Antibacterial and detoxicating modified polyester fiber and preparation method thereof

Abstract

The invention relates to an antibacterial and detoxicating modified polyester fiber and a preparation method thereof, and belongs to the technical field of polyester fiber preparation. In the process of preparing the antibacterial and detoxicating modified polyester fiber, the graphene oxide, the zinc nitrate hexahydrate, the tebuconazole, the dioctadecyl dimethyl ammonium chloride and other substances remarkably enhance the overall antibacterial and detoxicating performance through the synergistic effect, and the synergistic effect is reflected in complementation and enhancement of different antibacterial components; in addition, in the interaction between the materials and base materials such as polyurethane, the multi-layer and multi-target antibacterial network provides powerful support for preparation of high-performance antibacterial detoxification materials; the water vapor treatment, the ozone treatment and the nitrogen treatment respectively play roles in softening the fibers, sterilizing, drying and removing residual gas in the process of preparing the antibacterial and detoxicating modified polyester fibers, and the steps jointly ensure that the modified polyester fibers have good antibacterial and detoxicating performance and stable physical performance.

Description

Technical Field

[0001] The invention belongs to the technical field of polyester fiber preparation, and relates to an antibacterial and detoxifying modified polyester fiber and a preparation method thereof. Background Art

[0002] Antibacterial and detoxifying modified polyester fiber is made by adding antibacterial and detoxifying agents or performing special treatments during the preparation process of polyester fiber, so that the fiber has the ability to inhibit or kill harmful microorganisms such as bacteria and viruses.

[0003] Antibacterial and detoxifying modified polyester fiber has broad application prospects in the fields of textiles, medical treatment, health care, etc. For example, in the field of textiles, it can be used to make antibacterial and deodorizing underwear, socks, sportswear, etc.; in the medical field, it can be used to make surgical gowns, surgical covers, masks, medical bandages, etc. to reduce the risk of cross infection.

[0004] This type of fiber not only retains the original excellent properties of polyester fiber such as wear resistance, chemical corrosion resistance, water absorption, quick drying, etc., but also significantly enhances its health care function. Summary of the invention

[0005] The object of the present invention is to provide an antibacterial and detoxifying modified polyester fiber and a preparation method thereof, which has the characteristics of good detoxifying and antibacterial performance.

[0006] The purpose of the present invention can be achieved through the following technical solutions: A method for preparing antibacterial and detoxifying modified polyester fiber, the process of the method for preparing antibacterial and detoxifying modified polyester fiber is as follows: S1: dissolving graphene oxide in deionized water to obtain a graphene oxide solution with a mass fraction of 30-50%, adding 3-5 wt% zinc nitrate hexahydrate to the graphene solution, and stirring at a speed of 150 r / min for 2 h to obtain a mixed solution A; S2: Tebuconazole and dioctadecyl dimethyl ammonium chloride were mixed in a mass ratio of 2:1, dispersed in an ethanol solution, stirred at a speed of 150-180 r / min, and the temperature was slowly raised from room temperature to 40°C while stirring for 1-2 h to obtain a mixed solution B; S3: heating the polyurethane to 170-190°C, stirring at a speed of 200 r / min for 0.5-1 h, mixing the molten polyurethane and deionized water at a volume ratio of 2:1 to obtain a polyurethane solution, and cooling the solution to 40°C at a speed of 5°C / min, stirring the solution at a speed of 150 r / min for 0.5 h at 40°C; S4: Add mixed solution A and mixed solution B to the polyurethane solution at 40° C., wherein the volume ratio of the polyurethane solution, the mixed solution A and the mixed solution B is 2:1:1, and then add 1wt% of a dispersant and 0.5wt% of a silane coupling agent, and continue to stir at a speed of 250 r / min for 3-4 hours to obtain a mixed solution C; S5: passing water vapor into the polyester fiber for heat treatment, then passing ozone for sterilization, and then passing nitrogen gas at 70° C. for 4 to 6 hours after the sterilization to obtain dry polyester fiber; S6: soaking the dried polyester fiber in the mixed solution C, heating it to 45-55° C., ultrasonicating it for 3-4 hours, taking it out, and drying the polyester fiber using a laser drying method to obtain the antibacterial and detoxifying modified polyester fiber.

[0007] Furthermore, the mass fraction of the ethanol solution in S2 is 60-80%.

[0008] Furthermore, the slow heating rate in S2 is 2°C / min.

[0009] Furthermore, the dispersant in S4 is polyethylene glycol, and its number average molecular weight is 2000-4000.

[0010] Furthermore, the silane coupling agent in S4 is one or more of vinyltriethoxysilane, γ-aminopropyltriethoxysilane, and vinyltrimethoxysilane.

[0011] Furthermore, the parameters of the water vapor heat treatment in S5 are as follows: treatment time of 0.5-2 h, treatment temperature of 200-300° C., and water vapor introduction rate of 1.5-2 kg / h.

[0012] Furthermore, the flow rate of ozone in S5 is 20 m / s, and the purge time is 1 h.

[0013] Furthermore, the nitrogen in S5 has an inlet flow rate of 15 m / s.

[0014] Furthermore, the parameters of the laser drying method in S6 are: laser power 300 W, temperature 50° C., and irradiation time 30 min.

[0015] Graphene oxide has good antibacterial properties, while zinc nitrate hexahydrate can serve as a synergist for antimicrobial agents or provide other functions. Dissolving them in deionized water can ensure their uniform distribution in subsequent steps; after the polyurethane is heated to a molten state, it can be mixed with deionized water to form a stable solution. This solution can be used as a coating substrate in subsequent steps to firmly attach the antimicrobial agent to the polyester fiber; mixing all antimicrobial ingredients and the polyurethane solution together can ensure their uniform distribution on the polyester fiber. Polyurethane, as a coating substrate, can firmly attach the antimicrobial agent to the fiber, improving its durability and antimicrobial effect; By introducing water vapor for heat treatment, impurities and oil stains on the surface of polyester fibers can be removed. By introducing ozone for sterilization, bacteria and viruses on the fibers can be further killed. Finally, by introducing nitrogen for purging, residual ozone and moisture can be removed to obtain dry polyester fibers.

[0016] The dried polyester fiber is immersed in the mixed solution C, so that the antibacterial and detoxifying modifier can be evenly attached to the fiber. Heating and ultrasonic treatment can promote the penetration and fixation of the modifier into the fiber. Finally, the laser drying method can quickly remove the moisture on the fiber surface and further fix the modifier, thereby obtaining a modified polyester fiber with significant antibacterial and detoxifying effects.

[0017] In the present invention, graphene oxide, zinc nitrate hexahydrate, tebuconazole and dioctadecyl dimethyl ammonium chloride are used in combination, so that the prepared modified polyester fiber has better antibacterial and detoxification effects.

[0018] Graphene oxide has sharp edges and planes that can pierce the bacterial cell membrane, causing bacterial death; graphene oxide's large specific surface area and rich functional groups enable it to interact with multiple sites on the bacterial cell surface, thereby enhancing the antibacterial effect.

[0019] Zinc ions are the main antibacterial component released by zinc nitrate hexahydrate. They can combine with various enzymes in bacterial cells and inhibit their activity, thereby interfering with the normal physiological functions of bacteria. In addition, zinc ions can also destroy the replication and transcription process of bacterial DNA, further inhibiting the growth and reproduction of bacteria.

[0020] Graphene oxide pierces the bacterial cell membrane with its sharp edges, causing physical damage; while zinc ions released by zinc nitrate hexahydrate can enter bacterial cells, inhibit enzyme activity, interfere with DNA replication and other processes, causing chemical inhibition. The combination of the two acts on bacteria from both inside and outside, enhancing the antibacterial effect; the large specific surface area and rich functional groups of graphene oxide may help zinc ions to better adsorb on its surface, thereby promoting the penetration of zinc ions into bacterial cells, improving the utilization rate of zinc ions and antibacterial efficiency.

[0021] Tebuconazole is a broad-spectrum fungicide that can inhibit the biosynthesis of ergosterol in pathogenic bacteria and destroy the cell membrane structure of the bacteria, thereby achieving a bactericidal effect. Tebuconazole can also achieve a detoxification effect by destroying the structure of virus particles or interfering with their replication process.

[0022] Graphene oxide physically destroys the bacterial cell membrane, while tebuconazole inhibits the biosynthesis process of pathogens. The combination of the two forms a multiple bactericidal mechanism that can kill bacteria more effectively. Tebuconazole helps stabilize the dispersion state of graphene oxide in the solution and prevent it from agglomerating, thereby maintaining its good antibacterial activity.

[0023] As a surfactant, dioctadecyl dimethyl ammonium chloride can reduce the surface tension of water, making it easier for antibacterial ingredients to penetrate into bacterial cells. It may also enhance the antibacterial effect by destroying the integrity of bacterial cell membranes.

[0024] As a surfactant, dioctadecyl dimethyl ammonium chloride can reduce the surface tension of water, promote the adsorption and penetration of antibacterial ingredients such as tebuconazole on the surface of bacterial cells, and improve the utilization rate and antibacterial effect of antibacterial ingredients. Tebuconazole has broad-spectrum bactericidal properties, and dioctadecyl dimethyl ammonium chloride may further improve the overall broad-spectrum antibacterial performance through its antibacterial effect or enhance the scope of action of other antibacterial ingredients.

[0025] Graphene oxide, zinc nitrate hexahydrate, tebuconazole and dioctadecyl dimethyl ammonium chloride each have different antibacterial mechanisms and targets. When they work together, they can form a multi-level, multi-target antibacterial network, significantly improving the antibacterial and detoxification effects. Polyurethane, as a coating substrate, can firmly attach the antibacterial ingredients to polyester fibers to prevent them from falling off or inactivating during use, thereby maintaining long-term antibacterial and detoxification effects. At the same time, the addition of polyurethane may also improve the physical properties and durability of the fibers.

[0026] Steam heat treatment can soften polyester fibers, improve their hygroscopicity, and help with subsequent antibacterial and detoxification modification treatments. At the same time, steam can also help remove some impurities and oil stains on the fiber surface, creating better conditions for subsequent sterilization treatments; ozone is a strong oxidant with a broad-spectrum bactericidal effect. Passing ozone into polyester fibers can effectively kill bacteria and viruses on the fiber surface, further improving the hygienic properties of the fibers. Ozone can destroy the cell membrane and DNA of microorganisms, thereby achieving a sterilization effect; after the sterilization treatment, 70°C nitrogen is passed in for purging, which mainly plays the role of drying and removing residual gas. Nitrogen is an inert gas and will not react chemically with polyester fibers. At the same time, its purging action can take away moisture and residual ozone on the fiber surface, allowing the fibers to dry quickly and prevent the residual gas from affecting the fiber properties. In addition, a temperature of 70°C also helps to accelerate the fiber drying process.

[0027] Beneficial effects of the present invention: (1) In the process of preparing antibacterial and detoxifying modified polyester fibers, graphene oxide, zinc nitrate hexahydrate, tebuconazole and dioctadecyl dimethyl ammonium chloride significantly enhanced the overall antibacterial and detoxifying performance through synergistic effects. This synergistic effect is not only reflected in the complementarity and enhancement between different antibacterial components, but also in the interaction between them and substrates such as polyurethane. This multi-level, multi-target antibacterial network provides strong support for the preparation of high-performance antibacterial and detoxifying materials. (2) The treatments of water vapor, ozone and nitrogen play the roles of softening the fibers, sterilizing and drying to remove residual gases respectively in the process of preparing antibacterial and detoxifying modified polyester fibers. These steps together ensure that the modified polyester fibers have good antibacterial and detoxifying properties and stable physical properties. DETAILED DESCRIPTION

[0028] In order to further illustrate the technical means and effects adopted by the present invention to achieve the predetermined invention purpose, the specific implementation methods, structures, features and effects of the present invention are described in detail below in combination with the embodiments.

[0029] Example 1

[0030] S1: dissolving graphene oxide in deionized water to obtain a graphene oxide solution with a mass fraction of 40%, adding 4wt% zinc nitrate hexahydrate to the graphene solution, and stirring at a speed of 150r / min for 2h to obtain a mixed solution A; S2: Tebuconazole and dioctadecyl dimethyl ammonium chloride were mixed in a mass ratio of 2:1, dispersed in an ethanol solution with a mass fraction of 70%, stirred at a speed of 160 r / min, and slowly heated from room temperature to 40°C while stirring, with a heating rate of 2°C / min and a stirring time of 1 h to obtain a mixed solution B; S3: The polyurethane was heated to 180°C, stirred at a speed of 200 r / min for 0.5 h, the molten polyurethane and deionized water were mixed at a volume ratio of 2:1 to obtain a polyurethane solution, and the temperature was reduced to 40°C at a speed of 5°C / min, and stirred at a speed of 150 r / min for 0.5 h at 40°C; S4: adding mixed solution A and mixed solution B to the polyurethane solution at 40° C., wherein the volume ratio of the polyurethane solution, the mixed solution A and the mixed solution B is 2:1:1, and then adding 1 wt % of polyethylene glycol 2000 and 0.5 wt % of vinyl triethoxysilane, and continuing to stir at a speed of 250 r / min for 3 h to obtain a mixed solution C; S5: introducing water vapor into the polyester fiber for heat treatment, the parameters of the water vapor heat treatment are as follows: treatment time of 1 hour, treatment temperature of 250° C., water vapor introduction amount of 1.5 kg / h, and then introducing ozone for sterilization treatment, the ozone introduction flow rate is 20 m / s, the purge time is 1 hour, and after the sterilization treatment, 70° C. nitrogen is introduced for 6 hours, and the nitrogen introduction flow rate is 15 m / s to obtain dry polyester fiber; S6: Immerse the dried polyester fiber in mixture C, heat it to 50°C, and ultrasonicate it for 6 hours. After taking it out, use a laser drying method to dry the polyester fiber. The parameters of the laser drying method are laser power 300W, temperature 50°C, and irradiation time 30 minutes to obtain the antibacterial and detoxification modified polyester fiber.

[0031] Example 2

[0032] S1: dissolving graphene oxide in deionized water to obtain a graphene oxide solution with a mass fraction of 30%, then adding 3wt% zinc nitrate hexahydrate to the graphene solution, stirring at a speed of 150r / min for 2h, and obtaining a mixed solution A; S2: Tebuconazole and dioctadecyl dimethyl ammonium chloride were mixed in a mass ratio of 2:1, dispersed in an ethanol solution with a mass fraction of 60%, stirred at a speed of 150 r / min, and slowly heated from room temperature to 40°C while stirring, with a heating rate of 2°C / min and a stirring time of 2 h to obtain a mixed solution B; S3: The polyurethane was heated to 170°C, stirred at a speed of 200 r / min for 1 h, the molten polyurethane and deionized water were mixed at a volume ratio of 2:1 to obtain a polyurethane solution, and the temperature was reduced to 40°C at a speed of 5°C / min, and stirred at a speed of 150 r / min for 0.5 h at 40°C; S4: adding mixed solution A and mixed solution B to the polyurethane solution at 40° C., wherein the volume ratio of the polyurethane solution, the mixed solution A and the mixed solution B is 2:1:1, and then adding 1wt% polyethylene glycol 4000 and 0.5wt% γ-aminopropyltriethoxysilane, and continuing to stir at a speed of 250r / min for 4h to obtain a mixed solution C; S5: introducing water vapor into the polyester fiber for heat treatment, the parameters of the water vapor heat treatment are as follows: treatment time of 0.5 h, treatment temperature of 300° C., water vapor introduction amount of 2 kg / h, and then introducing ozone for sterilization treatment, the ozone introduction flow rate is 20 m / s, the purge time is 1 h, and after the sterilization treatment, 70° C. nitrogen is introduced for 4 h, and the nitrogen introduction flow rate is 15 m / s to obtain dry polyester fiber; S6: Immerse the dried polyester fiber in mixture C, heat it to 60°C, and ultrasonicate it for 3 hours. After taking it out, use a laser drying method to dry the polyester fiber. The parameters of the laser drying method are laser power 300W, temperature 50°C, and irradiation time 30 minutes to obtain the antibacterial and detoxification modified polyester fiber.

[0033] Example 3

[0034] S1: dissolving graphene oxide in deionized water to obtain a graphene oxide solution with a mass fraction of 50%, then adding 5wt% zinc nitrate hexahydrate to the graphene solution, stirring at a speed of 150r / min for 2h, and obtaining a mixed solution A; S2: Tebuconazole and dioctadecyl dimethyl ammonium chloride were mixed in a mass ratio of 2:1, dispersed in an ethanol solution with a mass fraction of 80%, stirred at a speed of 180 r / min, and slowly heated from room temperature to 40°C while stirring, with a heating rate of 2°C / min and a stirring time of 2 h to obtain a mixed solution B; S3: The polyurethane was heated to 190°C, stirred at a speed of 200 r / min for 1 hour, the molten polyurethane and deionized water were mixed at a volume ratio of 2:1 to obtain a polyurethane solution, and the temperature was reduced to 40°C at a speed of 5°C / min, and stirred at a speed of 150 r / min for 0.5 hour at 40°C; S4: adding mixed solution A and mixed solution B to the polyurethane solution at 40° C., wherein the volume ratio of the polyurethane solution, the mixed solution A and the mixed solution B is 2:1:1, and then adding 1 wt % of polyethylene glycol 2000 and 0.5 wt % of vinyl trimethoxy silane, and continuing to stir at a speed of 250 r / min for 4 h to obtain a mixed solution C; S5: introducing water vapor into the polyester fiber for heat treatment, the parameters of the water vapor heat treatment are as follows: treatment time of 2 hours, treatment temperature of 200° C., water vapor introduction amount of 2 kg / h, and then introducing ozone for sterilization treatment, the ozone introduction flow rate is 20 m / s, the purge time is 1 hour, and after the sterilization treatment, 70° C. nitrogen is introduced for 6 hours, and the nitrogen introduction flow rate is 15 m / s, to obtain dry polyester fiber; S6: Immerse the dried polyester fiber in mixture C, heat it to 60°C, and ultrasonicate it for 3 hours. After taking it out, use a laser drying method to dry the polyester fiber. The parameters of the laser drying method are laser power 300W, temperature 50°C, and irradiation time 30 minutes to obtain the antibacterial and detoxification modified polyester fiber.

[0035] Comparative Example 1 In this comparative example, graphene oxide was not added during the preparation process, and the remaining steps were consistent with those in Example 1.

[0036] Comparative Example 2 In this comparative example, zinc nitrate hexahydrate was not added during the preparation process, and the remaining steps were consistent with those of Example 1.

[0037] Comparative Example 3 In this comparative example, tebuconazole was not added during the preparation process, and the remaining steps were consistent with those in Example 1.

[0038] Comparative Example 4 In this comparative example, no dioctadecyl dimethyl ammonium chloride was added during the preparation process, and the remaining steps were consistent with those of Example 1.

[0039] Comparative Example 5 In this comparative example, the polyester fiber is not subjected to heat treatment with steam during the preparation process, and the remaining steps are consistent with those of Example 1.

[0040] Comparative Example 6 In this comparative example, the polyester fiber was not treated with ozone during the preparation process, and the remaining steps were consistent with those in Example 1.

[0041] The performance of the embodiments and comparative examples was tested, and the antibacterial rate (%) was tested according to GB / T 20944.3-2008. The experimental results are summarized in the following table:

[0042] Experimental data show that graphene oxide, zinc nitrate hexahydrate, tebuconazole and dimethyl disodium octadecyl ammonium chloride all make the modified polyester fiber have better antibacterial and detoxification effects. The addition of graphene oxide, zinc nitrate hexahydrate and dimethyl disodium octadecyl ammonium chloride effectively improves the inhibition rate of Escherichia coli, and the addition of tebuconazole effectively improves the inhibition rate of Candida albicans and Staphylococcus aureus. The steam heat treatment and ozone sterilization treatment of polyester fibers also effectively improve the performance of the modified polyester fibers.

[0043] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. Although the present invention has been disclosed as a preferred embodiment as above, it is not used to limit the present invention. Any technical personnel in this field can make some changes or modify the technical contents disclosed above into equivalent embodiments without departing from the scope of the technical solution of the present invention. However, any brief modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention are still within the scope of the technical solution of the present invention.

Claims

1. A method for preparing antibacterial and detoxifying modified polyester fiber, characterized in that: The process of the preparation method of the antibacterial and detoxifying modified polyester fiber is as follows: S1: dissolving graphene oxide in deionized water to obtain a graphene oxide solution with a mass fraction of 30-50%, adding 3-5 wt% zinc nitrate hexahydrate to the graphene solution, and stirring at a speed of 150 r / min for 2 h to obtain a mixed solution A; S2: Tebuconazole and dioctadecyl dimethyl ammonium chloride were mixed in a mass ratio of 2:1, dispersed in an ethanol solution, stirred at a speed of 150-180 r / min, and the temperature was slowly raised from room temperature to 40°C while stirring for 1-2 h to obtain a mixed solution B; S3: heating the polyurethane to 170-190°C, stirring at a speed of 200 r / min for 0.5-1 h, mixing the molten polyurethane and deionized water at a volume ratio of 2:1 to obtain a polyurethane solution, and cooling the solution to 40°C at a speed of 5°C / min, stirring the solution at a speed of 150 r / min for 0.5 h at 40°C; S4: Add mixed solution A and mixed solution B to the polyurethane solution at 40° C., wherein the volume ratio of the polyurethane solution, the mixed solution A and the mixed solution B is 2:1:1, and then add 1wt% of a dispersant and 0.5wt% of a silane coupling agent, and continue to stir at a speed of 250 r / min for 3-4 hours to obtain a mixed solution C; S5: passing water vapor into the polyester fiber for heat treatment, then passing ozone for sterilization, and then passing nitrogen gas at 70° C. for 4 to 6 hours after the sterilization to obtain dry polyester fiber; S6: soaking the dried polyester fiber in the mixed solution C, heating it to 45-55° C., ultrasonicating it for 3-4 hours, taking it out, and drying the polyester fiber using a laser drying method to obtain the antibacterial and detoxifying modified polyester fiber.

2. The method for preparing an antibacterial and detoxifying modified polyester fiber according to claim 1, characterized in that: The mass fraction of the ethanol solution in the S2 is 60-80%.

3. The method for preparing an antibacterial and detoxifying modified polyester fiber according to claim 1, characterized in that: The slow heating rate in S2 is 2°C / min.

4. The method for preparing an antibacterial and detoxifying modified polyester fiber according to claim 1, characterized in that: The dispersant in S4 is polyethylene glycol, and its number average molecular weight is 2000-4000.

5. The method for preparing an antibacterial and detoxifying modified polyester fiber according to claim 1, characterized in that: The silane coupling agent in S4 is one or more of vinyl triethoxy silane, γ-aminopropyl triethoxy silane, and vinyl trimethoxy silane.

6. The method for preparing an antibacterial and detoxifying modified polyester fiber according to claim 1, characterized in that: The parameters of the water vapor heat treatment in S5 are as follows: the treatment time is 0.5-2 hours, the treatment temperature is 200-300° C., and the amount of water vapor introduced is 1.5-2 kg / h.

7. The method for preparing an antibacterial and detoxifying modified polyester fiber according to claim 1, characterized in that: The ozone flow rate in S5 is 20 m / s, and the purge time is 1 h.

8. The method for preparing an antibacterial and detoxifying modified polyester fiber according to claim 1, characterized in that: The nitrogen inlet flow rate in S5 is 15 m / s.

9. The method for preparing an antibacterial and detoxifying modified polyester fiber according to claim 1, characterized in that: The parameters of the laser drying method in S6 are: laser power 300 W, temperature 50° C., and irradiation time 30 min.

10. An antibacterial and detoxifying modified polyester fiber, characterized in that: Prepared by the preparation method described in any one of claims 1 to 9.

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