A method for shikimic acid antibacterial finishing of wool fabrics based on click reaction

Abstract

The present invention provides a method for shikimic acid antibacterial finishing of wool fabrics based on click reaction, which relates to the technical field of textile materials. The method for shikimic acid antibacterial finishing of wool fabrics based on click reaction provided by the present invention comprises the following steps: placing the wool fabric in a reducing solution for reduction reaction to obtain a pretreated wool fabric containing mercapto groups; mixing shikimic acid, isophorone diisocyanate, a catalyst and an organic solvent for addition reaction to obtain an antibacterial finishing solution; placing the pretreated wool fabric containing mercapto groups in the antibacterial finishing solution and carrying out click reaction under the action of triethylamine to obtain an antibacterial wool fabric. The present invention can endow the wool fabric with good antibacterial performance, and has a low reaction temperature, a high grafting rate and little damage to the strength of the wool fabric.

Description

Technical Field

[0001] The present invention relates to the technical field of textile materials, and particularly relates to a method for shikimic acid antibacterial finishing of wool fabrics based on click reaction. Background Art

[0002] Wool belongs to protein fiber and is highly favored by consumers due to its good warmth retention, smooth handfeel, and excellent stiffness. However, wool fibers contain a large amount of amino acids and have a microporous structure, providing the necessary environment, carbon source, and nitrogen source for bacterial growth, greatly limiting its application range. Therefore, antibacterial finishing of wool fabrics is of great significance.

[0003] There are many types of antibacterial agents. Inorganic antibacterial agents have poor durability and are prone to oxidation and discoloration, such as gold, silver, copper, mercury, etc. Organic antibacterial agents have a wide antibacterial spectrum but poor heat resistance, such as quaternary ammonium salt antibacterial agents, phenol antibacterial agents, etc. Summary of the Invention

[0004] The purpose of the present invention is to provide a method for shikimic acid antibacterial finishing of wool fabrics based on click reaction, which can endow wool fabrics with good antibacterial properties, with low reaction temperature, high grafting rate, and little damage to the strength of wool fabrics.

[0005] In order to achieve the above-mentioned invention purpose, the present invention provides the following technical solutions:

[0006] The present invention provides a method for shikimic acid antibacterial finishing of wool fabrics based on click reaction, including the following steps:

[0007] Place the wool fabric in a reducing solution for reduction reaction to obtain a pretreated wool fabric containing mercapto groups;

[0008] Mix shikimic acid, isophorone diisocyanate, a catalyst, and an organic solvent for addition reaction to obtain an antibacterial finishing solution;

[0009] Place the pretreated wool fabric containing mercapto groups in the antibacterial finishing solution and carry out a click reaction under the action of triethylamine to obtain an antibacterial wool fabric.

[0010] Preferably, the reducing agent in the reducing solution is tricarboxyethylphosphine.

[0011] Preferably, the concentration of the reducing solution is 15 - 20 mmol / L.

[0012] Preferably, the temperature of the reduction reaction is 20 - 40 °C; the time of the reduction reaction is 3 - 6 h.

[0013] Preferably, the mass ratio of shikimic acid to isophorone diisocyanate is 10 - 22:1.74 - 8.70.

[0014] Preferably, the catalyst is an organotin catalyst.

[0015] Preferably, the organic solvent includes N,N-dimethylformamide or methyl ethyl ketone.

[0016] Preferably, the temperature of the addition reaction is 45-85 °C; the time of the addition reaction is 30-150 min.

[0017] Preferably, the mass of triethylamine is 0.05-0.15% of the mass of the organic solvent.

[0018] Preferably, the temperature of the click reaction is 20-50 °C; the time of the click reaction is 0.5-1.5 h.

[0019] The present invention provides a method for antibacterial finishing of wool fabric based on click reaction, comprising the following steps: placing the wool fabric in a reducing solution for a reduction reaction to obtain a pretreated wool fabric containing mercapto groups; mixing shikimic acid, isophorone diisocyanate, a catalyst and an organic solvent for an addition reaction to obtain an antibacterial finishing solution; placing the pretreated wool fabric containing mercapto groups in the antibacterial finishing solution and carrying out a click reaction under the action of triethylamine to obtain an antibacterial wool fabric. The present invention reduces the disulfide bonds in wool to mercapto groups by using a reducing solution, uses isophorone diisocyanate (IPDI) as a crosslinking agent and shikimic acid as an antibacterial agent, and incorporates shikimic acid into the wool fabric through click chemical reaction to achieve antibacterial finishing of the wool fabric. The present invention can endow the wool fabric with good antibacterial properties, and has a low reaction temperature, a high grafting rate and little damage to the strength of the wool fabric. Description of the Drawings

[0020] Figure 1 It is the energy spectrum analysis diagram of the original wool fabric, the pretreated wool fabric and the antibacterial wool fabric in Example 1; (a) is the original wool fabric; (b) is the pretreated wool fabric; (c) is the antibacterial wool fabric;

[0021] Figure 2 It is the antibacterial test effect diagram of the original wool fabric and the antibacterial wool fabric in Example 1; (a) is the result diagram of the antibacterial test of the original wool fabric against Escherichia coli; (b) is the result diagram of the antibacterial test of the antibacterial wool fabric after antibacterial finishing against Escherichia coli; (c) is the result diagram of the antibacterial test of the original wool fabric against Staphylococcus aureus; (d) is the result diagram of the antibacterial test of the antibacterial wool fabric after antibacterial finishing against Staphylococcus aureus;

[0022] Figure 3 It is the scanning electron microscope diagram of the original wool fabric, the pretreated wool fabric and the antibacterial wool fabric in Example 1; (a) is the original wool fabric; (b) is the pretreated wool fabric; (c) is the antibacterial wool fabric;

[0023] Figure 4 It is the infrared spectrogram before and after the finishing of the wool fabric and before and after the reaction with the finishing solution; Figure 4 In (a) of, (I) is the original wool fabric of Example 1, (II) is the pretreated wool fabric of Example 1; (III) is the antibacterial wool fabric of Example 1; Figure 4 In (b) of, (I) is the infrared spectrogram when the finishing solution has not reacted, and (II) is the infrared spectrogram after the finishing solution reacts at 65 °C for 2 h;

[0024] Figure 5 It is the temperature-k value effect curve graph;

[0025] Figure 6 It is the time-k value effect curve graph;

[0026] Figure 7 It is the triethylamine dosage of catalyst-k value effect curve graph;

[0027] Figure 8 It is the crosslinking agent dosage-k value effect curve graph;

[0028] Figure 9 It is the antibacterial agent-k value effect curve graph. Detailed implementation manners

[0029] The present invention provides a shikimic acid antibacterial finishing method for wool fabrics based on click reaction, comprising the following steps:

[0030] Placing the wool fabric in a reducing solution for reduction reaction to obtain a pretreated wool fabric containing mercapto groups;

[0031] Mixing shikimic acid, isophorone diisocyanate, a catalyst and an organic solvent for addition reaction to obtain an antibacterial finishing solution;

[0032] Placing the pretreated wool fabric containing mercapto groups in the antibacterial finishing solution, and carrying out click reaction under the action of triethylamine to obtain an antibacterial wool fabric.

[0033] The present invention places the wool fabric in a reducing solution for reduction reaction to obtain a pretreated wool fabric containing mercapto groups. In the present invention, the specification of the wool fabric is preferably 200 g / m 2 .

[0034] In the present invention, the preparation method of the reducing solution preferably includes: mixing a reducing agent and a mixed solvent to obtain a reducing solution. In the present invention, the reducing agent in the reducing solution is preferably tris(2-carboxyethyl)phosphine (TCEP). In the present invention, the concentration of the reducing solution is preferably 15 - 20 mmol / L. The present invention uses a reducing agent to reduce the disulfide bonds in wool to thiol groups. In the present invention, tris(2-carboxyethyl)phosphine is a weak reducing agent. Since TCEP can form a coordination covalent bond with an oxygen atom through the lone pair of electrons carried by the central atom "P", it has selective reducibility and can reduce the disulfide bonds in wool fibers to thiol groups.

[0035] In the present invention, the mixed solvent is preferably a mixed solvent of ethanol and water; the volume ratio of ethanol to water in the mixed solvent is preferably 1:1. In the present invention, the water is preferably deionized water. In the present invention, the pH value of the reducing solution is preferably 7.

[0036] In the present invention, the mass ratio of the wool fabric to the reducing solution is preferably 1:50 - 60.

[0037] In the present invention, the temperature of the reduction reaction is preferably 20 - 40 °C, more preferably 30 °C; the time of the reduction reaction is preferably 3 - 6 h, more preferably 4 - 5 h.

[0038] In the present invention, preferably after the reduction reaction, the obtained fabric is dried to obtain a pretreated wool fabric containing thiol groups. In the present invention, the temperature of the drying is preferably 60 °C; the time of the drying is preferably 2 h.

[0039] In the present invention, shikimic acid, isophorone diisocyanate, a catalyst and an organic solvent are mixed to carry out an addition reaction to obtain an antibacterial finishing solution. In the present invention, the catalyst is an organotin catalyst, more preferably including dibutyltin dilaurate (DBTDL) or stannous octoate. In the present invention, the organic solvent preferably includes N,N-dimethylformamide (DMF) or methyl ethyl ketone.

[0040] In the present invention, the mass ratio of shikimic acid to isophorone diisocyanate (IPDI) is preferably 10 - 22:1.74 - 8.70, more preferably 16:5.22. In the mixed solution of shikimic acid, isophorone diisocyanate, the catalyst and the organic solvent, the concentration of shikimic acid is preferably 10 - 22 g / L, more preferably 16 g / L; the concentration of isophorone diisocyanate is preferably 1.74 - 8.70 g / L, more preferably 5.22 g / L; the mass of the catalyst is preferably 0.06 - 0.07% of the mass of the organic solvent.

[0041] In the present invention, the temperature of the addition reaction is preferably 45 to 85 °C, more preferably 55 to 75 °C; the time of the addition reaction is preferably 30 to 150 min, more preferably 110 to 130 min. In the present invention, the addition reaction is preferably carried out under stirring conditions. In the present invention, the stirring is preferably magnetic stirring; the rotation speed of the stirring is preferably 50 r / min.

[0042] During the addition reaction process of the present invention, the hydroxyl group of shikimic acid reacts with the isocyanate group, and its function is to facilitate the introduction into the wool fabric after reacting with the isocyanate crosslinking agent to achieve antibacterial finishing.

[0043] After obtaining the pretreated wool fabric containing a mercapto group and the antibacterial finishing solution, the present invention places the pretreated wool fabric containing a mercapto group in the antibacterial finishing solution and carries out a click reaction under the action of triethylamine to obtain an antibacterial wool fabric. In the present invention, the mass ratio of the pretreated wool fabric containing a mercapto group to the antibacterial finishing solution is preferably 1:30 to 70, more preferably 1:40 to 60.

[0044] In the present invention, the mass of the triethylamine is preferably 0.05 to 0.15% of the mass of the organic solvent, more preferably 0.075%.

[0045] In the present invention, the temperature of the click reaction is preferably 20 to 50 °C, more preferably 30 to 40 °C; the time of the click reaction is preferably 0.5 to 1.5 h, more preferably 1 h.

[0046] The present invention preferably dries the obtained fabric after the click reaction to obtain an antibacterial wool fabric. In the present invention, the drying temperature is preferably 60 °C.

[0047] The present invention grafts the antibacterial agent shikimic acid onto the surface of the wool fabric through the click reaction of the mercapto group with the crosslinking agent isophorone diisocyanate (IPDI). There are two isocyanate groups in the IPDI structure. One undergoes a click chemical reaction with the mercapto group after the wool fiber is reduced, and the other reacts with the antibacterial agent shikimic acid. It is designed according to the influence of temperature and catalyst on the two -NCO. First, the secondary isocyanate group in the IPDI crosslinking agent reacts with the hydroxyl group in shikimic acid. The organic solvent preferably uses N,N - dimethylformamide (DMF). DMF does not react with the crosslinking agent IPDI, and shikimic acid is easily soluble in DMF. Under the action of an organotin catalyst, the secondary isocyanate group will undergo an addition reaction with the hydroxyl group in shikimic acid; after the reaction ends, under the action of triethylamine, the primary isocyanate group will react with the mercapto group on the surface of the wool fabric to introduce shikimic acid into the wool fabric to achieve antibacterial finishing.

[0048] The technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0049] Examples 1-6

[0050] (1) Pretreatment of wool fabric

[0051] Mix absolute ethanol and deionized water in a volume ratio of 1:1, add 0.72 g of tricarboxyethylphosphine to prepare a reducing solution with a concentration of 20 mmol / L, and adjust the pH value to 7 with Na2CO3; immerse 2.5 g of wool fabric in the reducing solution, with a liquor ratio of 1:50, react at a constant temperature of 30 °C for 4 h, and then dry at 60 °C to obtain the pretreated wool fabric.

[0052] (2) Antibacterial finishing of wool fabric

[0053] Using 142 g of DMF as an organic solvent, add the antibacterial agent shikimic acid, the crosslinking agent IPDI, and 0.0994 g of the catalyst DBTDL to prepare a finishing solution, and carry out an addition reaction under magnetic stirring conditions to obtain an antibacterial finishing solution; among them, the dosages of the antibacterial agent shikimic acid and the crosslinking agent IPDI are shown in Table 1; the temperature and time of the addition reaction are shown in Table 1;

[0054] (3) Add the catalyst triethylamine to the antibacterial finishing solution, place the pretreated wool fabric in the finishing solution, with a liquor ratio of 1:60, react at 30 °C for 1 h, and then dry at 60 °C to obtain the antibacterial wool fabric; among them, the dosage of the catalyst triethylamine is shown in Table 1.

[0055] The dosage of the catalyst triethylamine in Table 1 refers to the percentage of the mass of triethylamine to the mass of the organic solvent DMF; the dosage of the antibacterial agent shikimic acid refers to the concentration of the antibacterial agent shikimic acid in the finishing solution.

[0056] Table 1 Raw materials and process parameters of Examples 1-6

[0057]

[0058] Test Example 1 Energy spectrum analysis

[0059] Perform energy spectrum analysis on the original wool fabric, pretreated wool fabric, and antibacterial wool fabric in Example 1, and test the changes in elements on the fibers at different stages through energy spectrum analysis. The test results are as Figure 1 shown.

[0060] Figure 1(a) is the energy spectrum diagram of the original wool fabric, from which the contents of C, N, O, and S can be seen; Figure 1 (b) is the energy spectrum diagram of the pretreated wool fabric. Compared with the original wool fabric, after pretreatment, the weight of the wool fiber decreases and the elemental content changes. However, the contents of C, N, and O change little, and a small amount of TCEP remains. Therefore, the fiber contains S element; Figure 1 (c) is the energy spectrum diagram of the antibacterial wool fabric after antibacterial finishing. It can be clearly seen from the data that the contents of carbon, nitrogen, and oxygen increase significantly. This is because shikimic acid is grafted onto the wool fiber, so the contents of C and N increase slightly. The fiber weight increases, and the increased part does not contain sulfur element, so the sulfur element content decreases. Through energy spectrum analysis, the change of the elemental content of the wool fiber and the grafting of shikimic acid onto the wool fiber can be clearly seen.

[0061] Test Example 2 Antibacterial Test Analysis

[0062] The original wool fabric and the antibacterial wool fabric of Example 1 were subjected to antibacterial tests, and the test results are as Figure 2 shown. The colony counts and antibacterial rates of the samples before and after finishing are shown in Table 2. Figure 2 (a) is the result diagram of the antibacterial test of the original wool fabric against Escherichia coli; (b) is the result diagram of the antibacterial test of the antibacterial wool fabric after antibacterial finishing against Escherichia coli; (c) is the result diagram of the antibacterial test of the original wool fabric against Staphylococcus aureus; (d) is the result diagram of the antibacterial test of the antibacterial wool fabric after antibacterial finishing against Staphylococcus aureus.

[0063] The method for antibacterial performance test is as follows: Taking GB / T 20944 "Evaluation of Antibacterial Properties of Textiles - Part 3: Oscillation Method" as the standard, 0.75 g of the original wool fabric and the antibacterial wool fabric were weighed respectively. Staphylococcus aureus was selected as the Gram-positive bacterium, and Escherichia coli was selected as the Gram-negative bacterium. The calculation formula for the antibacterial rate is shown in Equation (1):

[0064]

[0065] In Equation (1): Q1 is the colony count of the original wool fabric; Q0 is the colony count of the antibacterial wool fabric.

[0066] By comparing Figure 2 (a) and (b), it can be clearly seen that after antibacterial finishing, the number of colonies in Petri dish (b) decreases significantly, proving that shikimic acid has antibacterial effect on Escherichia coli, and the antibacterial rate against Escherichia coli is 74.1%; by comparing Figure 2 (c) and (d), it can be clearly seen that after antibacterial finishing, the number of colonies in Petri dish (d) decreases significantly, proving that shikimic acid has antibacterial effect on Staphylococcus aureus, and the antibacterial rate of shikimic acid against Staphylococcus aureus is 74.9%.

[0067] Table 2 Antibacterial properties and colony counts of wool fabrics

[0068]

[0069] Test Example 3 Fabric Breaking Strength Analysis

[0070] According to GB / T 3923.1-2013 “Tensile properties of textile fabrics Part 1: Strip method for determination of breaking strength and breaking elongation”, the breaking strength of the original wool fabric, pretreated wool fabric and antibacterial wool fabric of Example 1 was measured using an electronic fabric strength meter. The test sample size was 25 cm × 5 cm, the clamping length was set to 100 mm, and the rate was 250 mm / min. The test results are shown in Table 3.

[0071] Table 3 Changes in breaking strength of wool fabrics

[0072] Sample Breaking strength / N Original wool fabric 255.5 Pre-treated wool fabric 166.3 Antibacterial wool fabric 324.2

[0073] It can be clearly seen from Table 3 that the strength of wool fabrics has changed. After treatment with tricarboxyethylphosphine, the disulfide bonds are reduced to thiol groups, and the strength decreases from 255.5N to 166.3N. After antibacterial finishing, the strength increases to 324.2N, indicating that isocyanate (IPDI) as a cross-linking agent can not only successfully graft the antibacterial agent to the wool fabric, but also increase the strength of the wool fabric after finishing, thereby improving the breaking strength of the wool fabric after antibacterial finishing.

[0074] Test Example 4 Scanning Electron Microscope Analysis

[0075] In order to analyze the main changes in the surface of wool fibers after treatment at each stage, scanning electron microscopy tests were performed on the original wool fabric, pretreated wool fabric and antibacterial wool fabric in Example 1 to observe the changes in the surface morphology of the wool fabrics treated under different conditions. The test results are shown in Figure 2. Figure 3 shown. Figure 3 (a) is the original wool fabric; (b) is the pretreated wool fabric; (c) is the antibacterial wool fabric.

[0076] from Figure 3 As can be seen in (a), the scales on the surface of the wool fiber that has not been treated are neatly arranged and covered in layers; in (b), the edges of some scales of the wool fiber of the pretreated wool fabric are curled outward and fallen off, and there is a certain amount of damage; in (c), the clarity of the fiber surface of the antibacterial wool fabric is slightly blurred compared with (a) and (b), indicating that the surface is coated with the antibacterial agent shikimic acid.

[0077] Test Example 5 Fourier Transform Infrared Spectroscopy Analysis

[0078] The original wool fabric, pretreated wool fabric, and antibacterial wool fabric in Example 1 were tested using a Fourier transform infrared spectrometer, with a scanning range of 500 - 4000 cm -1 , 70 scans, and a resolution of 16 cm -1 . By analyzing the changes in the groups of the wool fabric through infrared spectroscopy, it was further determined whether the antibacterial agent shikimic acid was successfully grafted onto the wool fabric. The infrared spectra of the wool fabric under different treatment conditions are shown as Figure 4 follows. Figure 4 In (a) of Figure 4 , (I) is the original wool fabric of Example 1, (II) is the pretreated wool fabric of Example 1; (III) is the antibacterial wool fabric of Example 1;

[0079] In (b) of Figure 4 , the infrared spectra before and after the reaction of the finishing solution are shown. -1 As can be seen from -1 , two peaks at 3285 cm -1 and 3073 cm -1 appear in the infrared spectrum of the original wool fabric, which are the characteristic peaks of wool fibers. Compared with the pretreated wool fabric (II), there is an additional peak at 2564 cm -1 in II, which is the peak of the mercapto group, indicating that the disulfide bond in the wool fiber is reduced to a mercapto group after reduction. Compared with (I) and (II), the antibacterial wool fabric (III) shows three new peaks at 1306 cm -1 , 1110 cm

[0080] Figure 4 , and the characteristic peak of the mercapto group disappears, indicating that the two - NCO groups in the isocyanate react with - SH and shikimic acid respectively and the reaction is relatively complete, with no other new peaks appearing. -1 In (b) of

[0081] , (I) is the infrared spectrum of the finishing solution before the reaction, with the solvent being N,N - dimethylformamide. When the cross - linker IPDI, antibacterial agent shikimic acid, and catalyst dibutyltin dilaurate are added to the solvent, a peak appears at 2260 cm

[0082] which is the characteristic peak of the isocyanate group; (II) is the infrared spectrum of the above - mentioned finishing solution after reacting at 65 °C for 2 h. Compared with (I), the peak of the isocyanate group becomes smaller, indicating that the secondary isocyanate group of IPDI reacts with shikimic acid, but at the same time, the primary isocyanate group remains slightly, causing the primary isocyanate group to react with the reduced mercapto group on the wool fiber. Analysis of the test results of the weight gain rate in the orthogonal experiment of Test Example 6​​It is judged whether shikimic acid as an antibacterial agent is grafted onto the wool fabric based on the weight gain rate after antibacterial finishing of the pretreated wool fabric. Experiments are carried out according to the orthogonal test design table, and the results obtained from the orthogonal test are analyzed. The experimental results are shown in Table 4.

[0083] The calculation method of the weight gain rate of the wool fabric grafted with shikimic acid is shown in Equation (2):

[0084] G = (M - M0) / M0 × 100% Equation (2);

[0085] In Equation (2): G is the weight gain rate; M0 is the weight of the pretreated wool fabric; M is the weight of the antibacterial wool fabric.

[0086] Table 4 Orthogonal experimental results of the grafting weight gain rate of wool fabric

[0087]

[0088]

[0089] According to the magnitude of the range R in Table 4, the influence degree of each factor on the weight gain rate G is obtained. Among them, the influence degree from large to small is the time of addition reaction > the temperature of addition reaction > the dosage of catalyst triethylamine > the dosage of antibacterial agent shikimic acid > the dosage of crosslinking agent IPDI. According to the average value k of the experimental results and the five levels of each factor, an effect curve graph is made, and it is determined that the best process for antibacterial finishing is Example 1.

[0090] Test Example 7 Influence of the temperature of addition reaction on the weight gain rate

[0091] According to the analysis of the orthogonal test results, the effect curve graph of temperature and k value is as Figure 5 shown. It can be seen from Figure 5 that as the temperature increases, the k value continuously increases and reaches the highest at 65 °C, and then decreases. The molecular motion intensifies with the increase of temperature, which is beneficial to the reaction. However, when the temperature is too high, the wool fabric will be deformed, and at the same time, the structure will become loose, and part of the wool will fall off, resulting in a decrease in the grafting weight gain rate. Therefore, the temperature is selected at 65 °C as the best.

[0092] Test Example 8 Influence of the time of addition reaction on the weight gain rate

[0093] According to the analysis of the orthogonal test results, the effect curve graph of time and k value is as Figure 6 shown. It can be seen from Figure 6 that the k value continuously increases with the increase of the reaction time, and the k value is the largest at 120 min, and the weight gain rate is the largest at this time. This is because the IPDI molecule contains primary - NCO and secondary - NCO. Due to steric hindrance, the reaction activity of the secondary - NCO group is higher than that of the primary - NCO, and the cross - linking effect is good.

[0094] Test Example 9 Effect of Catalyst Amount on Weight Gain Rate

[0095] The catalyst for the click reaction is triethylamine, which is mainly used to catalyze the click chemistry reaction of thiol-isocyanate. According to the analysis of the orthogonal test results, the effect curve of catalyst dosage and k value is as follows: Figure 7 As shown. Figure 7 It can be seen that the k value increases with the increase of the catalyst. When the catalyst dosage is 0.075% of the solvent DMF, the weight gain rate is the highest. After that, as the dosage increases, the weight gain rate decreases. When the catalyst dosage is small, the click chemistry reaction of mercapto-isocyanate is incomplete, and the effect of the cross-linking antibacterial agent is poor. When the catalyst dosage is too large, shikimic acid will be catalytically oxidized to ketone, and the antibacterial agent attached to the wool fabric will be reduced, thereby reducing the weight gain rate.

[0096] Test Example 10 Effect of crosslinking agent dosage on weight gain rate

[0097] Isophorone diisocyanate (IPDI) was used as a crosslinking agent. Based on the results of the orthogonal test, the effect curve of the crosslinking agent dosage and k value was obtained. Figure 8 shown.

[0098] Depend on Figure 8 It can be seen that when the amount of cross-linking agent is 0.75g, the k value is the largest and the weight gain rate is the best, indicating that the functional base contained in 0.75g of IPDI just meets the grafting needs of the antibacterial agent, so the best amount of cross-linking agent IPDI is 0.75g.

[0099] Test Example 11 Effect of Antimicrobial Agent Dosage on Weight Gain Rate

[0100] According to the orthogonal test results, the antimicrobial dosage-k value effect curve is as follows: Figure 9 As shown. Figure 9 It can be seen that with the increase of the concentration of the antibacterial agent shikimic acid, the k value continues to increase, and the weight gain rate also continues to increase. When the antibacterial agent concentration is 19g / L, it tends to be stable, but the weight gain rate is smaller than when the shikimic acid concentration is 16g / L. When the shikimic acid concentration is too high, the weight gain rate decreases, and at the same time, the solution contains residual unreacted. In order to save costs, the best shikimic acid concentration is 16g / L.

[0101] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A method for antibacterial finishing of wool fabric based on click reaction, comprising the following steps: Placing the wool fabric in a reducing solution for a reduction reaction to obtain a pretreated wool fabric containing mercapto groups; Mixing shikimic acid, isophorone diisocyanate, a catalyst and an organic solvent for an addition reaction to obtain an antibacterial finishing solution; the organic solvent is N,N-dimethylformamide; the temperature of the addition reaction is 45-85 °C; the time of the addition reaction is 30-150 min; the catalyst is an organotin catalyst; Placing the pretreated wool fabric containing mercapto groups in the antibacterial finishing solution and carrying out a click reaction under the action of triethylamine to obtain an antibacterial wool fabric; the temperature of the click reaction is 20-50 °C; the time of the click reaction is 0.5-1.5 h.

2. The shikimic acid antibacterial finishing method for wool fabric according to claim 1, wherein The reducing agent in the reducing solution is tris(carboxyethyl)phosphine.

3. The method for antibacterial finishing of wool fabric with shikimic acid according to claim 1 or 2, characterized in that, The concentration of the reducing solution is 15-20 mmol / L.

4. The shikimic acid antibacterial finishing method for wool fabric according to claim 1, characterized in that, The temperature of the reduction reaction is 20-40 °C; the time of the reduction reaction is 3-6 h.

5. The shikimic acid antibacterial finishing method for wool fabric according to claim 1, characterized in that, The mass ratio of shikimic acid to isophorone diisocyanate is 10-22:1.74-8.

70.

6. The shikimic acid antibacterial finishing method for wool fabric according to claim 1, characterized in that, The mass of triethylamine is 0.05-0.15% of the mass of the organic solvent.

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