Apocynum venetum fiber biological dyeing method based on laccase catalytic polymerization reaction

Abstract

The invention discloses an apocynum venetum fiber biological dyeing method based on laccase catalytic polymerization reaction, which comprises the following steps: S1, preparing a template acid agent solution: adding a template into the acid agent solution, and fully stirring to dissolve the template to obtain the template acid agent solution; s2, pretreatment of apocynum venetum fibers by a template method: soaking the apocynum venetum fibers in a template acid solution, taking out the apocynum venetum fibers after 24 hours, baking for a period of time, and airing at room temperature; step S3, dyeing the apocynum venetum fiber: dissolving a phenolic monomer and a biological enzyme in a buffer solution to obtain a natural polymer dye solution, and then adding the apocynum venetum fiber pretreated by the template method in the step S2 into the natural polymer dye solution for dyeing to obtain the apocynum venetum fiber dyed by the natural polymer dye. According to the method for dyeing the apocynum venetum fibers, the natural phenol monomers are catalyzed by the biological enzyme to polymerize to generate the colored polymer, and the apocynum venetum fibers have the characteristics of high dye uptake, high color fastness, high efficiency, environmental friendliness and the like after being dyed.

Description

Technical Field

[0001] The invention relates to the technical field of cleaning dyeing and finishing, and in particular to a biological dyeing method for apocynum fiber based on laccase-catalyzed polymerization reaction. Background Art

[0002] Apocynum ramie is a characteristic plant resource in Xinjiang. It is a natural functional fiber with antibacterial, far-infrared radiation effect, medical and health care functions, good hygroscopicity, breathable and warm, antistatic, soft and comfortable, and is particularly suitable for summer clothing and thermal underwear fabrics. Synthetic dyes such as reactive dyes and acid dyes are mostly used in the dyeing process of apocynum ramie fiber. Traditional synthetic dyes are cheap, have a complete color spectrum, bright colors, and high fastness, but many synthetic dyes are environmentally toxic and threaten human health. Compared with synthetic dyes, natural dyes are widely present in nature and can be extracted from plants, animals, microorganisms, minerals and some other materials. Most natural dyes have poor affinity and directness to fibers, which makes the fiber dyeing rate and dyeing fastness not high. In order to improve the dyeing performance of natural dyes, cationic modifiers or different metal ion mordants are generally used to improve the dyeing rate of dyes, but the dye wastewater generated has a large environmental pollution and does not conform to the concept of ecological dyeing and finishing.

[0003] With the development of ecological dyeing and finishing technology, the use of enzyme-catalyzed synthesis of colored polymer dyes for fiber or textile dyeing has become a research hotspot. Treating textiles with enzymes and giving them a certain color can solve the serious environmental pollution caused by synthetic dyes during industrial production and dyeing, thereby achieving clean dyeing of textiles. Natural phenolic monomers are suitable substrates for enzyme catalysis, which can catalyze phenolic monomers to generate colored polymers and attach them to fibers for in-situ dyeing. As people choose a healthier lifestyle, natural polyphenols are becoming more and more popular. Natural polyphenols are a kind of bioactive substance and secondary metabolite, which is widely found in plant sources such as fruits and vegetables, and has antioxidant, antibacterial, anti-inflammatory and anti-cancer effects. However, due to the low affinity between cellulose fibers and colored polymers generated by enzyme-catalyzed natural phenolic monomers, templates are used to promote the degree of polymerization of enzyme-catalyzed colored polymers or the degree of adsorption of colored polymers by fibers.

[0004] The use of synthetic dyes for dyeing in the textile industry produces highly polluted wastewater, causing serious environmental problems and prompting people to look for dyes and dyeing methods that are acceptable to the environment. Enzyme-catalyzed polymerization dyeing is a new type of energy-saving and environmentally friendly biological dyeing technology, which has received widespread attention in the field of polymer chemistry. The use of enzymatic dyeing technology, due to its high efficiency, environmental protection, and mild treatment conditions, provides an efficient and environmentally friendly alternative to traditional textile dyeing. Apocynum ramie is a cellulose fiber that contains a large number of hydroxyl groups and has a negative charge on the surface. Enzymatically polymerized natural phenolic monomers lack affinity for it and can only bind to dyes through hydrogen bonds and intermolecular forces, resulting in low dyeing fastness. Therefore, Apocynum ramie fibers are pretreated with a template agent to increase active groups, or a template agent is used to promote the degree of polymerization of enzyme-catalyzed colored polymers, so as to facilitate the dyeing of enzymatic phenolic polymers. Summary of the invention

[0005] The present invention provides a biological dyeing method for apocynum fiber based on laccase-catalyzed polymerization reaction, so as to solve the problems raised in the above-mentioned background technology.

[0006] In order to achieve the above object, the present invention adopts the following technical solutions: A method for biological dyeing of apocynum venetum fiber based on laccase-catalyzed polymerization reaction comprises the following steps: Step S1, preparing a template acid solution: adding the template into the acid solution, stirring sufficiently to dissolve the template, and obtaining the template acid solution; Step S2, pre-treating the apocynum venetum fiber by template method: immersing the apocynum venetum fiber in a template acid solution, taking it out after 24 hours, baking it for a period of time and then drying it at room temperature; Step S3, dyeing of apocynum fiber: dissolving phenolic monomers and biological enzymes in a buffer solution to obtain a natural polymer dye solution, and then adding the apocynum fiber pretreated by the template method in step S2 into the natural polymer dye solution for dyeing to obtain apocynum fiber dyed with a natural polymer dye.

[0007] As a further improvement of the technical solution: the template includes one or more of chitosan, chitosan oligosaccharide, polyethylene glycol, polyvinyl alcohol, gelatin, sulfonated polystyrene, polyethylene glycol monododecyl ether, and sodium polystyrene sulfonate.

[0008] As a further improvement of the technical solution: the acid agent includes one or more of acetic acid, phosphoric acid, carbonic acid, hydrochloric acid, oxalic acid (oxalic acid), carbonic acid, citric acid, malic acid, gluconic acid, formic acid, lactic acid, benzoic acid, propionic acid, and stearic acid.

[0009] As a further improvement of the technical solution: the phenolic monomers include one or more of syringic acid, vanillic acid, gallic acid, tea polyphenols, caffeic acid, guaiacol, vanillin, catechol, syringaldehyde, ferulic acid, acetosyringone, homovanillyl alcohol, p-coumaric acid, vanillin syringaldehyde, vanillyl acetone, salicylic acid, tyramine, anthocyanin, and curcumin.

[0010] As a further improvement of the technical solution: the biological enzyme includes one or more of laccase, horseradish peroxidase, tyrosinase, hemicellulase, xylanase and pectinase.

[0011] As a further improvement of the present technical solution: the described ramie belongs to cellulose fiber, and other cellulose fibers include ramie, flax, ramie, jute, hemp, cotton, bamboo fiber, Tencel, Modal, soybean fiber, cuprammonia fiber, cotton / flax, cotton / hemp, cotton / ramie, cotton / Tencel, cotton / viscose, cotton / bamboo, cotton / Modal, flax / viscose, jute / viscose, one or more thereof.

[0012] As a further improvement of the technical solution: the color fastness of the cellulose fiber dyed with the template-based polyphenol natural dye is 4-5, and the K / S value is 10-30.

[0013] As a further improvement of the technical solution: in step S3, the dyeing bath ratio of the apocynum fiber after template pretreatment and the natural polymer dye solution is 1:10 to 1:200, the dye weight to fabric (owf) is 1% to 20%, the concentration of the biological enzyme is 1g / L to 20g / L, the pH of the dye bath after adding the acidifier is 1 to 8, the dyeing temperature is 20°C to 80°C, and the dyeing time is 10min to 600min.

[0014] Compared with the prior art, the present invention has the following beneficial effects: In view of the problems of low dye uptake, poor color fastness, and environmental pollution caused by heavy metal mordant wastewater in traditional natural dye dyeing, the present invention designs a cellulose fiber dyeing method based on template enzymatic natural polyphenol dyes. Compared with the traditional natural dye mordant dyeing method, the cellulose fiber dyeing method of the present invention, which uses biological enzymes to catalyze the polymerization of polyphenol natural dyes to generate colored polymers, has the characteristics of high dye uptake, high color fastness, green environmental protection, etc. after dyeing.

[0015] The above description is only an overview of the technical solution of the present invention. In order to more clearly understand the technical means of the present invention and implement it according to the contents of the specification, the following is a detailed description of the preferred embodiments of the present invention in conjunction with the accompanying drawings. The specific implementation of the present invention is given in detail by the following embodiments and their accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] The drawings described herein are used to provide a further understanding of the present invention and constitute a part of this application. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention. In the drawings: Figure 1 A schematic diagram of the steps of a biological dyeing method for apocynum venetum fiber based on laccase-catalyzed polymerization reaction proposed by the present invention; Figure 2 The antibacterial properties of Apocynum venetum fiber against Escherichia coli; Figure 3 The antibacterial properties of rhubarb fiber against Staphylococcus aureus. DETAILED DESCRIPTION

[0017] The principles and features of the present invention are described below in conjunction with the accompanying drawings. The examples given are only used to explain the present invention and are not used to limit the scope of the present invention. The present invention is described in more detail by way of example with reference to the accompanying drawings in the following paragraphs. It should be noted that the accompanying drawings are all in a very simplified form and are not in precise proportions, and are only used to facilitate and clearly assist in explaining the purpose of the embodiments of the present invention.

[0018] Test method: (1) K / S value: The K / S value of the dyed sample was measured using a computer colorimeter. The average value was taken after 3 measurements, and the maximum K / S value in the range of 360-750nm was read under D65 light source and 10° standard viewing angle.

[0019] (2) Fabric color fastness test: Refer to GB / T 3921-2008 "Textiles. Color fastness test. Color fastness to washing with soap" to test the color fastness of the sample to washing with soap.

[0020] Refer to GB / T 3920-2008 "Textiles. Tests for colour fastness. Colour fastness to rubbing" to test the colour fastness of the samples.

[0021] Refer to GB / T 8427-2019 "Textiles - Tests for colour fastness - Colour fastness to artificial light: Xenon arc fading lamp" to test the colour fastness of the test samples to sunlight.

[0022] Refer to GB / T 3922-2013 “Test method for colour fastness of textiles to perspiration” for colour fastness test to perspiration.

[0023] (3) Fabric antibacterial performance test: The test was conducted in accordance with the antibacterial performance test of GB / T 20944.3-2008 “Evaluation of antibacterial properties of textiles - Part 3: Oscillation method”.

[0024] (4) Fabric UV resistance test: The anti-ultraviolet performance test is carried out in accordance with GB / T18830-2009 "Evaluation of the Anti-ultraviolet Performance of Textiles".

[0025] The anti-ultraviolet performance of the fabric is tested by the textile anti-ultraviolet performance tester YG (B) 912E.

[0026] Example 1 A method for dyeing apocynum fiber with an enzymatic natural phenolic monomer comprises the following steps: Add 0.21g chitosan to 30mL diluted acetic acid solution, stir thoroughly to dissolve chitosan, and obtain chitosan acetic acid solution; immerse 0.3g apocynum fiber in chitosan acetic acid solution, take out after 24h, bake at 120℃ for 5min, and then dry at room temperature; add 6mg syringic acid to 30mL acetic acid-sodium acetate (pH=5) buffer, add 0.18g laccase, stir evenly, and obtain dye solution; put the treated apocynum fiber into the dye solution for dyeing, keep warm at 50℃ for 7h, wash with water, and dry.

[0027] The color depth (K / S) and color fastness of the apocynum ramie fiber dyed by laccase-catalyzed syringic acid polymerization chromogenic template method were tested. The K / S of the dyed apocynum ramie fiber was 28.37, which had a high color depth.

[0028] Example 2 A method for dyeing apocynum fiber with an enzymatic natural phenolic monomer comprises the following steps: 0.21g chitosan was added to 30mL diluted acetic acid solution, and the chitosan was dissolved by stirring, and chitosan acetic acid solution was obtained; 0.3g apocynum fiber was immersed in the chitosan acetic acid solution, and taken out after 24h, baked at 120℃ for 5min, and then dried at room temperature; 18mg syringic acid was added to 30mL acetic acid-sodium acetate (pH=5) buffer, and 0.48g laccase was added, and stirred evenly to obtain dye solution; the treated apocynum fiber was placed in the dye solution for dyeing, and kept warm at 50℃ for 7h. After dyeing, it was washed with water and dried.

[0029] The color depth (K / S) and color fastness of the apocynum ramie fiber dyed by laccase-catalyzed syringic acid polymerization chromogenic template method were tested. The K / S of the dyed apocynum ramie fiber was 29.55, which had a high color depth.

[0030] Example 3 A method for dyeing apocynum fiber with an enzymatic natural phenolic monomer comprises the following steps: 0.21g chitosan was added to 30mL diluted acetic acid solution, and the chitosan was dissolved by stirring, and chitosan acetic acid solution was obtained; 0.3g apocynum fiber was immersed in the chitosan acetic acid solution, and taken out after 24h, baked at 120℃ for 5min, and then dried at room temperature; 6mg syringic acid was added to 30mL acetic acid-sodium acetate (pH=4) buffer, and 0.18g laccase was added, and stirred evenly to obtain dye solution; the treated apocynum fiber was placed in the dye solution for dyeing, and kept warm at 50℃ for 7h. After dyeing, it was washed with water and dried.

[0031] The color depth (K / S) and color fastness of the apocynum ramie fiber dyed by laccase-catalyzed syringic acid polymerization chromogenic template method were tested. The K / S of the dyed apocynum ramie fiber was 22.06, which had a high color depth.

[0032] Example 4 A method for dyeing apocynum fiber with an enzymatic natural phenolic monomer comprises the following steps: 0.21g chitosan was added to 30mL diluted acetic acid solution, and the chitosan was dissolved by stirring to obtain chitosan acetic acid solution; 0.3g apocynum fiber was immersed in the chitosan acetic acid solution, taken out after 24h, baked at 120℃ for 5min, and then dried at room temperature; 6mg syringic acid was added to 30mL acetic acid-sodium acetate (pH=5) buffer, and then 0.18g laccase was added and stirred to obtain dye solution; the treated apocynum fiber was placed in the dye solution for dyeing, and kept warm at 30℃ for 7h. After dyeing, it was washed with water and dried.

[0033] The color depth (K / S) and color fastness of the apocynum ramie fiber dyed by laccase-catalyzed syringic acid polymerization chromogenic template method were tested. The K / S of the dyed apocynum ramie fiber was 18.46, which had a high color depth.

[0034] Example 5 A method for dyeing apocynum fiber with an enzymatic natural phenolic monomer comprises the following steps: Add 0.21g chitosan to 30mL diluted acetic acid solution, stir thoroughly to dissolve chitosan, and obtain chitosan acetic acid solution; immerse 0.3g apocynum fiber in chitosan acetic acid solution, take out after 24h, bake at 120℃ for 5min, and then dry at room temperature; add 6mg syringic acid to 30mL acetic acid-sodium acetate (pH=5) buffer, add 0.18g laccase, stir evenly, and obtain dye solution; put the treated apocynum fiber into the dye solution for dyeing, keep warm at 50℃ for 3h. After dyeing, wash with water and dry.

[0035] The color depth (K / S) and color fastness of the apocynum ramie fiber dyed by laccase-catalyzed syringic acid polymerization chromogenic template method were tested. The K / S of the dyed apocynum ramie fiber was 19.68, which had a high color depth.

[0036] Comparative Example 1 A method for dyeing apocynum fiber with an enzymatic natural phenolic monomer comprises the following steps: 0.21g chitosan was added to 30mL diluted acetic acid solution, and the chitosan was dissolved by stirring to obtain chitosan acetic acid solution; 0.3g apocynum fiber was immersed in the chitosan acetic acid solution, taken out after 24h, baked at 120℃ for 5min, and then dried at room temperature; 6mg syringic acid was added to 30mL acetic acid-sodium acetate (pH=5) buffer, and stirred evenly to obtain dye solution; the treated apocynum fiber fabric was placed in the dye solution for dyeing, and kept warm at 50℃ for 7h. After dyeing, it was washed with water and dried.

[0037] The color depth (K / S) and color fastness of the apocynum venetum fiber dyed by the laccase-catalyzed polymerization of syringic acid were tested, and the K / S of the dyed apocynum venetum fiber was 3.52. Compared with Example 1, Control Example 1 had a poorer dyeing depth. The reason is that without the catalytic action of biological enzymes, the color of syringic acid is close to colorless; while syringic acid generates colored polymers under the catalysis of laccase and adsorbs on the fiber, making the fiber darker in color and having higher color fastness.

[0038] Comparative Example 2 A method for dyeing apocynum fiber with an enzymatic natural phenolic monomer comprises the following steps: 0.21g chitosan was added to 30mL diluted acetic acid solution, and the chitosan was dissolved by stirring, and chitosan acetic acid solution was obtained; 0.3g apocynum fiber was immersed in the chitosan acetic acid solution, and taken out after 24 hours, baked at 120℃ for 5 minutes, and then dried at room temperature; 6mg syringic acid was added to 30mL water, and then 0.18g laccase was added, and stirred evenly to obtain dye solution; the treated apocynum fiber was placed in the dye solution for dyeing, and kept warm at 50℃ for 7 hours. After dyeing, it was washed with water and dried.

[0039] The color depth (K / S) and color fastness of the apocynum venetum fiber dyed by the laccase-catalyzed syringic acid polymerization color template method were tested, and the K / S of the dyed apocynum venetum fiber was 16.64. Compared with Example 1, Control Example 2 had a poorer dyeing depth. The reason is that laccase is more stable under acidic conditions, the activity of laccase is reduced in water, the degree of polymerization of syringic acid catalyzed by laccase is low, the fiber color is lighter, and the color fastness is poor.

[0040] Comparative Example 3 A method for dyeing apocynum fiber with an enzymatic natural phenolic monomer comprises the following steps: 6 mg of syringic acid was added to 30 mL of acetic acid-sodium acetate (pH=5) buffer, and then 0.18 g of laccase was added and stirred evenly to obtain a dye solution; 0.3 g of apocynum fiber was put into the dye solution for dyeing, and the dyeing was kept warm at 50°C for 7 hours. After dyeing, the fiber was washed with water and dried.

[0041] The color depth (K / S) and color fastness of the apocynum ramie fiber dyed by the laccase-catalyzed syringic acid polymerization color template method were tested, and the K / S of the dyed apocynum ramie fiber was 4.67. Compared with Example 1, Control Example 2 had a poorer dyeing depth. The reason is that the apocynum ramie fiber has a low affinity with the colored polymer generated by the lacquer-catalyzed polyphenol compound; the template method is used to deposit chitosan on the fiber surface, improve the fiber's adsorption performance of the dye, and obtain a darker color.

[0042] Table 1 L*, a*, b* values ​​of syringic acid on apocynum venetum fiber after dyeing with different methods Case Staining method L* a* b* color Example 1 Template-based enzyme staining 59.67 12.83 8.06 Dark purple Comparative Example 1 Laccase-free 86.35 2.98 -8.65 Light beige Comparative Example 2 The solvent is water 69.45 9.57 6.3 Dark purple Comparative Example 3 No template 83.50 3.23 -6.99 Light beige Table 2 Color fastness test results Case Soap-resistant Dry friction resistance Resistant to wet friction Sun resistant Acid sweat resistance Alkaline sweat resistance Example 1 4-5 5 4-5 6-7 4-5 3-4 Example 2 4-5 4-5 4 6 4-5 3-4 Example 3 4 4-5 4 6 4-5 3 Example 4 4-5 4-5 4-5 5-6 4-5 3-4 Example 5 4 4 3-4 5-6 4 3-4 Comparative Example 1 4-5 4-5 4 6 4-5 3-4 Comparative Example 2 4 4-5 4 5-6 4-5 4 Comparative Example 3 4 4 3-4 6 4-5 3-4 Table 3 Anti-ultraviolet properties of apocynum fiber Case UPF UVA% UVB% Example 1 90.36 1.68 1.9 Example 2 98.40 1.32 1.38 Example 3 81.89 1.86 1.99 Example 4 70.9 2.28 2.40 Example 5 74.57 1.88 2.09 Comparative Example 1 10.93 7.36 8.97 Comparative Example 2 73.78 2.35 2.33 Comparative Example 3 14.28 6.70 7.01 The apocynum ramie fiber prepared by the embodiment of the present invention presents dark purple, and the dyed apocynum ramie fiber has high color depth and good color fastness, and has good antibacterial and anti-ultraviolet properties.

[0043] Although the present invention has been disclosed as above in the form of a preferred embodiment, 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 scope of protection of the present invention should be based on the definition of the claims.

Claims

1. A biological dyeing method for apocynum venetum fiber based on laccase-catalyzed polymerization reaction, It is characterized in that The steps include: Step S1, preparing a template acid solution: adding the template into the acid solution, stirring sufficiently to dissolve the template, and obtaining the template acid solution; Step S2, pre-treating the apocynum venetum fiber by template method: immersing the apocynum venetum fiber in a template acid solution, taking it out after 24 hours, baking it for a period of time and then drying it at room temperature; Step S3, dyeing of apocynum fiber: dissolving phenolic monomers and biological enzymes in a buffer solution to obtain a natural polymer dye solution, and then adding the apocynum fiber pretreated by the template method in step S2 into the natural polymer dye solution for dyeing to obtain apocynum fiber dyed with a natural polymer dye.

2. A method for biological dyeing of apocynum venetum fiber based on laccase-catalyzed polymerization according to claim 1, It is characterized in that The template comprises one or more of chitosan, chitosan oligosaccharide, polyethylene glycol, polyvinyl alcohol, gelatin, sulfonated polystyrene, polyethylene glycol monododecyl ether, and sodium polystyrene sulfonate.

3. The method for biological dyeing of apocynum venetum fiber based on laccase-catalyzed polymerization according to claim 1, It is characterized in that The acid agent includes one or more of acetic acid, phosphoric acid, carbonic acid, hydrochloric acid, oxalic acid, carbonic acid, citric acid, malic acid, gluconic acid, formic acid, lactic acid, benzoic acid, propionic acid, and stearic acid.

4. The method for biological dyeing of apocynum venetum fiber based on laccase-catalyzed polymerization reaction according to claim 1, It is characterized in that The phenolic monomers include one or more of syringic acid, vanillic acid, gallic acid, tea polyphenols, caffeic acid, guaiacol, vanillin, catechol, syringaldehyde, ferulic acid, acetosyringone, homovanillyl alcohol, p-coumaric acid, vanillin syringaldehyde, vanillyl acetone, salicylic acid, tyramine, anthocyanin, and curcumin.

5. The method for biological dyeing of apocynum venetum fiber based on laccase-catalyzed polymerization according to claim 1, It is characterized in that The biological enzyme includes one or more of laccase, horseradish peroxidase, tyrosinase, hemicellulase, xylanase and pectinase.

6. The method for biological dyeing of apocynum venetum fiber based on laccase-catalyzed polymerization reaction according to claim 1, It is characterized in that The described apocynum belongs to cellulose fiber, and other cellulose fibers include apocynum, flax, ramie, jute, hemp, cotton, bamboo fiber, Tencel, Modal, soybean fiber, cuprammonia fiber, cotton / flax, cotton / hemp, cotton / apocynum, cotton / Tencel, cotton / viscose, cotton / bamboo, cotton / Modal, flax / viscose, jute / viscose.

7. The method for biological dyeing of apocynum venetum fiber based on laccase-catalyzed polymerization according to claim 1, It is characterized in that The color fastness of the cellulose fiber dyed with the template-based polyphenol natural dye is 4-5, and the K / S value is 10-30.

8. The method for biological dyeing of apocynum venetum fiber based on laccase-catalyzed polymerization according to claim 1, It is characterized in that In step S3, the dyeing bath ratio of the apocynum fiber after template pretreatment and the natural polymer dye solution is 1:10-1:200, the dye weight to fabric is 1%-20%, the concentration of the biological enzyme is 1g / L-20g / L, the pH of the dye bath after adding the acidifier is 1-8, the dyeing temperature is 20°C-80°C, and the dyeing time is 10min-600min.

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