participation of copper, and could not effectively produce activated particles such as singlet oxygen, so the grease degradation ability and blood stain decolorization ability were poor. No tetravalent vanadium salt was added to the fabric of comparative example 2. Similarly, the Cu-V catalytic center in the nanoparticles on the surface of the cotton fiber lacked the participation of vanadium, and could not effectively produce activated particles such as singlet oxygen. Its grease degradation and blood stain decolorization effects were similar to those of the fabric of comparative example 1. Melamine was not used in the preparation of the fabric of comparative example 3, so that the catalytically active nanoparticles and copper, vanadium and other ions could not be closely combined with the cotton fibers, there was no catalytic activity, and activated particles such as singlet oxygen could not be produced, and the grease degradation ability and blood stain decolorization ability 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. It 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 an idea and method for an active antibacterial self-cleaning fabric and a preparation method thereof. There are many methods and approaches to implement the technical solution. The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as the protection scope of the present invention. All components not specified in this embodiment can be implemented by existing technologies.

Claims

1. A method for preparing an active antibacterial self-cleaning fabric, characterized in that: The steps include: S1. Add melamine, copper sulfate and ammonium chloride to water, add ethanol, adjust the pH to 3.0-4.5, raise the temperature to 60-70°C, add genipin, stir well, and obtain a prepolymer finishing agent; S2. Take the washed and dried cotton fabric base cloth, immerse it in the prepolymer finishing agent prepared in step S1, and after two immersions and two rollings, perform microwave reaction, then wash and dry; 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 carry out a hydrothermal reaction, then wash with water 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 oxydiacetylacetonate and vanadyl methyl maltol.

7. The preparation method according to claim 1, characterized in that: In the N,N-dimethylformamide solution containing 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. An active antibacterial self-cleaning fabric prepared according to the preparation method according to any one of claims 1 to 9.

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