WO2022012012A1 - Strongly hydrophobic real silk fabric and preparation method therefor - Google Patents

Abstract

Disclosed is a method for preparing a strongly hydrophobic real silk fabric. A specially designed grafting system is used and comprises laccase, an acetate buffer having a pH of 4-5, lauryl gallate, ethanol, a reaction medium, a catalytic mediator and a copper salt. The method comprises preheating the grafting system at 30-60°C for 10-15 min, maintaining the temperature, then adding a pretreated silk fabric according to a liquor ratio of 1:50, reacting for 2-6 h, sequentially washing with cold water and warm water, then drying, and extracting to obtain said strongly hydrophobic real silk fabric. The method of the present invention features simple reaction, mild reaction, strong catalytic activity, a fast grafting rate, and a high monomer grafting rate. The hydrophobic performance of the real silk fabric is significantly increased. Also disclosed is a strongly hydrophobic real silk fabric prepared by the described method. Said real silk fiber has low surface energy, strong hydrophobic performance, and a lasting hydrophobic effect.

Description

A kind of strong hydrophobic silk fabric and preparation method thereof technical field

The invention relates to the technical field of real silk fabrics, in particular to a strong hydrophobic real silk fabric and a preparation method and preparation process thereof.

Background technique

As an ecological non-polluting natural protein fiber, silk has many advantages such as moisture absorption, breathability, softness and elegance, and has been popular in the field of clothing for thousands of years. With the progress of society, people's requirements for high performance and multi-functionality of silk are constantly increasing. Therefore, it is urgent to modify silk fibers and their products to improve their natural defects, and to give them new functional properties, so as to improve the quality and added value of silk to meet the ever-changing social needs.

The hydrophobic modification of silk can reduce its surface energy, improve its hydrophobicity and anti-fouling ability, reduce the number of fabric washing, and improve the ease of care. While breaking the seasonal boundaries of silk fabrics, it can expand its application in many fields such as high-end home textiles, medical care and interior decoration, and improve the market share and social competitiveness of silk products.

At present, the hydrophobic modification of silk fabrics is still mainly concentrated in the finishing stage. Commonly used hydrophobic modification methods include padding/dipping finishing, coating finishing and grafting modification finishing. At present, there are many studies on graft hydrophobic modification. As a protein fiber containing multiple reactive groups, silk can react with hydrophobic monomers to combine with the reactive groups of silk fibers in the form of covalent bonds to improve the hydrophobic properties of silk. The traditional physical/chemical modification methods all have defects such as high process requirements, large fiber damage, and easy residual harmful substances to a certain extent, and the hydrophobic strength cannot meet the growing market demand. Therefore, it is of great practical significance to explore new methods for modifying the strong hydrophobicity of fibroin.

SUMMARY OF THE INVENTION

In order to overcome the deficiencies of the prior art, one of the objects of the present invention is to provide a method for preparing a strong hydrophobic silk fabric, using a specially designed grafting system, the reaction is simple and mild, the catalytic activity is strong, the grafting rate is fast, the monomeric The grafting rate is high, and the hydrophobic properties of silk fabrics are significantly improved;

The second purpose of the present invention is to provide a strong hydrophobic silk fabric prepared by the above method, the silk fiber has low surface energy, strong hydrophobicity and lasting hydrophobic effect.

One of the objects of the present invention adopts the following technical scheme to realize:

A preparation method of strong hydrophobic silk fabric, comprising the following steps:

Preheat the grafting system at 30-60℃ for 10-15min, keep the temperature, then add the pretreated silk fabric according to the liquor ratio of 1:50, the grafting reaction is 2-6h, washed with cold water and warm water in turn, and then dried. Dry and extract to obtain the strong hydrophobic silk fabric;

The grafting system includes laccase, acetate buffer at pH 4-5, lauryl gallate, ethanol, reaction medium, catalytic mediator and copper salt.

Preferably, the catalytic mediator is 2,6-dimethoxyphenol.

Further, in the grafting system, the concentration of laccase is 1.5-2.25U/ml, the concentration of lauryl gallate is 8-15mM, the concentration of mediator is 0.13-0.2M, and the concentration of copper salt is 10-25mM .

Preferably, in the grafting system, the concentration of laccase is 2U/ml, the concentration of lauryl gallate is 12mM, the concentration of catalytic mediator is 0.15M, and the concentration of copper salt is 15mM.

Preferably, the pH of the acetate buffer is 4.

Further, the reaction medium includes 0.2M acetic acid-sodium acetate and ethanol at pH 3.5-5.5, and the volume ratio of the acetic acid-sodium acetate and ethanol is 4:1.

Preferably, the preheating temperature of the grafting system is 50°C, the preheating time is 10min, and the grafting reaction time is 5h.

Further, the grafting system is prepared by the following method:

1) mixing laccase with acetate buffer to prepare a laccase solution;

2) dissolving lauryl gallate in ethanol to obtain a monomer solution;

3) The grafting system is obtained by uniformly mixing the laccase solution, the monomer solution, the reaction medium, the catalytic mediator and the copper salt.

The pretreatment includes the following steps: adding the silk fabric to a soaping solution at 55-65° C. according to a liquor ratio of 1:50, soaping for 30 minutes, and drying it for later use; the soaping solution contains 2g/l soap flakes .

The second purpose of the present invention is achieved through the following technical solutions:

A strong hydrophobic real silk fabric is prepared by the above-mentioned preparation method of the strong hydrophobic real silk fabric.

Compared with the prior art, the beneficial effects of the present invention are:

1. The present invention utilizes laccase to catalyze the oxidation of tyrosine phenolic hydroxyl groups that are rich in the surface layer and subsurface layer of silk to generate active phenolic oxygen radicals, and then cause the grafting of exogenous monomers with hydrophobic structures to silk fibers, and the silk fibers A hydrophobic polymer layer is formed on the surface, which reduces the surface tension of silk fibers, imparts hydrophobic properties to silk, increases the added value of silk products, expands its scope of use, reduces energy consumption of production enterprises, and relieves environmental pressure. This invention provides a brand-new method and route for other functional modification of fibroin fibers and other natural fibers in the fields of textiles, chemicals, materials, etc.

2. The present invention uses lauryl gallate as the grafting monomer, which can generate tiny grooves on the surface of the silk fibers, and quickly disperse on the fibers, improve the accessibility of the fibers, form more grafting sites, and increase the number of grafting sites. The grafting rate of macromonomer on the fiber surface greatly reduces the surface energy of the fiber and improves the hydrophobicity of the fiber.

3. The catalytic mediator 2,6-dimethoxyphenol is also added to the grafting system of the present invention to form a laccase/mediator catalytic system with laccase, which improves the efficiency of laccase catalytic grafting and makes the surface of silk fibers The grooves are deepened and the grafted solid particles increase significantly, which greatly reduces the surface energy of the fibers. At the same time, since the structure of laccase itself is a copper-containing polyphenol oxidase, a certain amount of exogenous copper salt is also added to the grafting system of the present invention to assist in increasing the number of grafting sites of silk fibers and improving the grafting of fabrics. rate and improve hydrophobicity.

4. The present invention optimizes the grafting system and reaction process, keeps the grafting reaction rate in the best state, and can quickly complete the enzymatic grafting reaction of silk laccase, and the grafting reaction efficiency of gallate monomer and silk fiber. High, high grafting efficiency, endows silk fabrics with strong hydrophobic properties, low moisture regain, and excellent and durable hydrophobicity.

Description of drawings

Fig. 1 is the SEM photograph of the test example of the present invention.

detailed description

Hereinafter, the present invention will be further described with reference to the accompanying drawings and specific embodiments. It should be noted that, on the premise of no conflict, the embodiments or technical features described below can be arbitrarily combined to form new embodiments. .

A preparation method of strong hydrophobic silk fabric, comprising the following steps:

Preheat the grafting system at 30-60℃ for 10-15min, keep the temperature, then add the pretreated silk fabric according to the liquor ratio of 1:50, the grafting reaction is 2-6h, washed with cold water and warm water in turn, and then dried. Dry and extract to obtain the strong hydrophobic silk fabric;

The grafting system comprises laccase, acetate buffer at pH 4-5, lauryl gallate, ethanol, reaction medium, catalytic mediator and copper salt, and is prepared by the following steps:

1) mixing laccase with acetate buffer to prepare a laccase solution;

2) dissolving lauryl gallate in ethanol to obtain a monomer solution;

3) The grafting system is obtained by uniformly mixing the laccase solution, the monomer solution, the reaction medium, the catalytic mediator and the copper salt.

The pretreatment of the above-mentioned silk fabric includes the following steps: adding the silk fabric to a soaping liquid at 55-65° C. according to a liquor ratio of 1:50, soaping for 30 minutes, and drying for later use. Among them, the soap cooking liquid contains 2g/l of soap flakes.

The laccase in the graft system, as a kind of oxidoreductase preparation with safety, high efficiency, energy saving and environmental protection, and a wide range of substrates, can disintegrate or polymerize textile materials or waste structures to achieve the purpose of treatment. It can be used as a bioinitiator to replace some chemicals for functional modification of textile materials. The rich tyrosine (≥11%) of silk is a suitable substrate for laccase, which can catalyze the formation of active free radicals from tyrosine and initiate a series of graft polymerization reactions.

The above-mentioned catalytic mediator is preferably 2,6-dimethoxyphenol (DMP), which forms a laccase/mediator catalytic system with laccase, improves the efficiency of laccase catalyzed grafting, and enhances the superficial and subsurface layers of silk fibers. The activation of the phenolic hydroxyl group of tyrosine generates more active phenolic oxygen radicals.

In the grafting system, the concentration of laccase is 1.5-2.25U/ml, the concentration of lauryl gallate is 8-15mM, the concentration of mediator is 0.13-0.2M, and the concentration of copper salt is 10-25mM.

As a further preferred solution, in the grafting system, the concentration of laccase is 2U/ml, the concentration of lauryl gallate is 12mM, the concentration of catalytic mediator is 0.15M, and the concentration of copper salt is 15mM.

The pH of the acetate buffer is 4.

The reaction medium included 0.2M acetic acid-sodium acetate and ethanol at pH 3.5-5.5, and the volume ratio of acetic acid-sodium acetate and ethanol was 4:1.

As a further preferred solution, the preheating temperature of the grafting system is 50°C, the preheating time is 10min, and the grafting reaction time is 5h.

A strong hydrophobic real silk fabric is prepared by the above-mentioned preparation method of the strong hydrophobic real silk fabric.

Example 1

A preparation method of strong hydrophobic silk fabric, comprising the following steps:

(1) Pretreatment of silk fabrics:

The soaping liquid was prepared according to 2g/l of soap flakes. After heating the prepared soaping liquid to 60°C on an induction cooker, it was put into electric spinning of silk according to the liquor ratio of 1:50. Equilibrate for 24 hours in a desiccator.

(2) Preparation of grafting system:

The grafting system in this example includes 2U/ml laccase, acetate buffer at pH 4, 12mM lauryl gallate, ethanol, reaction medium, 0.15M DMP and 15mM copper sulfate; wherein, the reaction medium includes 0.2M acetic acid- Sodium acetate and ethanol, the volume ratio of acetic acid-sodium acetate and ethanol is 4:1, prepared by the following steps:

1) mixing above-mentioned laccase with acetate buffer to prepare a laccase solution;

2) dissolving lauryl gallate in ethanol to obtain a monomer solution;

3) The laccase solution, monomer solution, reaction medium, DMP and copper sulfate are mixed uniformly to obtain.

(3) Modification treatment:

①Preheat the above grafting system at 50°C for 10min, keep the temperature unchanged, add the treated silk electrospinning in step (1) according to the liquor ratio of 1:50, and react for 5h;

②Take out the silk electrospinning obtained in ①. After washing with cold water, wash it twice with warm water at 80°C for about 20 minutes each time. After drying, extract it with acetone solution at 75°C for 12 hours, and place it in a fume hood to dry. .

Infrared spectrum scanning was carried out on the silk electrospinning before and after grafting in this example, and it was detected that the silk fiber had been successfully grafted to lauryl gallate monomer.

Example 2

A preparation method of a strong hydrophobic silk fabric, except for the grafting system and modification time, the remaining steps are the same as those in Example 1.

The grafting system of this embodiment includes: 1U/ml laccase, acetate buffer at pH 3.5, 10mM lauryl gallate, ethanol and reaction medium; wherein, the reaction medium includes 0.2M acetic acid-sodium acetate and ethanol, acetic acid- The volume ratio of sodium acetate and ethanol is 4:1.

The modification time of this example is 1h, 2h, 3h, 4h, 5h, 6h.

Calculate the grafting rate under different modification times of the present embodiment, and the calculation formula of the grafting rate is as follows:

According to calculation, the optimal reaction time of laccase enzymatic grafting silk in this example is 5h.

Example 3

A preparation method of a strong hydrophobic silk fabric, except for the grafting system, the remaining steps are the same as in Example 1.

The grafting system of this embodiment includes: 1 U/ml laccase, acetate buffer with pH of 2.5, 3.0, 3.5, 4.0, 4.5, 5.0 in sequence, 10 mM lauryl gallate, ethanol and a reaction medium; wherein, the reaction medium includes 0.2M acetic acid-sodium acetate and ethanol, the volume ratio of acetic acid-sodium acetate and ethanol is 4:1.

According to the method for calculating the grafting rate of Example 2, the grafting rate under different pH values of the present example was calculated. Experiments have shown that the ideal pH value of laccase-activated silk fiber grafting lauryl gallate is 4.0, and the pH value is lower The enzyme-catalyzed silk grafting activity reached its peak, and the reaction rate was the best.

Example 4

A preparation method of a strong hydrophobic silk fabric, except for the grafting system and the preheating temperature of the grafting system, the remaining steps are the same as those in Example 1.

The grafting system of this embodiment includes: 1U/ml laccase, pH 4.0 acetate buffer, 10mM lauryl gallate, ethanol and reaction medium; wherein, the reaction medium includes 0.2M acetic acid-sodium acetate and ethanol, acetic acid- The volume ratio of sodium acetate and ethanol is 4:1.

The preheating temperature of the grafting system in this embodiment is 30°C, 40°C, 50°C, 60°C, and 70°C in sequence.

According to the method for calculating the grafting ratio of Example 2, the grafting ratios under different preheating temperatures of the grafting systems in the present embodiment were calculated. The experiment proved that the optimal reaction temperature of the laccase catalyzed lauryl gallate graft-modified silk fabric was 50°C. At this temperature, the laccase activity is high, the thermal motion of the monomer lauryl gallate is low, the monomer is not easy to undergo a homopolymerization reaction, and the grafting rate with real silk is fast and efficient.

Example 5

A preparation method of a strong hydrophobic silk fabric, except for the grafting system, the remaining steps are the same as in Example 1.

The grafting system of this embodiment includes: laccase (1.0U/ml, 1.5U/ml, 2.0U/ml, 2.5U/ml, 3.0U/ml), pH 4.0 acetate buffer, 10mM lauryl gallate , ethanol and a reaction medium; wherein, the reaction medium includes 0.2M acetic acid-sodium acetate and ethanol, and the volume ratio of acetic acid-sodium acetate and ethanol is 4:1.

According to the method for calculating the grafting rate in Example 2, the grafting rate under different laccase concentrations in this example was calculated. Experiments proved that the optimal concentration of laccase catalyzing the graft modification of silk fabrics was 2.0U/mL. At this concentration, the polymerization efficiency of the monomer lauryl gallate itself is low, and the graft polymerization reaction efficiency between the monomer and the silk fiber is high.

Example 6

A preparation method of a strong hydrophobic silk fabric, except for the grafting system, the remaining steps are the same as in Example 1.

The grafting system of this embodiment includes: 2U/ml laccase, acetate buffer at pH 4.0, lauryl gallate (5mM, 8mM, 10mM, 12mM, 15mM), ethanol and reaction medium; wherein, the reaction medium includes 0.2M The volume ratio of acetic acid-sodium acetate and ethanol, acetic acid-sodium acetate and ethanol is 4:1.

According to the method for calculating the grafting rate of Example 2, the grafting rate under different concentrations of lauryl gallate in this example was calculated. The experiment proved that the optimum dosage of the monomer lauryl gallate in this experiment was 12 mM. At this concentration, the monomer can be dispersed on the fiber with maximum efficiency, forming more grafting sites, and the grafting efficiency is high.

Example 7

A preparation method of a strong hydrophobic silk fabric, except for the grafting system, the remaining steps are the same as in Example 1.

The grafting system of this example includes: 2U/ml laccase, acetate buffer at pH 4.0, 12mM lauryl gallate, ethanol, reaction medium and copper sulfate (5mM, 10mM, 15mM, 20mM, 25mM); wherein, the reaction The medium consists of 0.2 M acetic acid-sodium acetate and ethanol in a volume ratio of 4:1 acetic acid-sodium acetate and ethanol.

According to the method for calculating the grafting rate in Example 2, the grafting rate under different concentrations of lauryl gallate in this example was calculated. Experiments have shown that adding an appropriate amount of copper salt (15mM) can improve the grafting effect. After this example is added, the grafting rate is obviously higher than the highest grafting rate in Example 6, and the grafting rate when the copper salt concentration is 15mM is more than twice the highest grafting rate in Example 6.

Since the structure of laccase is a copper-containing polyphenol oxidase, adding a certain amount of exogenous copper ions into the reaction system can increase the number of grafting sites of silk fibers and improve the grafting rate of fabrics. However, when the amount of copper salt is higher than 15mM, the copper ion combines with the ω-carboxyl anion in the middle of the acid amino residue around the active site of the laccase, which reduces the binding rate between the active center and the substrate, and reduces the activity of laccase to a certain extent. , resulting in a decrease in the grafting rate of the fabric.

Example 8

A preparation method of a strong hydrophobic silk fabric, except for the grafting system, the remaining steps are the same as in Example 1.

The grafting system of this example includes: 2U/ml laccase, acetate buffer pH 4.0, 12mM lauryl gallate, ethanol, reaction medium, 15mM copper sulfate and DMP (0.05M, 0.10M, 0.15M, 0.20M , 0.25M); wherein, the reaction medium includes 0.2M acetic acid-sodium acetate and ethanol, and the volume ratio of acetic acid-sodium acetate and ethanol is 4:1.

According to the method for calculating the grafting rate of Example 2, the grafting rate under different lauryl gallate concentrations of the present embodiment is calculated. Experiments show that the addition of DMP in the present embodiment greatly improves the grafting rate of the reaction, and the optimum dosage is 0.15 M. This may be because with the addition of a certain concentration of mediator catalyst, DMP and laccase form a laccase/mediator catalytic system, which improves the efficiency of laccase grafting. The grafting rate was increased. When the amount of DMP is too much, the reaction between itself may be aggravated, and a large number of homopolymers formed adhere to the surface of the silk fiber, which affects the grafting reaction between the monomer and the silk fiber, resulting in a decrease in the grafting rate.

Comparative Example 1

A preparation method of hydrophobic silk fabric, comprising the following steps:

20ml ethanol, 15mM octadecylamine (OA) monomer, 80ml acetic acid-sodium acetate buffer (0.2M, pH=4), silk electrospinning (bath ratio 1:50), 1U/ml laccase, 15mM copper sulfate and 0.15M DMP were added to the round-bottomed flask in turn. After mixing and shaking, the reaction was carried out in a constant temperature shaking water bath at 50 °C for 5 h. After that, the fabric was taken out and washed twice with warm water at 80 °C for about 20 minutes each time, and then extracted with acetone. After extraction for 12h, the hydrophobic silk fabric was obtained.

test case

The following four groups of silk fabrics were selected for performance testing:

Group a: electrospinning of silk that has been pretreated but not grafted;

Group b: strong hydrophobic silk fabric with the best grafting rate in Example 6;

Group c: hydrophobic silk fabric of Comparative Example 1;

Group d: the strong hydrophobic silk fabric of Example 1.

(1) Calculate the wetting time, water repellency, moisture regain, etc. of the test sample through the hydrophobic performance test. The experimental data are shown in Table 1.

Wetting time: According to the method of AATCC 79-2000, the balanced silk fabric is tightly fixed, and a drop of deionized water is about 10mm away from the fabric. The time required for the deionized water droplet to contact the surface of the fabric until the water droplet completely wets the fabric is Wetting time.

Water repellency: Take a certain size of the silk sample to be tested, and measure the water repellency on a water wetness meter according to the test method of AATCC-22 (1977) 22 (1977). The water consumption for spraying is about 250ml.

Moisture regain: Put the weighed sample m ₀ in an oven, raise the temperature to 140-145°C, take out the fabric after drying for 90 minutes, weigh its dry weight m ₁ , calculate the moisture regain of the fabric, the formula is as follows:

Table 1 Hydrophobic performance calculation table

test group Wetting time/s water repellency Moisture regain/% a 3 0 8.63 b 60 50 7.95 c 125 60 6.88 d 380 80 6.67

It can be seen from Table 1 that the fabrics grafted with lauryl gallate and stearylamine as monomers have obvious hydrophobicity, indicating that laccase catalyzes silk tyrosine to realize the modification of silk. By comparing the contact angles of the silk fabrics of group b and group d, it can be seen that the addition of copper ions and DMP in d, the degree of grafting is significantly improved, and the corresponding hydrophobicity is also better; by comparing the same process conditions, the silk grafted octadecylamine (c) Contact angle with lauryl gallate (d), it can be seen that the hydrophobic effect of grafted stearylamine is not as good as that of grafted lauryl gallate, and the hydrophobicity and water repellency of grafted silk is also slightly worse. a little.

The water repellency and contact angle of the grafted silk are basically consistent. In the case of grafting the same monomer, the higher the grafting rate, the better the hydrophobicity; under the same process conditions, compared with the silk-grafted lauryl gallate (d), the The silk fabric of lauryl gallate can obtain more excellent and lasting hydrophobic effect.

According to the moisture regain data, the moisture regain of the silk fabric of the present invention can be reduced by nearly 23%, and the moisture regain of the silk fabric of Comparative Example 1 can be reduced by nearly 20%. The smaller the moisture regain, the worse the hydrophilic performance of the fabric, that is, the better the hydrophobicity. This is consistent with the contact angle measurements and the water repellency measurements.

(2) Scanning Electron Microscope (SEM)

The structure and morphology of the samples were observed with a Japanese TM-3030 scanning electron microscope. The test acceleration voltage was 5kV and the magnification was 2000 times. The results are shown in Figure 1.

It can be seen from Figure 1 that the surface of the silk fiber (a) that has only been pretreated is complete and smooth without obvious grooves. After group b is grafted with lauryl gallate, tiny grooves are formed on the surface of silk fibers, and solid particles, that is, monomer grafts, are attached to the surface of silk fibers, reducing the surface energy and increasing its hydrophobicity. After adding the mediator in group d, the solid particles increased significantly, the grooves deepened, and the surface energy of the fibers decreased.

The above-mentioned embodiments are only the preferred embodiments of the patent of the present invention, and cannot be used to limit the protection scope of the patent of the present invention. Any insubstantial changes and substitutions made by those skilled in the art on the basis of the patent of the present invention belong to The scope of protection claimed by the patent of the present invention.

Claims (10)

A preparation method of strong hydrophobic silk fabric, is characterized in that, comprises the following steps: Preheat the grafting system at 30-60℃ for 10-15min, keep the temperature, then add the pretreated silk fabric according to the liquor ratio of 1:50, the grafting reaction is 2-6h, washed with cold water and warm water in turn, and then dried. Dry and extract to obtain the strong hydrophobic silk fabric; The grafting system includes laccase, acetate buffer at pH 4-5, lauryl gallate, ethanol, reaction medium, catalytic mediator and copper salt. The method for preparing a strong hydrophobic silk fabric according to claim 1, wherein the catalytic mediator is 2,6-dimethoxyphenol. The preparation method of strong hydrophobic silk fabric according to claim 1, characterized in that, in the grafting system, the concentration of laccase is 1.5-2.25U/ml, the concentration of lauryl gallate is 8-15mM, and the concentration of mediator is 1.5-2.25U/ml. The concentration of the copper salt is 0.13-0.2M, and the concentration of the copper salt is 10-25mM. The preparation method of strong hydrophobic silk fabric according to claim 3, is characterized in that, in described graft system, the concentration of laccase is 2U/ml, the concentration of lauryl gallate is 12mM, and the concentration of catalytic mediator is 0.15 M, the concentration of copper salt was 15 mM. The preparation method of strong hydrophobic silk fabric according to claim 1, is characterized in that, the pH of described acetic acid buffer solution is 4. The preparation method of strong hydrophobic silk fabric according to claim 1, is characterized in that, described reaction medium comprises 0.2M acetic acid-sodium acetate and ethanol, and the volume ratio of described acetic acid-sodium acetate and ethanol is 4:1. The preparation method of strong hydrophobic silk fabric according to claim 1, wherein the preheating temperature of the grafting system is 50°C, the preheating time is 10min, and the grafting reaction time is 5h. The preparation method of strong hydrophobic silk fabric according to claim 1, is characterized in that, described grafting system is prepared by following method: 1) mixing laccase with acetate buffer to prepare a laccase solution; 2) dissolving lauryl gallate in ethanol to obtain a monomer solution; 3) The grafting system is obtained by uniformly mixing the laccase solution, the monomer solution, the reaction medium, the catalytic mediator and the copper salt. The method for preparing a strong hydrophobic silk fabric according to claim 1, wherein the pretreatment comprises the following steps: adding the silk fabric to a soaping liquid at 55-65°C according to a liquor ratio of 1:50, and performing a soaping treatment 30min, dry for later use; the soap cooking liquid contains 2g/l soap flakes. A strong hydrophobic silk fabric is prepared by the preparation method of the strong hydrophobic silk fabric according to any one of claims 1-9.

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