CN112647317B

CN112647317B - Biological enzymatic dyeing method for improving strength of wool fibers

Info

Publication number: CN112647317B
Application number: CN202011510926.7A
Authority: CN
Inventors: 苏静; 王鸿博; 李洁; 李宇; 李楠楠
Original assignee: Jiangnan University
Current assignee: Jiangnan University
Priority date: 2020-12-18
Filing date: 2020-12-18
Publication date: 2021-12-28
Anticipated expiration: 2040-12-18
Also published as: CN112647317A; WO2022127940A1; US20220356643A1

Abstract

The invention discloses a biological enzymatic dyeing method for improving the strength of wool fibers, and belongs to the technical field of textile material modification. The method utilizes the characteristic that protein fiber macromolecules contain a large number of active groups such as hydroxyl, amino, carboxyl and the like, and are easy to react with polyphenol pigments formed by enzyme catalysis phenolic compounds to form covalent bonding, so that the low-temperature dyeing of wool fibers is realized, and the fiber strength is improved. The method has mild operation condition and easy control, and the biological enzyme is utilized to dye wool fibers safely, environment-friendly and efficiently at present with increasing emphasis on environmental protection, thereby having long-term development prospect.

Description

Biological enzymatic dyeing method for improving strength of wool fibers

Technical Field

The invention relates to a biological enzymatic dyeing method for improving the strength of wool fibers, belonging to the textile material modification technology.

Background

Protein fiber such as wool fiber has excellent hygroscopicity and heat retention, is soft to wear, and is widely applied in textile industry. In the processing process, such as wool scouring, spinning, weaving, dyeing and the like, fibers are damaged, the mechanical property is deteriorated, and the wool surface scale layer has hydrophobicity, so that the dyeing is carried out by a high-temperature process, so that strong damage is caused, the subsequent processing of the fibers and the wearability of fabrics are seriously influenced, the energy consumption is high, and the environment is unfavorable. Therefore, the important significance is achieved by finding a mild and effective dyeing method for preventing and repairing wool fiber damage.

In the prior art, the reports on the repair of the strong damage of the wool fibers are less, and chemical cross-linking agents such as glyoxal, glutaraldehyde, dioctyl ester, carbodiimide and the like are reported to be used, and the cross-linking agents are cheap and are easy to improve the tensile property of the fibers, but have great threats to the environment and the health of users. Currently, studies on the repair of wool damage by Transglutaminase (TG) have been widely conducted, and TG has the ability to absorb primary amines and graft peptide chains (containing glutamine or lysine residues) onto proteins, and can repair multiple damages such as chemical damage and biological damage of wool, but has a single use.

The protein fiber dyeing mainly takes acid dye and reactive dye as main materials, and the dyeing is carried out through physical or chemical combination with the fiber. However, with the worldwide energy exhaustion and the increasing deterioration of environmental problems, the development of synthetic dyes and printing and dyeing industry faces many problems such as environmental pollution and high labor cost, and the search for novel eco-friendly dyes becomes a new development direction.

Disclosure of Invention

The technical problem to be solved is as follows:

the method for dyeing and improving the strength of the wool fiber by the biological enzymatic method comprises the steps of pretreating the wool yarn by a physical or chemical method, dyeing the pretreated wool yarn in a laccase-phenol compound reaction system, wherein protein fiber macromolecules contain a large amount of active groups such as hydroxyl, amino, carboxyl and the like, and the protein fiber macromolecules are easy to react with colored enzymatic phenol polymerization products to form covalent bonding, so that the wool fiber is dyed at low temperature, the fiber is endowed with good dyeing performance and mechanical performance, the reaction condition is mild, and the method is easy to control, green and environment-friendly and has wide development prospect.

The invention uses natural animal and plant dyes to replace chemical dyes. Laccases are copper-containing oxidoreductases found in many plants, fungi and microorganisms. In textile processing, laccase is used for improving whiteness of fabrics, decoloration of colored wastewater, refining of fibers, wool anti-felting and the like in a bleaching process, but reports for improving and enhancing wool fiber strength do not exist.

The technical scheme is as follows:

the first object of the present invention is to provide a method for bio-enzymatic enhancing strength and dyeing of wool fibers, which comprises the following steps: adding laccase-phenolic compounds into a buffer solution, and dyeing wool fibers in a reaction system containing the laccase-phenolic compounds.

In one embodiment of the present invention, the phenolic compound is catechol, hydroquinone, gallic acid, vanillin, guaiacol, or the like.

In one embodiment of the present invention, the wool fibers are pretreated before the enzyme catalyzes the reaction of the phenolic compound with the wool: the pretreatment comprises a chemical method, an enzymatic method or a physical method.

In one embodiment of the invention, the pretreatment may be performed with sodium carbonate, and the treatment process recipe and conditions are as follows: weighing wool fibers and sodium carbonate, dissolving the sodium carbonate in deionized water to prepare a 0.5-1g/L sodium carbonate solution, wherein the bath ratio is 1: 20-1: 50. soaking wool fiber in 30-80 deg.C sodium carbonate solution for 15-30min, washing with 40 deg.C anhydrous ethanol for 5-15min, rinsing with deionized water for several times, and oven drying at 40-60 deg.C.

In one embodiment of the present invention, the pretreatment may be performed by using low temperature plasma, and the treatment process recipe and conditions are as follows: placing the wool fibers on a frame in a low-temperature plasma treatment machine, starting a vacuum pump, introducing a path of oxygen, and performing low-temperature plasma treatment on the wool fibers in an automatic click mode, wherein the treatment power is 100-.

In one embodiment of the present invention, the method for bio-enzymatic dyeing and enhancing strength of wool fibers comprises: sequentially adding the biological catalyst laccase and the phenolic compound into the buffer solution to prepare a reaction system with the pH value of 4.0-6.0, adding the pretreated wool fibers into the reaction system, and reacting for 2-10 hours at the temperature of 30-80 ℃.

In one embodiment of the invention, the buffer solution is an acetic acid-sodium acetate buffer.

In one embodiment of the invention, the concentration of the acetic acid-sodium acetate buffer solution is 0.1 to 0.3 mol/L.

In one embodiment of the invention, the process recipe and conditions for bio-enzymatic dyeing and wool fiber strength improvement are as follows: preparing acetic acid-sodium acetate buffer solution with pH of 4.0-6.0, sequentially adding a catalyst laccase and a substrate into the buffer solution to ensure that the concentration of the laccase is 25-125U/mL and the concentration of the phenolic compound is 0.04-0.20mol/L, adding the pretreated wool fibers into a reaction system, wherein the bath ratio is 1: 20-1: 50, heating to 30-80 ℃, and reacting for 2-10 hours in a heat preservation way.

In one embodiment of the invention, the laccase is used in an amount of (25-125U) U/(0.04-0.20) mmol of phenolic compounds.

The second purpose of the invention is to provide a protein fiber prepared by the method.

In one embodiment of the invention, the protein fiber is wool.

It is a third object of the present invention to provide a yarn, thread and fabric comprising the above wool.

Has the advantages that:

according to the invention, a biocatalyst, namely laccase, is used for catalyzing and oxidizing the phenolic compound to generate a colored polymerization product, protein fiber macromolecules contain a large number of active groups such as hydroxyl, amino, carboxyl and the like, and the active groups are easy to react with the enzymatic phenolic colored polymerization product to form covalent bonding, so that wool fiber dyeing is realized, wool is endowed with good dyeing performance, the strength of the dyed wool is obviously improved, the alkali resistance is improved, and the oxidation resistance is realized. The reaction condition is mild, easy to control, environment-friendly and has good development prospect.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following will briefly introduce the embodiments or drawings used in the description of the prior art, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.

FIG. 1 is an SEM image of both unmodified wool yarn and modified wool yarn at 10 μm scale, where a is the blank, b is example 1, and c is example 2.

FIG. 2 is a cross-sectional view (1000 times magnification) of unmodified wool yarn and modified wool yarn, where a is blank control, b is example 1, and c is example 2.

FIG. 3 is a graph of unmodified wool yarn and modified wool yarn dyeing, where a is blank, b is example 1, and c is example 2.

FIG. 4 is a schematic representation of the bio-enzymatic staining process.

Detailed Description

The following description of the preferred embodiments of the present invention is provided for the purpose of better illustrating the invention and is not intended to limit the invention thereto.

And (3) testing the breaking strength: the test is carried out on a tensile testing machine, the holding length is selected to be 180mm, the tensile speed is 100mm/min, the test is carried out for multiple times, and the average value is taken. Alkali solubility determination: and (4) calculating the solubility of the yarn by using the weight and solubility formula of the yarn after alkali treatment, and testing the alkali damage resistance of the yarn. And (3) oxidation resistance measurement: and determining the oxidation resistance of the yarn by adopting an ABTS method. The K/S value of the wool yarn was measured with a color tester.

Example 1

(1) Pretreatment:

the processing process formula and conditions are as follows: weighing 1g of wool yarn and sodium carbonate, dissolving the sodium carbonate in deionized water to prepare 1g/L sodium carbonate solution, wherein the bath ratio is 1: 30. soaking wool fiber in 40 deg.C sodium carbonate solution for 15min, cleaning with 40 deg.C anhydrous ethanol for 10min, rinsing with deionized water, and oven drying at 40 deg.C.

(2) Enzymatic reaction of phenolic compounds with wool:

preparing a solution: preparing 0.2mol/L acetic acid-sodium acetate buffer solution, adjusting the pH to 5.0, sequentially adding 0.04mol/L catechol and 75U/mL laccase, wherein the bath ratio is 1: and 30, placing the wool yarns into a reactor, uniformly shaking, placing the pretreated wool yarns into a prepared buffer solution, and carrying out constant-temperature shaking reaction for 5 hours at 40 ℃.

(3) And (3) post-treatment:

and (4) taking out the wool yarns obtained in the step (3), freezing for 12h at-50 ℃ to inactivate enzyme, washing with deionized water, and naturally drying.

Example 2

(1) Pretreatment:

the processing process formula and conditions are as follows: and (2) placing 1g of wool yarns in a low-temperature plasma treatment machine, starting a vacuum pump, introducing oxygen, clicking an automatic mode, and performing low-temperature plasma treatment on the protein fibers at the treatment power of 100W for 5 min.

(2) Enzymatic reaction of phenolic compounds with wool:

preparing a solution: preparing 0.2mol/L acetic acid-sodium acetate buffer solution, adjusting the pH value to 5.5, sequentially adding 0.04mol/L catechol and 75U/mL laccase, and carrying out bath ratio of 1: 50, placing the wool yarn in a reactor, uniformly shaking, placing the pretreated wool yarn in a prepared buffer solution, and carrying out constant-temperature shaking reaction for 5 hours at 40 ℃.

(3) And (3) post-treatment:

and (4) taking out the wool yarns obtained in the step (3), freezing for 12h at-40 ℃ to inactivate enzyme, then washing with deionized water, and naturally drying.

The properties of the wool obtained in examples 1-2 were examined and the results are shown in tables 1 and 2.

TABLE 1 results of measuring properties of wool fibers obtained in examples 1 to 2

TABLE 2 dyeing parameters of wool fibers obtained by different treatments in examples 1-2

According to the data in the table, the wool yarns subjected to different pretreatments can be dyed in a better dyeing depth through enzymatic polymerization dyeing, the strength of the wool yarns is improved in different degrees, the alkali solubility is reduced, and the oxidation resistance is improved. Obviously, the strength of the wool yarn dyed by the enzyme method after the plasma pretreatment is improved by 26 percent, and the wool yarn dyed by the enzyme method has better mechanical property than the wool yarn dyed by the enzyme method after the chemical pretreatment.

Example 3 investigation of the Effect of laccase dosage on wool fiber dyeing

Referring to example 1, the laccase dosage in step (2) was replaced with 25U/mL, 50U/mL, 100U/mL, 125U/mL, respectively, and other conditions were unchanged:

(1) pretreatment:

(2) Enzymatic reaction of phenolic compounds with wool:

preparing a solution: preparing 0.2mol/L acetic acid-sodium acetate buffer solution, adjusting the pH value to 5.0, sequentially adding 0.04mol/L catechol, 25U/mL laccase, 50U/mL laccase, 75U/mL laccase, 100U/mL laccase and 125U/mL laccase, wherein the bath ratio is 1: and 30, placing the wool yarns into a reactor, uniformly shaking, placing the pretreated wool yarns into a prepared buffer solution, and carrying out constant-temperature shaking reaction for 5 hours at 40 ℃.

(3) And (3) post-treatment:

The properties of the obtained wool were measured and the results are shown in tables 3 and 4.

TABLE 3 results of dyed wool fibers obtained at different enzyme concentrations

TABLE 4 dyeing parameters of wool fibers obtained with different enzyme concentrations

According to the data in the table, when the enzyme concentration is lower, the yarn can obtain higher dyeing depth and breaking strength, the L value is gradually reduced (brightness is reduced), a and b are positive values, and the yarn is dark brown. With the increase of enzyme concentration, alkali solubility of the yarn is reduced, and oxidation resistance is slightly increased, but the effect is not good. When the enzyme concentration exceeds 75U/mL, both the breaking strength and the staining depth tend to be stable. If the concentration of laccase is too high (150U/mL), the dyeing level becomes slightly deeper, but the effect of improving the dyeing power is reduced, and the reagent is wasted, which is uneconomical.

Example 4 investigation of the Effect of catechol concentration on wool fiber dyeing

Referring to example 1, the reaction concentrations of the phenolic substrates in step (2) were replaced with 0.08mol/L, 0.12mol/L, 0.16mol/L, and 0.20mol/L, respectively, and the other conditions were not changed:

(1) pretreatment:

(2) Enzymatic reaction of phenolic compounds with wool:

preparing a solution: preparing 0.2mol/L acetic acid-sodium acetate buffer solution, adjusting the pH value to 5.0, and sequentially adding 0.08mol/L, 0.12mol/L, 0.16mol/L, 0.20mol/L catechol and 75U/mL laccase, wherein the bath ratio is 1: and 30, placing the wool yarns into a reactor, uniformly shaking, placing the pretreated wool yarns into a prepared buffer solution, and carrying out constant-temperature shaking reaction for 5 hours at 40 ℃.

(3) And (3) post-treatment:

The properties of the obtained wool were measured and the results are shown in tables 5 and 6.

TABLE 5 results of dyed wool fibers obtained at different catechol concentrations

TABLE 6 dyeing parameters for wool fibers obtained at different catechol concentrations

According to the data in the table, under the catalysis of laccase, the dyeing depth of wool yarns is gradually increased along with the increase of the concentration of catechol monomer, the yarns are brownish, and the alkali resistance and the oxidation resistance are improved. However, as the amount of phenol is increased, the breaking strength of the yarn is increased and then decreased, and the elongation at break is decreased as the amount of phenol is increased. When the substrate concentration is low (e.g., 0.02mol/L), the dyeing and strength are not significantly improved; when the substrate concentration is too high (for example, 0.4mol/L), the dyeing depth becomes large, but the dyeing unevenness causes a decrease in yarn strength and elongation at break, resulting in deterioration in hard touch and elasticity.

Example 5 investigation of the Effect of reaction temperature on wool fiber dyeing

Referring to example 1, the method of step (2)Reaction temperatureRespectively replacing the temperature of the mixture to 30 ℃, 50 ℃, 60 ℃, 70 ℃ and 80 ℃, and keeping other conditions unchanged:

(1) pretreatment:

(2) Enzymatic reaction of phenolic compounds with wool:

preparing a solution: preparing 0.2mol/L acetic acid-sodium acetate buffer solution, adjusting the pH to 5.0, sequentially adding 0.04mol/L catechol and 75U/mL laccase, wherein the bath ratio is 1: and 30, placing the wool yarns in a reactor, uniformly shaking, placing the pretreated wool yarns in a prepared buffer solution, and carrying out constant-temperature shaking reaction for 5 hours at different temperatures.

(3) And (3) post-treatment:

The properties of the obtained wool were measured and the results are shown in tables 7 and 8.

TABLE 7 results of dyed wool fibers obtained at different temperatures

TABLE 8 dyeing parameters of wool fibers obtained at different temperatures

According to the data in the table, when the temperature is lower than 50 ℃, the dyeing depth and the breaking strength of the dyed yarn are increased along with the increase of the temperature, and after the temperature is higher than 50 ℃, the breaking strength and the dyeing depth of the wool yarn are slowly reduced along with the increase of the temperature.

Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made by those skilled in the art without departing from the spirit and scope of the invention.

Claims

1. A method for improving wool fiber strength by biological enzyme is characterized in that laccase and phenolic compounds are added into a buffer solution to form a mixed system; then placing the wool fibers in the mixed system, and preserving heat at 30-80 ℃ for reaction;

the concentration of the laccase in the mixed system is 25-125U/mL; the concentration of the phenolic compound is 0.04-0.20 mol/L.

2. The method of claim 1, wherein the phenolic compound is catechol, hydroquinone, gallic acid, vanillin, guaiacol.

3. The method of claim 1, wherein the buffer solution is an acetic acid-sodium acetate buffer.

4. The method according to claim 3, wherein the concentration of the acetic acid-sodium acetate buffer solution is 0.1-0.3 mol/L; the pH is 4.0-6.0.

5. The method of claim 1, wherein the ratio of the bath is 1: 20-1: 50, adding the wool fibers into the mixed system.

6. The method according to any one of claims 1 to 5, wherein the reaction is carried out at 30 to 80 ℃ for 2 to 10 hours.

7. Wool fibres produced by the method of any one of claims 1 to 6.

8. A yarn, thread or fabric comprising the wool fiber of claim 7.