A method for in-situ dyeing and antibacterial finishing of protein fiber products based on Fenton system catalysis

Abstract

The present invention discloses a method for in-situ dyeing and antibacterial finishing of protein fiber products based on Fenton system catalysis, belonging to the technical field of textile dyeing and finishing. The specific steps of the method of the present invention include: (1) treating protein fiber products with phenolic small molecules; (2) catalyzing in-situ chromogenesis of protein fibers by Fenton reagent; (3) in-situ depositing silver nanoparticles on the surface of protein fibers; mainly through the catalytic oxidation of phenolic small molecules by the Fenton system to graft and polymerize with protein fibers to form colored polyphenol polymers, improving the dyeing depth and color fastness of protein fiber products; further reducing and depositing silver nanoparticles through the colored polyphenol polymers to enhance the antibacterial property of protein fiber products. Compared with the traditional acid dyeing method for protein fiber products, the method of the present invention has the advantages of low production energy consumption, high color fastness and excellent antibacterial property.

Description

Technical Field

[0001] The present invention relates to a method for in-situ dyeing and antibacterial finishing of protein fiber products based on Fenton system catalysis, belonging to the technical field of textile dyeing and finishing. Background Art

[0002] Protein fiber products mainly include textile fiber products processed from raw materials such as silk and wool. Compared with synthetic fibers, protein fibers have excellent handfeel and good moisture absorption performance, and belong to the textile raw materials of high-grade fiber products. Their disadvantage is that they are prone to bacterial growth. When dyeing protein fiber products, acid dyes are usually used under high temperature conditions close to boiling, and the energy consumption during the dyeing process is relatively high. Since the dye binds to the fiber through hydrogen bonds, van der Waals forces and ionic bonds, the wet treatment fastness of the dyed product is relatively poor. To improve the dyeing fastness of acid dyes on protein fiber products, a chromium-containing mordant is usually added. After mordant treatment, the dyeing fastness of the fiber products will be improved to some extent, but there is also a risk of excessive residual amount of heavy metal chromium ions in the fiber, which affects the ecological safety of the fiber products.

[0003] The Fenton system is a catalytic oxidation system constructed by ferrous ions and hydrogen peroxide. The system contains various free radicals such as hydroxyl radicals and can catalyze and oxidize various reactions. At present, the Fenton system is widely used in the decolorization treatment of dye wastewater and industrial waste liquid. At the same time, some studies have used Fenton reagent for pretreatment of wool fiber products. By oxidizing and destroying the disulfide bonds and scale structures in wool fibers, the anti-felting effect of wool fabrics is imparted. Moreover, the two-bath process of using Fenton reagent for wool pretreatment and then dyeing can also improve the dyeing performance of protein fiber products and enhance the color yield of acid dyes and natural dyes on wool. However, in the implementation of this method, the binding mode between the dye and the fiber macromolecule is still mainly hydrogen bonds and van der Waals forces, and the dyeing fastness of protein fiber products is still relatively poor. Summary of the Invention

[0004] [Technical Problem]

[0005] In the prior art, there are technical problems such as low color fastness and easy bacterial growth of protein fiber products.

[0006] [Technical Solution]

[0007] In view of the above technical problems, the present invention provides a method for in-situ dyeing and antibacterial finishing of protein fiber products based on the catalysis of the Fenton system; based on the fact that the Fenton system has a catalytic oxidation effect on a variety of phenolic small molecules, it can catalytically oxidize a variety of phenolic compounds including tyrosine, caffeic acid, ferulic acid, gallic acid, and syringic acid to generate phenoxyl radicals, and through the mutual polymerization of phenoxyl radicals, a colored polyphenol polymer with a larger conjugated system is formed; and there is a relatively large amount of tyrosine in protein fiber macromolecules such as silk and wool. By using the Fenton system to catalytically oxidize the phenolic hydroxyl group of tyrosine to generate radicals, and further grafting and polymerizing with exogenous phenolic small molecules (such as caffeic acid, etc.), a colored polymer can be formed on the protein fiber to achieve in-situ dyeing. Since these polyphenolic colored polymers are bound to the protein fiber by covalent bonds, they can not only improve the color depth and color fastness of the fiber products, but also have certain antibacterial effects themselves, and have potential application prospects for enhancing the antibacterial properties of protein fiber products.

[0008] That is, the present invention can catalytically oxidize phenolic small molecules and protein fibers through the Fenton system to graft and polymerize, forming colored polyphenol polymers, and improving the dyeing depth and dyeing fastness of protein fiber products; on this basis, by means of the reduction and deposition of silver nanoparticles by colored polyphenol polymers, the antibacterial properties of protein fiber products can also be enhanced.

[0009] The first object of the present invention is to provide a method for in-situ dyeing and antibacterial finishing of protein fiber products based on the catalysis of the Fenton system. The method includes: impregnating the protein fiber products with a phenolic small molecule solution to promote its diffusion inside the fiber; then adding a Fenton reagent, and using the Fenton reagent to catalytically oxidize the protein fiber to promote the graft polymerization reaction between tyrosine and phenolic small molecules in the fiber, forming a colored polyphenol polymer to achieve in-situ dyeing of the protein fiber; finally, impregnating the colored polyphenol polymer in a silver nitrate solution to reduce and deposit silver nanoparticles, and then washing and drying.

[0010] In one embodiment, the phenolic small molecules include one or more of tyrosine, caffeic acid, ferulic acid, gallic acid, and syringic acid.

[0011] In one embodiment, the concentration of the phenolic small molecule solution is 2 - 20 mmol / L.

[0012] In one embodiment, the Fenton reagent is 0.05 - 0.20 mol / L of divalent iron salt and 6 - 24 g / L of 30% hydrogen peroxide.

[0013] In one embodiment, the divalent iron salt includes ferrous sulfate and / or ferrous chloride.

[0014] In one embodiment, the protein fiber products include woven or knitted fabrics made of silk, wool, or cashmere as raw materials.

[0015] In one embodiment, the method specifically includes the following steps:

[0016] (1) Treat the protein fiber product with phenolic small molecules: Immerse the protein cellulose product in a phenolic small molecule solution to allow it to fully diffuse into the fiber interior;

[0017] Treatment process prescription and conditions: The concentration of the phenolic small molecule solution is 2 - 20 mmol / L, the liquor ratio is 1:8 - 15, the impregnation solution temperature is 30 - 50 °C, and the impregnation time is 15 - 30 min;

[0018] (2) Catalyze the in - situ chromogenesis of protein fibers with Fenton's reagent: Add Fenton's reagent to the system in step (1), and initiate free - radical polymerization through catalytic oxidation to prepare a protein fiber product containing colored polyphenol polymers;

[0019] Treatment process prescription and conditions: Fenton's reagent (ferrous salt 0.05 - 0.20 mol / L, 30% hydrogen peroxide 6 - 24 g / L), liquor ratio 1:10 - 20; temperature 30 - 50 °C, pH range 3.5 - 7, polymerization reaction time 1 - 3 h;

[0020] (3) In - situ deposit silver nanoparticles on the surface of protein fibers: Immerse the protein fiber product treated in step (2) in a silver nitrate solution for treatment, carry out reduction deposition of silver nanoparticles, and finally take out the protein fiber product, wash it with water, and dry it;

[0021] Treatment process prescription and conditions: The concentration of silver nitrate is 1 - 5 mmol / L, the liquor ratio is 1:8 - 15, the impregnation temperature is 25 - 50 °C, pH 6.5 - 7.5, and the treatment time is 3 - 6 h.

[0022] The second object of the present invention is to provide a protein fiber product obtained by finishing with the above - mentioned method.

[0023] The third object of the present invention is to provide an application of the above - mentioned protein fiber product in the preparation of functional textiles.

[0024] [Beneficial effects]

[0025] The present invention first treats the protein fiber product with phenolic small molecules to promote diffusion inside the fiber; then, with the help of Fenton's reagent to catalyze and oxidize the protein fiber, promoting graft polymerization between tyrosine in the fiber and exogenous phenolic small molecules to form colored polyphenol polymers for in - situ dyeing of protein fibers; finally, reducing and depositing silver nanoparticles through the colored polyphenol polymers to enhance the antibacterial property of the fiber product. Compared with the traditional acid - dyeing method for protein fiber products, the method described in the present invention has the following advantages:

[0026] (1) Low production energy consumption: Small phenolic molecules can first diffuse into the interior of protein fibers at a relatively low temperature. The Fenton reagent can efficiently catalyze the oxidation of tyrosine in the fibers, initiate free radical polymerization with exogenous small phenolic molecules, and form colored polyphenol polymers.

[0027] (2) High dyeing fastness: In the catalytic oxidation of the Fenton system, tyrosine radicals in protein fibers first graft with exogenous small phenolic molecules, and then further undergo free radical polymerization to form colored polyphenol polymers covalently bonded to the fibers. Therefore, the dyeing fastness of protein fiber products is relatively high.

[0028] (3) Excellent antibacterial property: The colored polyphenol polymers deposited on protein fibers have antibacterial effects and also have reducibility. They can reduce and deposit silver nanoparticles on the fiber surface, further enhancing the antibacterial property of protein fiber products. Specific implementation mode

[0029] The following further details the technical solutions of the present invention through specific examples. However, it is necessary to point out that the following examples are only used for describing the content of the invention and do not constitute a limitation to the protection scope of the present invention.

[0030] Example 1

[0031] A method for in-situ dyeing and antibacterial finishing of protein fiber products based on the catalysis of the Fenton system, comprising the following steps:

[0032] (1) Treating protein fiber products with small phenolic molecules: Immerse silk woven fabrics in a caffeic acid solution to allow it to fully diffuse into the interior of the fibers;

[0033] Treatment process prescription and conditions: Caffeic acid 2 mmol / L, liquor ratio 1:8, temperature 30 °C, treatment time 15 min;

[0034] (2) Catalyzing in-situ chromogenesis of protein fibers by the Fenton reagent: Add the Fenton reagent to the system in step (1), initiate free radical polymerization through catalytic oxidation, and prepare silk woven fabrics containing colored polyphenol polymers;

[0035] Treatment process prescription and conditions: Fenton reagent (ferrous chloride 0.05 mol / L, 30% hydrogen peroxide 6 g / L), liquor ratio 1:10, temperature 30 °C, pH 3.5, polymerization reaction 1 h;

[0036] (3) In-situ deposition of silver nanoparticles on the surface of protein fibers: Immerse the silk woven fabrics treated in step (2) in a silver nitrate solution for treatment, perform reduction deposition of silver nanoparticles, and finally take out the silk fabrics, wash with water and dry, then it is done;

[0037] Treatment process prescription and conditions: silver nitrate 1 mmol / L, liquor ratio 1:8, temperature 25 °C, pH 6.5, treatment for 3 h.

[0038] Example 2

[0039] A method for in-situ dyeing and antibacterial finishing of protein fiber products based on Fenton system catalysis, comprising the following steps:

[0040] (1) Treating protein fiber products with phenolic small molecules: impregnating wool knitted fabric in gallic acid solution to allow it to fully diffuse into the fiber interior;

[0041] Treatment process prescription and conditions: gallic acid 20 mmol / L, liquor ratio 1:15, temperature 50 °C, treatment time 30 min;

[0042] (2) Catalyzing in-situ chromogenesis of protein fibers by Fenton reagent: adding Fenton reagent to the system in step (1), and initiating free radical polymerization through catalytic oxidation to prepare wool knitted fabric containing colored polyphenol polymers;

[0043] Treatment process prescription and conditions: Fenton reagent (ferrous sulfate 0.20 mol / L, 30% hydrogen peroxide 24 g / L), liquor ratio 1:20, temperature 50 °C, pH 7, treatment time 3 h;

[0044] (3) In-situ deposition of nano-silver on the surface of protein fibers: impregnating the wool knitted fabric treated in step (2) in silver nitrate solution for treatment, performing reduction deposition of nano-silver, and finally taking out the wool fabric, washing with water and drying, then it is ready;

[0045] Treatment process prescription and conditions: silver nitrate 5 mmol / L, liquor ratio 1:15, temperature 50 °C, pH 7.5, treatment time 6 h.

[0046] Comparative Example 1

[0047] The silk woven fabric in Example 1 is not subjected to any treatment.

[0048] Comparative Example 2

[0049] The silk woven fabric in Example 1 is only treated in step (1) and not treated in steps (2) and (3).

[0050] Comparative Example 3

[0051] The silk woven fabric in Example 1 is only treated in steps (1) and (2) and not treated in step (3).

[0052] Comparative Example 4

[0053] The silk woven fabric in Example 1 is treated in step (3) and not treated in steps (1) and (2).

[0054] Comparative Example 5

[0055] Referring to the color appearance of the silk woven fabric obtained in Example 1, acid yellow and acid red dyes were used for color matching, and the silk woven fabric was dyed at 95 °C for 30 min to make the silk woven fabric sample have the same hue and dyeing depth (K / S) as Example 1.

[0056] Comparative Example 6

[0057] The wool knitted fabric in Example 2 was not subjected to any treatment.

[0058] Comparative Example 7

[0059] The wool knitted fabric in Example 2 was only treated in step (1) and not treated in steps (2) and (3).

[0060] Comparative Example 8

[0061] The wool knitted fabric in Example 2 was only treated in steps (1) and (2) and not treated in step (3).

[0062] Comparative Example 9

[0063] The wool knitted fabric in Example 2 was treated in step (3) and not treated in steps (1) and (2).

[0064] Comparative Example 10

[0065] Referring to the color appearance of the wool knitted fabric obtained in Example 2, acid yellow and acid red dyes were used for color matching, and the wool knitted fabric was dyed at 95 °C for 30 min to make the wool knitted fabric sample have the same hue and dyeing depth (K / S) as Example 2.

[0066] The fabrics obtained in Examples 1-2 and Comparative Examples 1-10 were washed in water at 40 °C for 30 min and then dried, and the following tests were carried out:

[0067] (1) The surface dyeing depth (K / S value) of the test specimen was measured using a spectrophotometric colorimeter (D65 light source, 10° field of view);

[0068] (2) Referring to GB / T 3920-2008 and GB / T 3921-2008 respectively, the washing fastness and rubbing fastness of protein fiber products were measured;

[0069] (3) Referring to GB / T 20944.3-2008, the antibacterial rate of protein fiber products against Escherichia coli was measured; The above test results are shown in Table 1.

[0070] Table 1 Performance indexes of different fabrics

[0071]

[0072] As can be seen from Table 1:

[0073] a. The protein fiber products (Example 1, Example 2) obtained by the method of the present invention have a relatively high dyeing depth (K / S value), indicating that the Fenton system catalyzes the graft polymerization of phenolic small molecules with the fiber to generate more colored polyphenol polymers; the grades of washing fastness and rubbing fastness are both relatively high, verifying that the colored polymers are combined with the fiber macromolecules through covalent bonds; in addition, the antibacterial rates of the silk and wool fabric samples are both greater than 99%, indicating that the colored polyphenol polymers can promote the reduction and deposition of silver nanoparticles and improve the antibacterial property of the protein fiber products.

[0074] b. The samples without any treatment (Comparative Example 1, Comparative Example 6) maintained the natural color of the natural protein fiber, and the surface color depth of the fiber products was relatively light; since the fiber was not dyed, the measured color fastness results were all Grade 5; the samples had no antibacterial effect.

[0075] c. The samples (Comparative Example 2, Comparative Example 7) only treated with step (1) and not treated with steps (2) and (3) had a relatively light color on the surface of the samples, which was similar to the samples without any treatment, indicating that phenolic small molecules did not polymerize at a lower temperature and it was difficult to form colored polyphenol polymers with a larger conjugated system, so the K / S of the fabric was lower; the dyeing fastness was also similar to that of the untreated samples; due to the lack of polyphenol polymers on the fiber surface and the insignificant antibacterial effect of a small amount of adsorbed phenolic small molecules, the antibacterial rate of the samples against Escherichia coli was relatively low.

[0076] d. The samples (Comparative Example 3, Comparative Example 8) only treated with steps (1) and (2) and not treated with step (3) had a color depth on the surface of the samples that was similar to that of Example 1 and Example 2 respectively, verifying that colored polyphenol polymers were formed by graft polymerization on the fiber, and the washing and rubbing fastness were also good; in addition, the colored polyphenol polymers on the protein fiber made the samples have a certain antibacterial effect against Escherichia coli (antibacterial rate > 70%), reaching the standard value of the antibacterial effect mentioned in the test standard, but there was still a large gap in the antibacterial rate between the samples and Example 1 and Example 2.

[0077] e. The samples (Comparative Example 4, Comparative Example 9) only treated with step (3) and not treated with steps (1) and (2) had a relatively light color depth on the fiber surface due to the lack of reduction and deposition of silver nanoparticles caused by colored polyphenol polymers. The K / S value and dyeing color fastness were similar to those of the untreated samples respectively, and the antibacterial rate did not reach the value with antibacterial effect mentioned in the test standard.

[0078] f. Referring to the color appearance of the protein fiber products obtained in Example 1 and Example 2, the samples dyed with a mixture of acid yellow and acid red dyes (Comparative Example 5 and Comparative Example 10) have a similar dyeing depth to the former, but the color fastness is poor. This is because acid dyes can only bind to the fiber through hydrogen bonds, van der Waals forces and ionic bonds, and cannot form covalent bonds. Therefore, although the color depth is similar, the color fastness is poor, and the reference standard sample has no antibacterial effect.

[0079] It can be seen from this that the protein fiber products of Example 1 and Example 2 treated by the method of the present invention not only have a high dyeing depth, but also have excellent color fastness; the colored polyphenol polymer formed on the fiber not only has a certain antibacterial effect, but also can promote the reduction and deposition of silver nanoparticles, significantly improving the antibacterial property of the protein fiber products.

[0080] Although the present invention has been disclosed above with preferred embodiments, it is not intended to limit the present invention. Anyone familiar with this technology can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the protection scope of the present invention should be defined by the claims.

Claims

1. A method for in-situ dyeing and antibacterial finishing of protein fiber products based on Fenton system catalysis, characterized in that, The method includes: impregnating a protein fiber product with a phenolic small molecule solution to promote its diffusion inside the fiber; then adding a Fenton's reagent, and by means of the catalytic oxidation of the Fenton's reagent on the protein fiber, promoting the graft polymerization reaction between tyrosine and phenolic small molecules in the fiber to form a colored polyphenol polymer, so as to achieve in-situ dyeing of the protein fiber; finally, impregnating the colored polyphenol polymer in a silver nitrate solution to reduce and deposit nano-silver, followed by washing with water and drying, then it is completed; The protein fiber product includes a woven fabric or a knitted fabric made of silk, wool or cashmere as raw materials; The bath ratio of the protein fiber product to the phenolic small molecule solution is 1:8 - 15.

2. The method according to claim 1, wherein The phenolic small molecules include one or more of tyrosine, caffeic acid, ferulic acid, gallic acid and syringic acid.

3. The method according to claim 1, characterized in that, The concentration of the phenolic small molecule solution is 2 - 20 mmol / L.

4. The method according to claim 1, characterized in that, The Fenton's reagent is ferrous salt at 0.05 - 0.20 mol / L and 30% hydrogen peroxide at 6 - 24 g / L.

5. The method according to claim 4, wherein The ferrous salt includes ferrous sulfate and / or ferrous chloride.

6. The method according to claim 1, wherein The method specifically includes the following steps: (1) Treating the protein fiber product with phenolic small molecules: impregnating the protein fiber product in the phenolic small molecule solution to enable it to fully diffuse into the fiber interior; Treatment process prescription and conditions: the concentration of the phenolic small molecule solution is 2 - 20 mmol / L, the bath ratio is 1:8 - 15, the impregnation solution temperature is 30 - 50 °C, and the impregnation time is 15 - 30 min; (2) Catalytic in-situ chromogenesis of the protein fiber by the Fenton's reagent: adding the Fenton's reagent to the system in step (1), and initiating free radical polymerization through catalytic oxidation to prepare a protein fiber product containing a colored polyphenol polymer; Treatment process prescription and conditions: the Fenton's reagent, the bath ratio is 1:10 - 20, the temperature is 30 - 50 °C, the pH range is 3.5 - 7, and the polymerization reaction time is 1 - 3 h; the Fenton's reagent is ferrous salt at 0.05 - 0.20 mol / L and 30% hydrogen peroxide at 6 - 24 g / L; (3) In-situ deposition of nano-silver on the surface of the protein fiber: impregnating the protein fiber product treated in step (2) in a silver nitrate solution for treatment to carry out reduction and deposition of nano-silver, and finally taking out the protein fiber product, washing with water and drying it; Treatment process prescription and conditions: the concentration of silver nitrate is 1 - 5 mmol / L, the bath ratio is 1:8 - 15, the impregnation temperature is 25 - 50 °C, the pH is 6.5 - 7.5, and the treatment time is 3 - 6 h.

7. A protein fiber product obtained by the method according to any one of claims 1 - 6.

8. Use of the protein fiber product according to claim 7 in the preparation of functional textiles.

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