PBO fiber synergistically modified by polylysine and tannic acid and preparation method thereof

Abstract

The invention relates to the technical field of PBO fiber surface modification, in particular to a polylysine and tannic acid synergistically modified PBO fiber and a preparation method thereof.The preparation method comprises the steps that the PBO fiber is cut and then washed, then soaked in acetone to be subjected to ultrasonic cleaning and ethanol washing and then dried, the PBO fiber is put into a plasma treatment cavity, and plasma treatment is conducted to obtain activated PBO fiber; the preparation method comprises the following steps: soaking a PBO fiber in a FeCl3-TA (FeCl3-tannic acid) mixed solution, heating and stirring, cleaning and drying, soaking the PBO fiber in a polylysine (PLL) solution, heating and stirring for reaction, cleaning and drying to obtain the PLL-coated TA / PBO fiber. By adopting the steps, the surface of the PBO fiber is modified through plasma pretreatment, Fe-TA deposition and Schiff base reaction grafting of polylysine, and the surface activity of the PLL-coated TA / PBO fiber is enhanced compared with that of the PBO fiber under the condition that the mechanical property of the PBO fiber is not affected.

Description

Technical Field

[0001] This invention relates to the field of PBO fiber surface modification technology, and in particular to a polylysine and tannic acid synergistically modified PBO fiber and its preparation method. Background Technology

[0002] Polybenzoxazole (PBO) fiber, as a representative of current organic synthetic fibers, has a highly ordered liquid crystal structure formed by the coplanar arrangement of rigid benzoxazole rings and benzene rings in its molecular chain, endowing it with groundbreaking comprehensive properties: tensile strength up to 5.8 GPa, elastic modulus as high as 280–380 GPa, and density of only 1.54 g / cm³. 3 It also possesses exceptional heat resistance and a permanent flame-retardant property with a limiting oxygen index of 68%, thus having irreplaceable strategic value in multiple fields.

[0003] However, the lack of active functional groups and chemical inertness of PBO molecular chains result in extremely poor interfacial compatibility with matrices such as epoxy resins and bismaleimide resins. This manifests as a critical wetting angle >90° and an interfacial shear strength (IFSS) of less than 30 MPa. Under dynamic loads or humid and hot environments, it is highly susceptible to interfacial debonding and delamination failure, severely limiting its application potential in high-reliability structural components. Traditional modification methods all have significant drawbacks: strong acid / alkali etching, although it can introduce micropores (e.g., 98% H2SO4 treatment doubles the specific surface area), leads to a sharp drop in fiber strength of more than 40% (from 5.2 GPa to 3.1 GPa); plasma treatment is a highly efficient technique for activating the PBO fiber surface at room temperature, increasing surface active groups and roughness within seconds or minutes. Although it can temporarily improve surface polarity, the modified layer decays by 70% within 72 hours in air.

[0004] The numerous hydrophobic aromatic rings and phenolic hydroxyl groups in the tannic acid (TA) structure can interact with various molecules or groups, enabling self-polymerization under oxygen-rich and mildly alkaline conditions to form oligomers that deposit on solid supports. These oligomers can also chelate with metal ions, exhibiting excellent adhesion. However, PBO fibers have very few surface-active groups, resulting in a long deposition time. Therefore, how to maintain the surface activity of plasma-modified PBO fibers and shorten the deposition time requires further exploration by those skilled in the art. Summary of the Invention

[0005] The purpose of this invention is to provide a polylysine and tannic acid synergistic modification PBO fiber and its preparation method, which modifies the surface of PBO fiber by plasma pretreatment, Fe-TA deposition and Schiff base reaction grafting of polylysine.

[0006] To achieve the above objectives, the present invention provides a method for preparing polylysine and tannic acid synergistically modified PBO fibers, comprising the following steps:

[0007] S1. After cutting and rinsing the PBO fibers, immerse them in acetone for ultrasonic cleaning, rinse with ethanol, and dry to obtain clean PBO fibers.

[0008] S2. Place the clean PBO fibers obtained in S1 into the plasma treatment chamber and perform plasma treatment to obtain activated PBO fibers.

[0009] S3. The activated PBO fibers obtained in S2 are immersed in a FeCl3-TA mixed solution, heated and stirred, then washed and dried to obtain TA / PBO fibers.

[0010] S4. Immerse the TA / PBO fibers obtained in S3 into a polylysine solution (PLL), heat and stir to react, then wash and dry to obtain PLL@TA / PBO fibers.

[0011] Preferably, in S1, the ultrasonic cleaning time is 15-60 min, the drying temperature is 50-80℃, and the drying time is 3-8 h.

[0012] More preferably, in S1, the ultrasonic cleaning time is 20-40 min, the drying temperature is 65-75℃, and the drying time is 4-6 h.

[0013] More preferably, in S1, the ultrasonic cleaning time is 25-30 min, the drying temperature is 65-70℃, and the drying time is 5-6 h.

[0014] Preferably, in S1, the ratio of PBO fiber mass to acetone volume is 0.5-100 g / L.

[0015] More preferably, in S1, the ratio of PBO fiber mass to acetone volume is 10-80 g / L.

[0016] More preferably, in S1, the ratio of PBO fiber mass to acetone volume is 10-45 g / L.

[0017] Preferably, in S2, the plasma carrier gas is one or more of compressed air, oxygen, and nitrogen.

[0018] Preferably, in S2, the vacuum degree of plasma treatment is 5-100 Pa, the power is 50-300 W, and the time is 1-60 min.

[0019] More preferably, in S2, the vacuum degree of the plasma treatment is 10-50 Pa, the power is 100-200 W, and the time is 1-15 min.

[0020] More preferably, in S2, the vacuum degree of the plasma treatment is 15-20 Pa, the power is 120-180 W, and the time is 2-8 min.

[0021] Preferably, in S3, the FeCl3-TA mixed solution has a FeCl3 concentration of 0.1-0.5 mol / L, a TA concentration of 0.05-0.2 mol / L, and a pH value of 4.0-5.0.

[0022] More preferably, in S3, the FeCl3-TA mixed solution has a FeCl3 concentration of 0.15-0.35 mol / L, a TA (tannic acid) concentration of 0.08-0.15 mol / L, and a pH value of 4.4-4.7.

[0023] More preferably, in S3, the FeCl3-TA mixed solution has a FeCl3 concentration of 0.2-0.25 mol / L, a TA concentration of 0.1-0.13 mol / L, and a pH value of 4.5.

[0024] Preferably, in step S3, the heating and stirring temperature is 40-70℃, the stirring speed is 100-300rpm, and the stirring time is 1-3h.

[0025] More preferably, in S3, the heating and stirring temperature is 45-68°C, the stirring speed is 150-300 rpm, and the stirring time is 1.2-2.7 h.

[0026] More preferably, in S3, the heating and stirring temperature is 50-65℃, the stirring speed is 150-280rpm, and the stirring time is 1.2-2.5h.

[0027] Preferably, in step S4, polylysine is dissolved in a mixed solvent of ethanol and water, and the pH is adjusted to 8-8.5 to obtain a polylysine solution.

[0028] Preferably, in S4, the volume ratio of ethanol to water in the mixed solvent is 1:1, and the concentration of the polylysine solution is 0.02-0.2 mol / L.

[0029] More preferably, the concentration of the polylysine solution is 0.05-0.15 mol / L.

[0030] More preferably, the concentration of the polylysine solution is 0.05-0.1 mol / L.

[0031] Preferably, in step S4, the heating and stirring temperature is 40-70℃, the stirring speed is 150-300rpm, and the stirring time is 2-6h.

[0032] More preferably, in S4, the heating and stirring temperature is 40-70°C, the stirring speed is 175-275 rpm, and the stirring time is 3-4.5 h.

[0033] More preferably, in S4, the heating and stirring temperature is 40-70℃, the stirring speed is 200-270rpm, and the stirring time is 3.5-3.8h.

[0034] A polylysine and tannic acid synergistically modified PBO fiber, PLL@TA / PBO fiber, is prepared using the above-mentioned method for preparing a polylysine and tannic acid synergistically modified PBO fiber.

[0035] Therefore, the present invention employs the above-mentioned method for synergistic modification of PBO fiber with polylysine and tannins, and its preparation method has the following beneficial effects:

[0036] 1. This invention modifies the surface of PBO fibers by plasma pretreatment, Fe-TA deposition and Schiff base reaction grafting of polylysine, and enhances the surface activity of PLL@TA / PBO fibers compared to PBO fibers while keeping their mechanical properties unaffected.

[0037] 2. The preparation method provided by this invention is simple and efficient, effectively reduces the water contact angle of PBO fibers, requires no complex equipment, and is suitable for industrial production.

[0038] The technical solution of the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. Attached Figure Description

[0039] Figure 1 This is a schematic diagram of the preparation method of polylysine and tannic acid synergistically modified PBO fiber according to the present invention.

[0040] Figure 2 This is a water contact angle diagram of the PLL@TA / PBO fiber in Embodiment 1 of the present invention;

[0041] Figure 3 This is a water contact angle diagram of the PLL@TA / PBO fiber in Embodiment 2 of the present invention;

[0042] Figure 4 This is a water contact angle diagram of the PLL@TA / PBO fiber in Embodiment 3 of the present invention;

[0043] Figure 5 This is a water contact angle diagram of the PLL@TA / PBO fiber in Embodiment 4 of the present invention;

[0044] Figure 6 This is a water contact angle diagram of the PLL@TA / PBO fiber in Embodiment 5 of the present invention;

[0045] Figure 7 This is a water contact angle diagram of the PLL@TA / PBO fiber in Comparative Example 1 of the present invention;

[0046] Figure 8 These are combined SEM images of the original PBO fiber specimen, Comparative Example 1, and Example 1 of the present invention, wherein... Figure 8 In the image, 'a' represents the original SEM image of the PBO fiber. Figure 8 In the diagram, b is the SEM image of Comparative Example 1. Figure 8 In the image, 'c' represents the SEM image of Example 1.

[0047] Figure 9 These are combined SEM images from Examples 2-5, wherein, Figure 9 In the image, 'a' represents the SEM image of Example 2. Figure 9 In the image, b is the SEM image of Example 3. Figure 9 In the image, c represents the SEM image of Example 4. Figure 9 In the figure, d is the SEM image of Example 5. Detailed Implementation

[0048] The present invention will be further described below with reference to the accompanying drawings and embodiments. Unless otherwise defined, the technical or scientific terms used in this invention should be understood in their ordinary sense by those skilled in the art. The features mentioned above or in the specific examples mentioned in this invention can be combined arbitrarily, and these specific embodiments are only used to illustrate the invention and are not intended to limit the scope of the invention.

[0049] like Figure 1 As shown, this invention provides a method for preparing polylysine and tannic acid synergistically modified PBO fibers, comprising the following steps:

[0050] S1. After cutting and rinsing the PBO fibers, immerse them in acetone for ultrasonic cleaning, rinse with ethanol, and dry to obtain clean PBO fibers.

[0051] S2. Place the clean PBO fibers obtained in S1 into the plasma treatment chamber and perform plasma treatment to obtain activated PBO fibers.

[0052] S3. The activated PBO fibers obtained in S2 are immersed in a FeCl3-TA mixed solution, heated and stirred, then washed and dried to obtain TA / PBO fibers.

[0053] S4. Immerse the TA / PBO fibers obtained in S3 into a polylysine solution, heat and stir to react, then wash and dry to obtain PLL@TA / PBO fibers.

[0054] In some embodiments of the present invention, in step S1, the ultrasonic cleaning time is 15-60 minutes, the drying temperature is 50-80°C, and the drying time is 3-8 hours. Ultrasonic cleaning removes impurities and oil from the surface of the PBO fibers, while drying removes acetone and ethanol adsorbed on the fibers.

[0055] In some embodiments of the present invention, in step S1, the ratio of PBO fiber mass to acetone volume is 0.5-100 g / L. The PBO fibers are cleaned after being dispersed in acetone.

[0056] In some embodiments of the present invention, in step S2, the vacuum degree of the plasma treatment is 5-100 Pa, the power is 50-300 W, and the time is 1-60 min. High-energy particles in the plasma bombard the surface of the PBO fiber, introducing oxygen-containing functional groups such as hydroxyl and carboxyl groups, while simultaneously increasing surface roughness and improving the surface activity of the PBO fiber.

[0057] In some embodiments of the present invention, in S3, the FeCl3-TA mixed solution has a FeCl3 concentration of 0.1-0.5 mol / L, a TA concentration of 0.05-0.2 mol / L, and a pH value of 4.0-5.0. Utilizing Fe3... + The coordination interaction between TA (tannic acid) and PBO fibers forms a stable complex, constructing a uniform TA coating on the activated PBO fiber surface. This pH range is favorable for the dissociation of phenolic hydroxyl groups in TA, preventing Fe3+ ions from forming. + Hydrolysis precipitation.

[0058] In some embodiments of the present invention, in step S3, the heating and stirring temperature is 40-70°C, the stirring speed is 100-300 rpm, and the stirring time is 1-3 hours. This heating temperature accelerates the reaction rate, increasing Fe3+. + The Fe-TA reacts with TA on the surface of PBO fibers, uniformly depositing a dense Fe-TA layer while preventing TA oxidation and degradation at high temperatures. Stirring ensures uniform dispersion of PBO fibers in the FeCl3-TA mixed solution, preventing agglomeration and resulting in a uniform Fe-TA deposition layer thickness.

[0059] In some embodiments of the present invention, in step S4, polylysine (PLL) is dissolved in a mixed solvent of ethanol and water, and the pH is adjusted to 8-8.5 to obtain a polylysine solution. The ethanol-water mixed solvent system improves the wettability of TA / PBO fibers, and pH adjustment promotes the interaction between PLL and TA. Polylysine undergoes a Schiff base reaction with the active functional groups on the surface of the Fe-TA deposition layer, constructing a three-dimensional network interlocking structure.

[0060] In some embodiments of the present invention, in step S4, the volume ratio of ethanol to water in the mixed solvent is 1:1, and the concentration of the polylysine solution is 0.02-0.2 mol / L. This ensures good dissolution of PLL while effectively reducing the surface tension of the solvent and improving the wettability of TA / PBO fibers.

[0061] In some embodiments of the present invention, in step S4, the heating and stirring temperature is 40-70°C, the stirring speed is 150-300 rpm, and the stirring time is 2-6 hours. Stirring ensures that the TA / PBO fibers are uniformly dispersed in the polylysine solution, promoting a uniform reaction between the PLL and the Fe-TA deposition layer.

[0062] Example 1

[0063] S1. Cut 1g of PBO fiber to 8cm, rinse with deionized water, then immerse in 100mL of acetone for ultrasonic cleaning for 30min, rinse with ethanol, and dry at 60℃ for 6h to obtain clean PBO fiber.

[0064] S2. Place the clean PBO fibers obtained in S1 into a plasma treatment chamber. The vacuum degree of the plasma treatment is 15 Pa, the power is 120 W, the time is 8 min, and the carrier gas is oxygen to obtain activated PBO fibers.

[0065] S3. Weigh 5.41g FeCl3·6H2O and 10.0g TA, add water and stir until completely dissolved to prepare 100ml FeCl3-TA mixed solution. Immerse the activated PBO fibers obtained in S2 in the FeCl3-TA mixed solution. The pH of the FeCl3-TA mixed solution is 4.5. Heat and stir at 60℃ for 1.2h at a stirring speed of 150rpm. After washing, dry at 60℃ for 6h to obtain TA / PBO fibers.

[0066] S4. Weigh 1.45g of polylysine and dissolve it in a mixed solvent of ethanol and water (volume ratio of ethanol to water: 1:1) to obtain a polylysine solution. Adjust the pH of the polylysine solution to 8.5 using dilute sodium hydroxide solution. Immerse the TA / PBO fibers obtained in S3 into the polylysine solution, heat and stir at 60℃ for 3 hours at a stirring speed of 250 rpm, wash and dry for 6 hours to obtain PLL@TA / PBO fibers.

[0067] Example 2

[0068] S1. Cut 1g of PBO fiber to 8cm, rinse with deionized water, then immerse in 100mL of acetone for ultrasonic cleaning for 30min, rinse with ethanol, and dry at 60℃ for 6h to obtain clean PBO fiber.

[0069] S2. Place the clean PBO fibers obtained in S1 into a plasma treatment chamber. The vacuum degree of the plasma treatment is 15 Pa, the power is 130 W, the time is 2 min, and the carrier gas is oxygen to obtain activated PBO fibers.

[0070] S3. Weigh 5.41g FeCl3·6H2O and 10.0g TA, add water and stir until completely dissolved to prepare 100ml FeCl3-TA mixed solution. Immerse the activated PBO fibers obtained in S2 in the FeCl3-TA mixed solution. The pH of the FeCl3-TA mixed solution is 4.5. Heat and stir at 60℃ for 1.2h at a stirring speed of 150rpm. After washing, dry at 65℃ for 6h to obtain TA / PBO fibers.

[0071] S4. Weigh 1.25g of polylysine and dissolve it in a mixed solvent of ethanol and water (volume ratio of ethanol to water 1:1) to obtain a polylysine solution. Adjust the pH of the polylysine solution to 8.5 using dilute sodium hydroxide solution. Immerse the TA / PBO fiber obtained in S3 into the polylysine solution, heat and stir at 60℃ for 3 hours at a stirring speed of 250 rpm, wash and dry for 6 hours to obtain PLL@TA / PBO fiber.

[0072] Example 3

[0073] S1. Cut 1g of PBO fiber to 8cm, rinse with deionized water, then immerse in 100mL of acetone for ultrasonic cleaning for 30min, rinse with ethanol, and dry at 60℃ for 6h to obtain clean PBO fiber.

[0074] S2. Place the clean PBO fibers obtained in S1 into a plasma treatment chamber. The vacuum degree of the plasma treatment is 15 Pa, the power is 120 W, the time is 8 min, and the carrier gas is oxygen to obtain activated PBO fibers.

[0075] S3. Weigh 5.41g FeCl3·6H2O and 10.0g TA, add water and stir until completely dissolved to prepare 100mL FeCl3-TA mixed solution. Immerse the activated PBO fibers obtained in S2 in the FeCl3-TA mixed solution. The pH of the FeCl3-TA mixed solution is 4.5. Heat and stir at 60℃ for 1.2h at a stirring speed of 150rpm. After washing, dry at 65℃ for 6h to obtain TA / PBO fibers.

[0076] S4. Weigh 1.45g of polylysine and dissolve it in a mixed solvent of ethanol and water (volume ratio of ethanol to water: 1:1) to obtain a polylysine solution. Adjust the pH of the polylysine solution to 8.5 using dilute sodium hydroxide solution. Immerse the TA / PBO fibers obtained in S3 into the polylysine solution, heat and stir at 60℃ for 3 hours at a stirring speed of 250 rpm, wash and dry for 6 hours to obtain PLL@TA / PBO fibers.

[0077] Example 4

[0078] S1. Cut 1g of PBO fiber to 8cm, rinse with deionized water, then immerse in 100mL of acetone for ultrasonic cleaning for 30min, rinse with ethanol, and dry at 60℃ for 6h to obtain clean PBO fiber.

[0079] S2. Place the clean PBO fibers obtained in S1 into a plasma treatment chamber. The vacuum degree of the plasma treatment is 15 Pa, the power is 120 W, the time is 2 min, and the carrier gas is oxygen to obtain activated PBO fibers.

[0080] S3. Weigh 4.05g FeCl3·6H2O and 8.0g TA, add water and stir until completely dissolved to prepare 100mL FeCl3-TA mixed solution. Immerse the activated PBO fibers obtained in S2 in the FeCl3-TA mixed solution. The pH of the FeCl3-TA mixed solution is 4.5. Heat and stir at 60℃ for 2h at a stirring speed of 200rpm. After washing, dry at 65℃ for 6h to obtain TA / PBO fibers.

[0081] S4. Weigh 2.32g of polylysine and dissolve it in a mixed solvent of ethanol and water (volume ratio of ethanol to water 1:1) to obtain a polylysine solution. Adjust the pH of the polylysine solution to 8.5 using dilute sodium hydroxide solution. Immerse the TA / PBO fibers obtained in S3 into the polylysine solution, heat and stir at 50°C for 3 hours at a stirring speed of 250 rpm, wash and dry for 6 hours to obtain PLL@TA / PBO fibers.

[0082] Example 5

[0083] S1. Cut 1g of PBO fiber to 8cm, rinse with deionized water, then immerse in 100mL of acetone for ultrasonic cleaning for 20min, rinse with ethanol, and dry at 60℃ for 6h to obtain clean PBO fiber.

[0084] S2. Place the clean PBO fibers obtained in S1 into a plasma treatment chamber. The vacuum degree of the plasma treatment is 20 Pa, the power is 200 W, the time is 2 min, and the carrier gas is oxygen to obtain activated PBO fibers.

[0085] S3. Weigh 5.95g FeCl3·6H2O and 15.0g TA, add water and stir until completely dissolved to prepare a 100mL FeCl3-TA mixed solution. Immerse the activated PBO fibers obtained in S2 in the FeCl3-TA mixed solution (pH 4.5), heat and stir at 60℃ for 1.5h at a stirring speed of 200rpm, wash, and then dry at 65℃ for 6h to obtain TA / PBO fibers.

[0086] S4. Weigh 1.45g of polylysine and dissolve it in a mixed solvent of ethanol and water (volume ratio of ethanol to water: 1:1) to obtain a polylysine solution. Adjust the pH of the polylysine solution to 8.5 using dilute sodium hydroxide solution. Immerse the TA / PBO fibers obtained in S3 into the polylysine solution, heat and stir at 60℃ for 3 hours at a stirring speed of 250 rpm, wash and dry for 6 hours to obtain PLL@TA / PBO fibers.

[0087] Comparative Example 1

[0088] S1. Cut 1g of PBO fiber to 8cm, rinse with deionized water, then immerse in 100mL of acetone for ultrasonic cleaning for 30min, rinse with ethanol, and dry at 60℃ for 6h to obtain clean PBO fiber.

[0089] S2. Weigh 4.05g FeCl3·6H2O and 8.0g TA, add water and stir until completely dissolved to prepare 100ml FeCl3-TA mixed solution. Immerse the clean PBO fibers obtained in S1 in the FeCl3-TA mixed solution. The pH of the FeCl3-TA mixed solution is 4.5. Heat and stir at 60℃ for 2h at a stirring speed of 200rpm. After washing, dry at 65℃ for 6h to obtain TA / PBO fibers.

[0090] S3. Weigh 2.32g of polylysine and dissolve it in a mixed solvent of ethanol and water (volume ratio of ethanol to water 1:1) to obtain a polylysine solution. Adjust the pH of the polylysine solution to 8.5 using dilute sodium hydroxide solution. Immerse the TA / PBO fiber obtained in S2 into the polylysine solution, heat and stir at 50℃ for 3 hours at a stirring speed of 250 rpm, wash and dry for 6 hours to obtain PLL@TA / PBO fiber.

[0091] Test case

[0092] a. Water contact angle test

[0093] (1) Arrange the fiber to be tested in a single bundle and spread it evenly on the surface of the glass slide with double-sided tape. Place the glass slide with the fiber to be tested on the static water contact angle detection platform.

[0094] (2) Use a syringe to gently drop 2 μL of water onto the surface of the fiber to be tested. After the water droplet remains stationary on the surface of the fiber, use a high-speed camera to record the shape of the water droplet.

[0095] (3) The static contact angle is calculated by computer fitting; at least three different positions are taken for each sample to ensure the uniformity of crosslinking at different positions of the fiber to be tested, the average value is taken and the standard deviation is calculated to determine its final value.

[0096] The water contact angles of the PLL@TA / PBO fibers in Examples 1-5 and the PLL@TA / PBO fiber in Comparative Example 1 were tested using the above-described testing method. The results are as follows: Figure 2-7 As shown, the water contact angle in Example 1 is 71.1°, in Example 2 it is 85.7°, in Example 3 it is 72.1°, in Example 4 it is 95.0°, in Example 5 it is 74.6°, and in Comparative Example 1 it is 112.4°. The comparison shows that the hydrophilicity of Examples 1-5 is superior to that of Comparative Example 1.

[0097] b. SEM testing

[0098] The surface morphology of the obtained PBO fibers, Comparative Example 1, and PLL@TA / PBO fibers in Examples 1-5 was observed using scanning electron microscopy. Figure 8 As can be seen from the original PBO fiber and Comparative Example 1, in Example 1, a uniform coating was formed on the surface of the PBO fiber. Figure 9 It can be seen that the PLL@TA / PBO fibers prepared in Examples 2-4 also form a coating.

[0099] Therefore, the present invention employs the above-mentioned method for synergistic modification of PBO fiber with polylysine and tannic acid, and the modification of PBO fiber surface is achieved by plasma pretreatment, Fe-TA deposition and Schiff base reaction grafting of polylysine. Under the condition that its mechanical properties are not affected, the surface activity of PLL@TA / PBO fiber is enhanced compared with PBO fiber.

[0100] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can still be made to the technical solutions of the present invention, and these modifications or equivalent substitutions cannot cause the modified technical solutions to deviate from the spirit and scope of the technical solutions of the present invention.

Claims

1. A method for preparing polylysine and tannic acid synergistically modified PBO fibers, characterized in that: Includes the following steps, S1. After cutting and rinsing the PBO fibers, immerse them in acetone for ultrasonic cleaning, rinse with ethanol, and dry to obtain clean PBO fibers. S2. Place the clean PBO fibers obtained in S1 into the plasma treatment chamber and perform plasma treatment to obtain activated PBO fibers. S3. The activated PBO fibers obtained in S2 are immersed in a FeCl3-TA mixed solution, heated and stirred, then washed and dried to obtain TA / PBO fibers. S4. Immerse the TA / PBO fibers obtained in S3 into a polylysine solution, heat and stir to react, then wash and dry to obtain PLL@TA / PBO fibers.

2. The method for preparing polylysine and tannic acid synergistically modified PBO fiber according to claim 1, characterized in that: In S1, the ultrasonic cleaning time is 15-60 minutes, the drying temperature is 50-80℃, and the drying time is 3-8 hours.

3. The method for preparing polylysine and tannic acid synergistically modified PBO fiber according to claim 1, characterized in that: In S1, the ratio of PBO fiber mass to acetone volume is 0.5-100 g / L.

4. The method for preparing polylysine and tannic acid synergistically modified PBO fiber according to claim 1, characterized in that: In S2, the vacuum degree of plasma treatment is 5-100 Pa, the power is 50-300 W, and the time is 1-60 min.

5. The method for preparing polylysine and tannic acid synergistically modified PBO fiber according to claim 1, characterized in that: In S3, the FeCl3-TA mixed solution has a FeCl3 concentration of 0.1-0.5 mol / L and a TA concentration of 0.05-0.2 mol / L, and the pH value of the FeCl3-TA mixed solution is 4.0-5.

0.

6. The method for preparing polylysine and tannic acid synergistically modified PBO fiber according to claim 1, characterized in that: In S3, the heating and stirring temperature is 40-70℃, the stirring speed is 100-300rpm, and the stirring time is 1-3h.

7. The method for preparing polylysine and tannic acid synergistically modified PBO fiber according to claim 1, characterized in that: In S4, polylysine is dissolved in a mixed solvent of ethanol and water, and the pH is adjusted to 8-8.5 to obtain a polylysine solution.

8. The method for preparing polylysine and tannic acid synergistically modified PBO fiber according to claim 7, characterized in that: In S4, the volume ratio of ethanol to water in the mixed solvent is 1:1, and the concentration of the polylysine solution is 0.02-0.2 mol / L.

9. The method for preparing polylysine and tannic acid synergistically modified PBO fiber according to claim 1, characterized in that: In S4, the heating and stirring temperature is 40-70℃, the stirring speed is 150-300rpm, and the stirring time is 2-6h.

10. A polylysine and tannic acid synergistically modified PBO fiber, characterized in that: PLL@TA / PBO fibers are prepared using the method for preparing polylysine and tannic acid synergistically modified PBO fibers as described in any one of claims 1-9.

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