CN115160453B - Preparation method and application of biomolecule-based chelating film-forming agent - Google Patents

Preparation method and application of biomolecule-based chelating film-forming agent Download PDF

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CN115160453B
CN115160453B CN202210808571.2A CN202210808571A CN115160453B CN 115160453 B CN115160453 B CN 115160453B CN 202210808571 A CN202210808571 A CN 202210808571A CN 115160453 B CN115160453 B CN 115160453B
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amino acid
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CN115160453A (en
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郑栋
张瑞云
赵亚萍
苏醒
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Shanghai Jialaiduo Biotechnology Co ltd
Donghua University
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Donghua University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
    • C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
    • C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03—Polysaccharides or derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/32—Polyesters

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  • Textile Engineering (AREA)
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Abstract

The invention discloses a preparation method of a biomolecule based chelating film forming agent, belonging to the technical field of biomolecule based chelating film forming agents, and the preparation method comprises the following steps: the biomolecular based chelating film-forming agent is obtained by taking chitosan and amino acid as raw materials through graft polymerization reaction, not only has stronger chelating effect on metal ions, but also has active groups reacting with the surface of textile fiber, is beneficial to the adsorption-reduction of the metal ions on the surface of a fiber product, the deposited layer is firmly combined with the fiber, and the natural antibacterial property of the biomolecular endows the fiber product with certain antibacterial performance and the like, so that the problem that the conductivity and the service performance of the metallized fiber product cannot be simultaneously considered can be effectively solved.

Description

Preparation method and application of biomolecule-based chelating film-forming agent
Technical Field
The invention relates to the technical field of a biomolecule based chelating film forming agent, in particular to a preparation method and application of the biomolecule based chelating film forming agent.
Background
The development of modern science and technology causes the electromagnetic radiation to pollute the living space of human beings, which can damage the health of the human beings and easily cause the symptoms of fatigue, vision deterioration, headache, insomnia and the like. Therefore, the demand of electromagnetic radiation shielding fabrics is increasing, and the development of shielding materials is also in progress. In recent years, metallized fabrics with both protective and decorative properties have become the mainstream of novel electromagnetic shielding functional materials. Fabric metallization treatment technology attracts great attention of scientific research personnel, and the metallization structure is directly formed on the surface of the fabric by a coating vacuum coating method and a magnetron sputtering method; secondly, chemical plating, namely reducing the metal into atoms or molecules through chemical reaction and depositing the atoms or the molecules on the surface of the fiber or the yarn; and thirdly, carrying out metallization treatment on the fabric by using plasma.
At present, the chemical plating of textiles is mainly copper plating, nickel plating and silver plating. The chemical plating method is used to plate silver, copper, nickel and other metals on the surface of fabric, so that the fabric has metal luster incapable of being obtained in common printing and dyeing process and has more special functions, such as shielding electromagnetic wave, resisting heat radiation, resisting static electricity, resisting bacteria, reflecting and absorbing ultraviolet ray and infrared ray, etc.
The basic principle of chemical plating is to put the fabric in an aqueous solution of metal salt and add a reducing agent (such as hypophosphite or a boron hydride) to make the metal precipitate and plate on the surface of the fiber. The chemical plating solution consists of metal salt, reductant, complexing agent, stabilizer, etc. and the main reaction is that the reductant reduces metal ion into metal atom or molecule deposited on the surface of fiber while the noble metal adsorbed onto the fiber is catalyzed to form metal film. Namely, a reducing agent is adopted to ensure that metal ions are reduced and deposited on a substrate to form a metal film, and the method mainly comprises the steps of pretreatment, catalysis, activation and chemical plating. In order for the deposition process to continue spontaneously, both the plated substrate and the reducing metal should be catalytically active.
But the use cost of the noble metal salt in the chemical plating process in the surface metallization method of the textile fiber products is higher. Sensitizers (e.g. Sn) for noble metal ions adsorbed by the surface of the fabric as oxidizing agents 2+ ) The noble metal generated by reduction, such as Pd, ag and the like, is adhered to the surface of the fabric in the form of colloidal particles, has strong catalytic activity, and the particles become catalytic centers during subsequent chemical plating, so that the chemical plating can be performed spontaneously. However, the sensitization and activation steps in the chemical plating method have the problems of complicated operation, unstable plating solution and the like.
And the metal conductive layer on the surface of the metallized fiber product has the problem of bonding fastness. Many conductive fiber products have poor friction resistance and poor fastness to washing, and the requirements of long-term use and regular cleaning of the conductive fiber products of the current intelligent clothes are difficult to meet.
In addition, metallized textile fiber products have poor wearing comfort. The textile with the microporous structure is a hotbed which is most suitable for breeding and propagating microorganisms such as bacteria, fungi and the like, the vitality of the microorganisms of the diseases remained on the textile is enhanced by the temperature of a human body, the moisture, skin metabolites and the like of a wearer of the electronic textile, and the requirements of the comfort functions of antibiosis, deodorization and the like of the conductive fiber are difficult to meet at present.
Disclosure of Invention
The invention aims to provide a biomolecule-based chelating film-forming agent which takes biomolecules (natural micromolecules and macromolecules) as main raw materials, has stronger chelating effect on metal ions, has active groups which react with the surface of textile fibers, is beneficial to the adsorption-reduction of the metal ions on the surface of a fiber product, and has firm combination of a deposited layer and the fibers, and the natural antibacterial property of the biomolecules endows the fiber product with certain antibacterial performance and the like, so that the problem that the conductive performance and the service performance of the metallized fiber product cannot be considered at the same time can be effectively solved.
In order to achieve the purpose, the invention provides the following scheme:
the invention provides a preparation method of a biomolecule based chelating film forming agent, which comprises the following steps: the biomolecular based chelating film forming agent is obtained by taking chitosan and amino acid as raw materials through graft polymerization reaction.
Further, the preparation method specifically comprises the following steps:
mixing N-methylimidazole with brominated alkane to obtain liquid A; then pouring the liquid A into anion exchange resin, dropwise adding an amino acid aqueous solution, stirring at the temperature of 0-10 ℃, dropwise adding at the speed of 5d/s, and vacuum-drying at the temperature of 40-50 ℃ to obtain liquid B; dissolving the liquid B in water to prepare an aqueous solution C, dropwise adding chitosan into the aqueous solution C under stirring at normal temperature and normal pressure, separating a small amount of undissolved chitosan by using a high-speed centrifuge after the reaction is completed, and filtering by using a filter screen to obtain a light yellow transparent solution D, namely the biomolecule-based chelating film-forming agent.
Further, the mass ratio of the N-methylimidazole to the brominated alkane is 1.
Further, the mass ratio of the liquid A to the amino acid aqueous solution is 0.5-2;
the amount of the substance of the liquid A is 0.05-0.2 mol;
the amino acid aqueous solution is an aqueous solution of amino acid and hydrochloric acid with the concentration of 0.1mol/L, and the mass ratio of the amino acid in the amino acid aqueous solution is 2-10 wt%.
Further, the amino acid is one or two of glycine, alanine, leucine, glutamic acid, serine, tryptophan and histidine.
Further, the stirring time is 8 to 10 hours at 0 ℃.
Further, the conductivity 10 of the liquid B -6 ～10 -4 s/cm。
Further, the viscosity-average molecular weight of the chitosan is 10 4 ～10 6 。
Further, the liquid B and water are prepared into an aqueous solution C according to the mass ratio of 1.
Further, the mass ratio of the chitosan to the aqueous solution C is 0.04-0.08.
The invention also provides application of the biomolecule based chelating film-forming agent prepared by the preparation method in preparation of metallized fiber products.
Further, the application method comprises the following steps: dropwise adding 1-3% acetic acid solution into the solution D at a certain stirring speed, continuously stirring and performing ultrasonic defoaming after dropwise adding, continuously dropwise adding a small amount of cross-linking agent at a certain temperature, controlling the stirring speed and the dropwise adding speed, continuously stirring at room temperature for 30-60 min after dropwise adding, dipping the fiber product into the solution, performing dipping-rolling-drying treatment, dipping into a metal salt solution, adding a reducing solution, reacting for a certain time, taking out, washing and drying to obtain the metallized fiber product.
Furthermore, in the application method, certain stirring speed is 800-1000 r/min, and the dripping speed of the acetic acid solution is 10-15 d/min; the mass ratio of the solution D to the acetic acid solution is 0.01-0.03.
Furthermore, in the application method, the certain temperature is 5-15 ℃, the cross-linking agent is glyoxal or glutaraldehyde, the mass of the cross-linking agent is 5-10% of the solution D, the stirring speed is controlled at 600-800 r/min, and the dropping speed is 20-30D/min.
Further, in the application method, in the soaking-rolling-drying treatment, soaking and rolling are carried out, the soaking time is 10-20 min each time, the rolling residual rate is 80-100%, pre-drying is carried out for 30min at 40 ℃, and drying is carried out for 1h at 150 ℃.
Furthermore, the main components of the metal salt solution in the application method comprise one or more of silver nitrate, nickel chloride, copper oxalate, copper acetate, copper nitrate or copper chloride and the like, and auxiliary additives such as citric acid, polyethylene glycol, 2' -bipyridine, potassium sodium tartrate and the like; the reducing liquid is saccharide, hypophosphite, boron-containing compound, etc.; the reaction temperature is 40-60 ℃, and the reaction time is 20-40 min.
The invention discloses the following technical effects:
the biomolecule-based chelating film-forming agent which takes biomolecules (natural micromolecules and macromolecules) as main raw materials not only has stronger chelating effect on metal ions, but also has active groups (amino and hydroxyl) which react with the surface of textile fibers, is favorable for the adsorption-reduction of the metal ions on the surface of a fiber product, the deposited layer is firmly combined with the fibers, and the natural antibacterial property of the biomolecules endows the fiber product with certain antibacterial performance and the like, so that the problem that the conductivity and the service performance of the metallized fiber product cannot be considered at the same time can be effectively solved.
The sheet resistance of the metallized fiber product prepared by the biomolecule based chelating film forming agent reaches 100m omega/\9633 ~ -10 omega/\9633, the rubbing (dry and wet) color fastness is more than or equal to 4 grade, the perspiration (acid and alkali) color fastness is more than or equal to 4 grade, and the antibacterial rate is still kept above 99.62 percent after 200 times of washing.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without inventive exercise.
FIG. 1 is a scanning electron microscope image of the biomolecule-based chelating film former prepared in example 1 forming a film between two fibers;
FIG. 2 is an atomic force microscope photograph of the on-fiber state of the biomolecule-based chelating film formers prepared in example 1, wherein (a) -before the film former is not applied, (b) -after the film former is applied;
FIG. 3 is a scanning electron microscope image of the surface of the metallized fibrous article prepared in example 1.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in that stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. It is intended that the specification and examples be considered as exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including but not limited to.
In the embodiment of the invention, the amino acid aqueous solution is a mixed aqueous solution of amino acid and hydrochloric acid (0.1 mol/L).
In the examples of the present invention, the viscosity average molecular weight of chitosan is 10 4 ～10 6 。
Example 1
The ratio of N-methylimidazole to alkyl bromide according to the mass is 1:1 mixing to obtain liquid A, wherein the amount of the substance of the liquid A is 0.05mol; pouring the liquid A into anion exchange resin, dropwise adding glycine aqueous solution with the mass of 2wt% of glycine in the glycine aqueous solution, stirring at 0 deg.C for 10h, and vacuum drying at 40 deg.C to obtain liquid B with the conductivity of 10 -6 s/cm; mixing the liquid B with water according to a mass ratio of 1. The scanning electron microscope picture of the prepared biomolecule based chelating film forming agent forming layer between two fibers is shown in figure 1, the atomic force fiber mirror picture of the state on the fiber is shown in figure 2 ((a) -before the film forming agent is not applied, (b) -after the film forming agent is applied), and as can be seen from figures 1 and 2, the film forming agent can uniformly form a film on the surface of the fiber, and the roughness of the surface is increased, which is beneficial for the anchoring of metal particles on the surface.
The biomolecular based chelating film forming agent taking the terylene film as the substrate has obvious bacteriostatic effect on escherichia coli and staphylococcus aureus, the bacteriostatic rates are respectively as high as 99.87% and 99.90%, and the biomolecular based chelating film forming agent almost completely inhibits the growth of the escherichia coli and the staphylococcus aureus.
Dropwise adding 1% acetic acid solution into the solution D at the stirring speed of 800r/min at the dropwise adding speed of 10D/min, wherein the mass ratio of the solution D to the acetic acid solution is 0.01, continuously stirring and carrying out ultrasonic defoaming after the dropwise adding is finished, continuously dropwise adding a small amount of cross-linking agent glyoxal at the temperature of 10 ℃, wherein the mass of the crosslinking agent glyoxal is 5% of that of the liquid D, controlling the stirring speed to be 800r/min and the dropwise adding speed to be 20D/min, continuously stirring at room temperature for 30min after the dropwise adding is finished, soaking the fiber product into the solution, carrying out soaking-rolling-drying treatment, soaking and rolling, wherein the soaking time is 10min each time, the rolling residual rate is 100%, pre-drying at the temperature of 40 ℃ for 30min and baking at the temperature of 150 ℃ for 1h, soaking the fiber product into a metal salt solution containing silver nitrate and citric acid, adding reducing solution glucose, reacting at the temperature of 40 ℃ for 35min, taking out, washing and drying to obtain the metal chemical fiber product.
The surface electron microscope picture of the metallized fiber product prepared by the embodiment is shown in figure 3, the sheet resistance is lower than 1 omega/\9633andis 780 +/-200 m omega/\9633, the color fastness to rubbing (dry and wet) is more than or equal to grade 4, and the antibacterial rate is kept above 99.62 percent after 200 times of washing.
Example 2
The ratio of N-methylimidazole to alkyl bromide according to the mass is 1:1, mixing to obtain liquid A, wherein the substance amount of the liquid A is 0.1mol; pouring the liquid A into anion exchange resin, dropwise adding alanine water solution with alanine mass ratio of 5wt%, stirring at 0 deg.C for 8 hr, and vacuum drying at 40 deg.C to obtain liquid B with conductivity of 10 -5 s/cm; mixing the liquid B with water according to a mass ratio of 1.
Dropwise adding 1% acetic acid solution into the solution D at the stirring speed of 1000r/min, dropwise adding at the speed of 12D/min, wherein the mass ratio of the solution D to the acetic acid solution is 0.01, continuously stirring and ultrasonically defoaming after dropwise adding is finished, continuously dropwise adding a small amount of cross-linking agent glyoxal at 10 ℃, wherein the mass of the cross-linking agent glyoxal is 8% of that of the liquid D, controlling the stirring speed to be 700r/min, dropwise adding at the speed of 25D/min, continuously stirring at room temperature for 30min after dropwise adding is finished, soaking the fiber product into the solution, performing soaking-rolling-drying treatment, soaking and rolling, wherein the soaking time is 15min each time, the rolling residual rate is 90%, pre-drying at 40 ℃ for 30min, baking at 150 ℃ for 1h, soaking into metal salt solutions of silver nitrate, copper nitrate and polyethylene glycol, adding a reducing solution sodium hypophosphite, reacting at 40 ℃ for 35min, taking out, washing, and drying to obtain the metallic fiber product.
The biomolecular based chelating film forming agent with the terylene film as the substrate has obvious bacteriostatic effect on escherichia coli and staphylococcus aureus, the bacteriostatic rate is respectively as high as 99.95 percent and 99.96 percent, which shows that the biomolecular based chelating film forming agent almost completely inhibits the growth of the escherichia coli and the staphylococcus aureus.
The metalized fiber product prepared by the embodiment has the sheet resistance lower than 10 omega/\9633, 3.5 +/-1.2 omega/\9633, the rubbing (dry and wet) color fastness is more than or equal to grade 4, and the antibacterial rate is kept above 99.71 percent after 200 times of washing.
Example 3
And (2) mixing N-methylimidazole with bromoalkane according to the mass ratio of 1:1 mixing to obtain liquid A, wherein the amount of the substance of the liquid A is 0.2mol; then pouring the liquid A into anion exchange resin and dropwise adding leucine aqueous solution, wherein the mass ratio of leucine is 5wt%, stirring at 0 ℃ for 9h, and vacuum drying at 40 ℃ to obtain liquid B, wherein the conductivity of the liquid B is 10 -4 s/cm; and mixing the liquid B with water according to a mass ratio of 1.
Dropwise adding 1% acetic acid solution into the solution D at the stirring speed of 900r/min, the dropwise adding speed is 15D/min, the mass ratio of the solution D to the acetic acid solution is 0.03, continuously stirring and ultrasonic defoaming after the dropwise adding is finished, continuously dropwise adding a small amount of cross-linking agent glutaraldehyde at 10 ℃, the mass of the cross-linking agent glutaraldehyde is 10% of that of the liquid D, controlling the stirring speed to be 600r/min, the dropwise adding speed to be 25D/min, continuously stirring at room temperature for 30min after the dropwise adding is finished, soaking the fiber product into the above solution, carrying out soaking-rolling-drying treatment, soaking and rolling, wherein the soaking time is 20min each time, the rolling residue rate is 80%, pre-drying at 40 ℃ for 30min, baking at 150 ℃ for 1h, soaking into a metal salt solution containing silver nitrate, nickel nitrate, copper nitrate and 2,2' -bipyridine, adding reducing liquid sodium borohydride, reacting at 40 ℃ for 35min, taking out, washing and drying to obtain the metallic fiber product.
The biomolecular based chelating film forming agent with the terylene film as the substrate has obvious bacteriostatic effect on escherichia coli and staphylococcus aureus, the bacteriostatic rate is respectively as high as 99.97% and 99.96%, which shows that the biomolecular based chelating film forming agent almost completely inhibits the growth of the escherichia coli and the staphylococcus aureus.
The metallized fiber product prepared by the embodiment has the square resistance lower than 10 omega/\9633, 6.3 +/-2.2 omega/\9633, the rubbing (dry and wet) color fastness is more than or equal to 4 grades, and the antibacterial rate is kept above 99.75 percent after 200 times of washing.
Example 4
And (2) mixing N-methylimidazole with bromoalkane according to the mass ratio of 1:1 mixing to obtain liquid A, wherein the amount of the substance of the liquid A is 0.2mol; pouring the liquid A into anion exchange resin, dropwise adding tryptophan water solution with the tryptophan mass ratio of 10wt%, stirring at 0 deg.C for 8 hr, and vacuum drying at 40 deg.C to obtain liquid B with conductivity of 10 -5 s/cm; mixing the liquid B with water according to a mass ratio of 1.
Dropwise adding 1% acetic acid solution into the solution D at the stirring speed of 900r/min, dropwise adding at the speed of 12D/min, wherein the mass ratio of the solution D to the acetic acid solution is 0.02, continuously stirring and ultrasonically defoaming after dropwise adding is finished, continuously dropwise adding a small amount of cross-linking agent glutaraldehyde at 12 ℃, wherein the mass of the cross-linking agent glutaraldehyde is 10% of that of the liquid D, controlling the stirring speed to be 700r/min, dropwise adding at the speed of 30D/min, continuously stirring at room temperature for 30min after dropwise adding is finished, soaking the fiber product into the above solution, performing soaking-rolling-drying treatment, soaking and rolling, wherein the soaking time is 15min each time, the rolling residual rate is 100%, pre-drying at 40 ℃ for 30min, drying at 150 ℃ for 1h, soaking into a metal salt solution containing silver nitrate, nickel nitrate and potassium sodium tartrate, adding reducing liquid glucose, reacting at 40 ℃ for 35min, taking out, washing and drying to obtain the metallic fiber product.
The biomolecular based chelating film forming agent with the terylene film as the substrate has obvious bacteriostatic effect on escherichia coli and staphylococcus aureus, the bacteriostatic rate is respectively as high as 99.92% and 99.91%, which shows that the biomolecular based chelating film forming agent almost completely inhibits the growth of the escherichia coli and the staphylococcus aureus.
The metalized fiber product prepared by the embodiment has the sheet resistance lower than 10 omega/\9633, 4.6 +/-2.0 omega/\9633, friction (dry and wet) color fastness more than or equal to grade 4, and the antibacterial rate maintained above 99.65% after 200 times of washing.
Example 5
The difference from example 3 is only that the amino acids are glutamic acid and histidine, and the mass ratio of the two is 1:1.
the metallized fiber product prepared by the embodiment has the sheet resistance of 3.5 +/-1.8 omega/9633, the color fastness to rubbing (dry and wet) is more than or equal to 4 grade, and the antibacterial rate is kept above 99.81 percent after 200 times of washing.
Example 6
The difference from example 4 is only that the amino acids are serine and leucine in a mass ratio of 1:1.
the metallized fiber product prepared by the embodiment has the sheet resistance of 4.7 +/-2.3 omega/\9633, the rubbing (dry and wet) color fastness of more than or equal to 4 grade, and the antibacterial rate of over 99.82 percent after 200 times of washing.
Example 7
The ratio of N-methylimidazole to alkyl bromide according to the mass is 1:1 mixing to obtain liquid A, wherein the amount of the substance of the liquid A is 0.1mol; pouring the liquid A into anion exchange resin, dropwise adding glutamic acid aqueous solution at 0 deg.C under stirring, wherein the glutamic acid mass ratio is 6wt%Stirring for 9h, and vacuum drying at 40 deg.C to obtain liquid B with conductivity of 10 -5 s/cm; mixing the liquid B with water according to a mass ratio of 1.
Dropwise adding 1% acetic acid solution into the solution D at the stirring speed of 900r/min, the dropwise adding speed is 12D/min, the mass ratio of the solution D to the acetic acid solution is 0.02, continuously stirring and carrying out ultrasonic defoaming after the dropwise adding is finished, continuously dropwise adding a small amount of cross-linking agent glyoxal at 10 ℃, the mass of the crosslinking agent glyoxal is 8% of that of the liquid D, controlling the stirring speed to be 700r/min, the dropwise adding speed to be 25D/min, continuously stirring at room temperature for 30min after the dropwise adding is finished, soaking the fiber product into the solution, carrying out soaking-rolling-drying treatment, soaking and rolling, the soaking time is 15min each time, the rolling residual rate is 95%, pre-drying at 40 ℃ for 30min, baking at 150 ℃ for 1h, soaking into a metal salt solution containing silver nitrate and polyethylene glycol, adding reducing liquid sodium hypophosphite, reacting at 40 ℃ for 35min, taking out, washing and drying to obtain the metal chemical fiber product.
The biomolecular based chelating film forming agent with the terylene film as the substrate has obvious bacteriostatic effect on escherichia coli and staphylococcus aureus, the bacteriostatic rate is respectively as high as 99.98 percent and 99.97 percent, which shows that the biomolecular based chelating film forming agent almost completely inhibits the growth of the escherichia coli and the staphylococcus aureus.
The metallized fiber product prepared by the embodiment has the sheet resistance of 6.1 +/-3.6 omega/\9633, the rubbing (dry and wet) color fastness of more than or equal to 4 grade, and the antibacterial rate of over 99.78 percent after 200 times of washing.
Comparative example 1
Soaking the fiber product in 1 wt% chitosan solution, soaking, rolling and baking for 15min each time, the rolling residual rate is 95%, pre-baking at 40 deg.C for 30min, and baking at 150 deg.C for 1h; then dipped in 12g/LAgNO 3 8g/L NaOH and 100mL/LNH 3 ·H 2 Adding 3.0g/L glucose into the O solutionReacting at 40 ℃ for 50min, taking out, washing with water, and drying to obtain the metallized fiber product. The metallized fiber product prepared by the comparative example has the square resistance of 68.2 +/-23.2 omega/\9633, the color fastness to rubbing (dry and wet) is 3 grade, the antibacterial rate is 75.3 percent after 40 times of washing, and the antibacterial rate is 68.6 percent after 80 times of washing.
Comparative example 2
The same as example 4, except that no aqueous tryptophan solution was added.
The sheet resistance of the metallized fiber product prepared by the comparative example is 56.5 +/-21.2 omega/9633the rubbing (dry and wet) color fastness is 3 grade, the antibacterial rate is 85.2 percent after 40 times of washing and 76.4 percent after 80 times of washing.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.

Claims (5)

1. The application of the biomolecule based chelating film forming agent in the preparation of the metallized fiber product is characterized in that the preparation method of the biomolecule based chelating film forming agent comprises the following steps: mixing N-methylimidazole with bromoalkane to obtain liquid A; then pouring the liquid A into anion exchange resin, dropwise adding an amino acid aqueous solution, stirring at the temperature of 0-10 ℃, dropwise adding at the speed of 5d/s, and vacuum-drying at the temperature of 40-50 ℃ to obtain liquid B; dissolving the liquid B in water to prepare an aqueous solution C, dropwise adding chitosan into the aqueous solution C under stirring at normal temperature and normal pressure, centrifuging after complete reaction, and filtering to obtain a light yellow transparent solution D, namely the biomolecule-based chelating film-forming agent; the application method comprises the following steps: dropwise adding 1-3% acetic acid solution into the solution D under the stirring state, continuously stirring and performing ultrasonic defoaming after dropwise adding, continuously dropwise adding a cross-linking agent, continuously stirring at room temperature for 30-60 min after dropwise adding, soaking the fiber product into the solution, performing soaking-rolling-drying treatment, soaking the fiber product into a metal salt solution, adding a reducing solution, taking out after reaction, washing with water, and drying to obtain a metallized fiber product;
the mass ratio of the liquid A to the amino acid aqueous solution is 0.5-2;
the amount of the substance of the liquid A is 0.05-0.2 mol;
the amino acid aqueous solution is an aqueous solution of amino acid and hydrochloric acid with the concentration of 0.1mol/L, and the mass ratio of the amino acid in the amino acid aqueous solution is 2-10 wt%;
the mass ratio of the chitosan to the aqueous solution C is 0.04-0.08.
2. Use according to claim 1, characterized in that the mass ratio of the N-methylimidazole to the brominated alkane is 1.
3. The use according to claim 1, wherein the amino acid is one or two of glycine, alanine, leucine, glutamic acid, serine, tryptophan and histidine.
4. The use according to claim 1, wherein the biomolecule-based chelating film former is prepared by adding dropwise an aqueous solution of amino acid and stirring at 0 ℃ for 8-10 hours.
5. Use according to claim 1, wherein the chitosan has a viscosity average molecular weight of 10 4 ～10 6 。
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