An antibacterial and antiviral fiber, its preparation method and application

Abstract

This application discloses an antibacterial and antiviral fiber, its preparation method, and its application, belonging to the field of functional textile technology. The preparation method includes: mixing and reacting a polymeric guanidine salt, a cationic antibacterial agent, and a chloroolefin in an organic solvent to form an antibacterial and antiviral functional component; mixing a metal oxide, an amine-containing monomer, and an aminosilane coupling agent to obtain a modified amine-containing monomer; polymerizing and granulating the modified amine-containing monomer, a carboxylic acid-containing monomer, and the antibacterial and antiviral functional component to form an antibacterial and antiviral functional masterbatch; and finally, melt spinning polymer resin chips and the antibacterial and antiviral functional masterbatch to obtain the antibacterial and antiviral fiber. This application uses metal oxides as anchors to anchor the antibacterial and antiviral functional component to the resin matrix, greatly improving the dispersion uniformity and binding stability of the antibacterial functional groups in the resin matrix, endowing the fiber with excellent antibacterial and antiviral properties while significantly improving durability and washability.

Description

Technical Field

[0001] This application belongs to the field of functional textile technology, and in particular relates to an antibacterial and antiviral fiber, its preparation method and application. Background Technology

[0002] In recent years, the proliferation and cross-infection of pathogenic bacteria and viruses have posed immeasurable harm to human health, drawing greater attention to antibacterial and antiviral fibers and textile products. Among these methods, the preparation of antibacterial and antiviral functionalized modified fibers by combining antibacterial and antiviral functional ingredients with polymer matrices is one of the effective ways to achieve functional antibacterial and antiviral properties in fiber materials.

[0003] Currently, related technologies utilize different types / mechanisms of antibacterial and antiviral combinations, which are then compounded with polymer matrices to enhance the antibacterial and antiviral efficacy of functional ingredients. For example, prior art with publication number CN 115323522A discloses a method for preparing antibacterial polyamide fibers. This method involves dispersing acid-etched tourmaline in a solution of a guanidine-containing organic polymeric antibacterial agent, then mixing it with benzotriazole powder to introduce metal ions to form a stable protective film on the surface. Finally, an antibacterial functional polyamide masterbatch is prepared and melt-spun with polyamide resin, enabling the antibacterial polyamide fibers to maintain antibacterial activity in an environment containing a large number of anions.

[0004] However, the modification method described above has the following problems: First, the antibacterial functional components and the matrix are physically adsorbed and bound together by electrostatic forces and capillary effects, resulting in weak binding force and easy detachment of the antibacterial functional components. This leads to poor durability and washability of the modified fibers. Furthermore, the antibacterial functional components are poorly dispersed and unevenly distributed in the matrix, resulting in poor antibacterial performance of the modified fibers. Second, the introduction of benzotriazole and metal ion solution to form a protective film on the surface to slow down material corrosion is prone to damage during melt spinning. Summary of the Invention

[0005] This application discloses an antibacterial and antiviral fiber, its preparation method, and its application, aiming to solve the technical problems of poor durability, washability, and antibacterial properties of existing antibacterial and antiviral fibers.

[0006] To achieve the above objectives, the technical solution of this application is:

[0007] The first aspect of this application provides a method for preparing antibacterial and antiviral fibers, the method comprising:

[0008] By reacting high molecular weight guanidine salts, cationic antibacterial agents, and chloroolefins in an organic solvent, antibacterial and antiviral functional components are obtained.

[0009] The modified amine monomer was obtained by ultrasonically dispersing the metal oxide, amine-containing monomer and aminosilane coupling agent in water and then vacuum drying.

[0010] Under the action of a catalyst, the modified amine-containing monomer, antibacterial and antiviral functional components and carboxylic acid-containing monomer are mixed and reacted, and then granulated to obtain antibacterial and antiviral functional masterbatch.

[0011] The antibacterial and antiviral fibers are obtained by melt spinning polymer resin chips with the antibacterial and antiviral functional masterbatch.

[0012] Preferably, in conjunction with the first aspect, the polymeric guanidine salt is one or more of polyhexamethylene guanidine hydrochloride, polyhexamethylene biguanide hydrochloride, and polyhexamethylene guanidine phosphate.

[0013] Preferably, in conjunction with the first aspect, the cationic antibacterial agent is one or more of quaternary ammonium salt antibacterial agents, chlorhexidine salt antibacterial agents, and haloamine salt antibacterial agents.

[0014] Preferably, in conjunction with the first aspect, the chloroolefin is one or more of vinyl chloride, propylene chloride, and chloroprene.

[0015] Preferably, in conjunction with the first aspect, the metal oxide is one or more of titanium dioxide, manganese dioxide, and zinc oxide.

[0016] Preferably, in conjunction with the first aspect, the aminosilane coupling agent is one or more of aminopropyltriethoxysilane, aminopropyltrimethoxysilane, aminopropylmethyldimethoxysilane, aminopropyltriethoxysilane, aminopropylmethyldiethoxysilane, phenylaminomethyltriethoxysilane, phenylaminomethyltrimethoxysilane, and aminoethylaminoethylaminopropyltrimethoxysilane.

[0017] Preferably, in conjunction with the first aspect, the catalyst is one or more of manganese acetate, sodium caprolactam, and stannous octoate.

[0018] Preferably, in conjunction with the first aspect, the polymer resin chips are one or more of polyamide, polyethylene, polypropylene, polyester, polylactic acid, polyurethane, polyimide, and polyphenylene sulfide resin chips.

[0019] Preferably, in conjunction with the first aspect, when the modified amine-containing monomer, the antibacterial and antiviral functional component, and the carboxylic acid-containing monomer are mixed and reacted, the mass ratio of the modified amine-containing monomer, the antibacterial and antiviral functional component, and the carboxylic acid-containing monomer is 50:1-10:1-50.

[0020] Preferably, in conjunction with the first aspect, the mass ratio of the polymer resin chips to the antibacterial and antiviral functional masterbatch is 100:5-25.

[0021] The second aspect of this application provides antibacterial and antiviral fibers produced by the method described in the first aspect, the antibacterial and antiviral fibers including fine denier monofilaments, multifilaments, and profiled fibers.

[0022] The third aspect of this application provides the use of the antimicrobial and antiviral fibers described in the second aspect in the manufacture of antimicrobial and antiviral fiber articles.

[0023] Compared with the prior art, the advantages or beneficial effects of the embodiments of this application include at least the following:

[0024] The preparation method provided in this application enables the antibacterial and antiviral functional components to be uniformly dispersed and persistently anchored in the matrix resin, thereby giving the resin highly efficient and long-lasting antibacterial and antiviral functions. Firstly, a high-molecular-weight guanidine salt, a cationic antibacterial agent, and a chloroolefin are mixed and reacted in an organic solvent, allowing the high-molecular-weight guanidine salt and the cationic antibacterial agent to chemically bond to the chloroolefin molecules, forming a "macromolecule" antibacterial and antiviral functional component. Secondly, a metal oxide, an amine-containing monomer, and an aminosilane coupling agent are mixed and reacted, allowing the metal oxide to be uniformly and stably connected to the interface of the amine-containing monomer, forming a modified amine-containing monomer. Thirdly, the modified amine-containing monomer, the "macromolecule" antibacterial and antiviral functional component, and a carboxylic acid-containing monomer are mixed and reacted, allowing the "macromolecule" antibacterial and antiviral functional component to be anchored and bound to the metal oxide, thus forming a uniform, regular, and stable anchored structure. This process enables the composite functional components to bond firmly and locally to the resin surface, improving not only the stability of the bond between the composite functional components and the resin but also the dispersibility of the composite functional components on and within the resin surface. This significantly enhances the durability and washability of the finished antibacterial and antiviral fiber products. Furthermore, the synergistic effect between the high-molecular-weight guanidine salt and the cationic antibacterial agent greatly improves the antibacterial and antiviral properties of the prepared antibacterial and antiviral fibers. On the other hand, the polymerization reaction of modified amine-containing monomers and modified carboxylic acid-containing monomers forms long-chain polymers, enabling interconnection between the components and constructing a multi-component antibacterial and antiviral long-chain system. This effectively overcomes the performance and mechanism defects of each component, enhancing the synergistic antibacterial and antiviral effect. Attached Figure Description

[0025] To more clearly illustrate the technical solutions of the embodiments of this application, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments recorded in this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0026] Figure 1 This is an overall appearance view of the antibacterial and antiviral fiber αMPU1 provided in the embodiments of this application;

[0027] Figure 2 for Figure 1 The cross-sectional SEM image. Detailed Implementation

[0028] The technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of this application. All other embodiments obtained by those skilled in the art based on the embodiments of this application without creative effort are within the scope of protection of this application.

[0029] In the following description of this embodiment, the term "and / or" is used to describe the association relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, B existing alone, and A and B existing simultaneously. A and B can be singular or plural. The character " / " generally indicates that the preceding and following related objects have an "or" relationship.

[0030] In the following description of this embodiment, the term "at least one" means one or more, and "more than one" means two or more. "At least one of the following" or similar expressions refer to any combination of these items, including any combination of single or multiple items. For example, "at least one of a, b, or c", or "at least one of a, b, and c", can both mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be single or multiple.

[0031] Those skilled in the art should understand that, in the following description of the embodiments of this application, the sequence of numbers does not imply the order of execution. Some or all steps may be executed in parallel or sequentially. The execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of this application.

[0032] The terminology used in the embodiments of this application is for the purpose of describing particular embodiments only and is not intended to be limiting of this application. The singular forms "a" and "the" as used in the embodiments of this application and the appended claims are also intended to include the plural forms, unless the context clearly indicates otherwise.

[0033] It should be noted that all raw materials and / or reagents in the embodiments of this application are purchased from the market or prepared according to conventional methods known to those skilled in the art. For example, various resins, high molecular weight guanidine salts, cationic antibacterial agents, chloroolefins, metal oxides and aminosilane coupling agents are all purchased from the market.

[0034] In a first aspect, embodiments of this application provide an antibacterial and antiviral fiber, the preparation method of which includes:

[0035] A high molecular weight guanidine salt, a cationic antibacterial agent, and a chloroolefin are mixed in an organic solvent to obtain an antibacterial and antiviral functional component.

[0036] After ultrasonic dispersion of metal oxides, amine-containing monomers and aminosilane coupling agents in water, the mixture is vacuum dried to form modified amine-containing monomers.

[0037] Under the action of a catalyst, the modified amine-containing monomer, antibacterial and antiviral functional components and carboxylic acid-containing monomer are mixed and reacted, and then granulated to form an antibacterial and antiviral functional masterbatch.

[0038] The antibacterial and antiviral fibers are obtained by melt spinning polymer resin chips with the antibacterial and antiviral functional masterbatch.

[0039] It should be noted that the organic solvent in this application embodiment is preferably methanol with a volume concentration of less than 85%, so as to ensure that the polymeric guanidine salt can be uniformly and stably dispersed in the methanol solvent, which is beneficial to improving the uniformity of the mixing of cationic antibacterial agent, polymeric guanidine salt and chloroolefin, and effectively solving the problem of poor heat resistance of cationic antibacterial agent.

[0040] It should be noted that, unless otherwise specified, the vacuum drying in the embodiments of this application is carried out in accordance with the general process requirements of the relevant field. For example, the preferred drying temperature is 60°C, the drying time is 6 hours, and the pressure is 1.0 MPa. Vacuum drying can lower the boiling point of the organic solvent, thereby efficiently and safely evaporating and removing most of the organic solvent from the liquid phase, improving the processing performance of the modified fiber.

[0041] It should be noted that, unless otherwise specified, the blending granulation and melt spinning in the embodiments of this application are carried out in accordance with the general process requirements of the relevant fields. For example, blending granulation can be carried out using a twin-screw extruder at a process condition of 260±2℃ and then granulated; melt spinning can be carried out using a melt spinning machine at a process condition of 280±10℃ and a winding speed of 3000-5000m / min.

[0042] It should be noted that amine-containing monomers refer to small molecules containing amino functional groups used in the synthesis of polymer resin materials, such as ethylenediamine and pentanediamine; carboxylic acid-containing monomers refer to small molecules containing carboxyl functional groups used in the synthesis of polymer resin materials, such as lactic acid, adipic acid, and terephthalic acid.

[0043] In summary, the preparation method of this application involves mixing and reacting a polymeric guanidine salt, a cationic antibacterial agent, and a chloroolefin in an organic solvent. This allows the polymeric guanidine salt and the cationic antibacterial agent to chemically bond to the chloroolefin molecules, forming a "macromolecule" antibacterial and antiviral functional component. Furthermore, a metal oxide, an amine-containing monomer, and an aminosilane coupling agent are mixed and reacted, resulting in the metal oxide being uniformly and stably attached to the amine-containing monomer interface to form a modified amine-containing monomer. Finally, the modified amine-containing monomer, the "macromolecule" antibacterial and antiviral functional component, and a carboxylic acid-containing monomer are mixed and reacted, anchoring the antibacterial and antiviral functional component to the metal oxide. This results in a uniform, regular, and stable anchored structure for the antibacterial and antiviral functional component, and a significant synergistic effect between the polymeric guanidine salt and the cationic antibacterial agent, greatly improving the antibacterial and antiviral properties of the antibacterial and antiviral fiber. Specifically:

[0044] By mixing and reacting polymeric guanidine salts, cationic antibacterial agents, and chloroolefins in an organic solvent, the polymeric guanidine salts and cationic antibacterial agents can be chemically bonded to the chloroolefin molecules. The uniformity after mixing is significantly improved, which not only effectively overcomes the poor performance of single antibacterial agents, but also facilitates the formation of long-chain polymer functional components, making it easier to combine with the matrix resin and improve the dispersion uniformity.

[0045] Modified amine monomers are prepared by mixing and reacting metal oxides, amine monomers, and aminosilane coupling agents. Aminosilane coupling agents can be used for amination modification to improve the interfacial activity of amine monomers, so that metal oxides are uniformly and stably connected to the interface of amine monomers to form modified amine monomers. This can further improve the dispersion performance of antibacterial and antiviral functional components on the surface and inside the matrix.

[0046] Under the action of a catalyst, the modified amine-containing monomer, antibacterial and antiviral functional components and carboxylic acid-containing monomers are mixed and reacted to form a long carbon chain polymer, which enables the components to be interconnected and constructs a multi-component antibacterial system. This effectively overcomes the performance and mechanism defects of each component and amplifies the synergistic antibacterial and antiviral effect.

[0047] In specific embodiments, the polymeric guanidine salt is preferably one or more of polyhexamethylene guanidine hydrochloride, polyhexamethylene biguanide hydrochloride, and polyhexamethylene guanidine phosphate. These polymeric guanidine salts are highly efficient, non-toxic, and easy to prepare. Furthermore, the antibacterial active ingredient of these polymeric guanidine salts is the guanidine group, and the combined use of several does not affect the effect; several can be used in combination.

[0048] In specific embodiments, the cationic antibacterial agent is one or more of quaternary ammonium salt antibacterial agents, chlorhexidine salt antibacterial agents, or haloamine salt antibacterial agents. For example, the quaternary ammonium salt antibacterial agent can be benzalkonium chloride; the chlorhexidine salt antibacterial agent can be chlorhexidine acetate, chlorhexidine gluconate, etc.; and the haloamine salt antibacterial agent can be trichloroisocyanuric acid, 5,5-dimethylhydantoin, etc. These cationic antibacterial agents possess the characteristics of high efficiency, low toxicity, and minimal susceptibility to pH changes. Both the high molecular weight guanidine salt and the cationic antibacterial agent are hydrolyzed cationic systems. The high molecular weight guanidine salt and the cationic antibacterial agent are chemically bonded to the chloroolefin molecule to form antibacterial and antiviral functional components, thereby significantly enhancing the antibacterial range and efficiency of the antibacterial and antiviral fibers.

[0049] In a specific embodiment, the aminosilane coupling agent is preferably one of aminopropyltriethoxysilane, aminopropyltrimethoxysilane, aminopropylmethyldimethoxysilane, aminopropyltriethoxysilane, aminopropylmethyldiethoxysilane, phenylaminomethyltriethoxysilane, phenylaminomethyltrimethoxysilane, and aminoethylaminoethylaminopropyltrimethoxysilane. These aminosilane coupling agents improve the interfacial activity of the amine-containing monomers through amination modification, allowing the metal oxide to be uniformly and stably linked to the interface of the amine-containing monomers, thereby further improving the dispersion performance of the antibacterial and antiviral functional components on and within the resin surface.

[0050] In specific embodiments, the polymer resin is one or more of polyamide, polyethylene, polypropylene, polyester, polylactic acid, polyurethane, polyimide, and polyphenylene sulfide resin. These polymer resins possess organic functional groups that are identical to or have affinity with the polymer guanidine salt, allowing for excellent compatibility during blending, granulation, and melt spinning. This results in smooth and flat fiber surfaces and cross-sections, significantly improving the success rate of melt spinning. Furthermore, this type of fiber can be widely used in textiles, military applications, environmental protection, medical and health fields, and construction.

[0051] In a specific embodiment, the preferred mass ratio of the modified amine-containing monomer, the antibacterial and antiviral functional component, and the carboxylic acid-containing monomer is 50:1-10:1-50. If the mass ratio is less than 50:1-10, the antibacterial and antiviral component does not bind strongly to the metal oxide anchor points of the modified amine-containing monomer, significantly affecting the antibacterial and antiviral performance. If the mass ratio is greater than 50:1-10:1-50, the polymerization reaction is incomplete, significantly affecting the continuity of spinning. Therefore, in this application, the preferred mass ratio of the modified amine-containing monomer, the antibacterial and antiviral functional component, and the carboxylic acid-containing monomer is 50:1-10:1-50, thereby improving granulation performance while achieving ideal antibacterial and antiviral effects.

[0052] In a specific embodiment, the preferred mass ratio of polymer resin chips to antibacterial and antiviral functional masterbatch is 100:5-25. When the mass ratio is lower than 100:25, the modified fiber exhibits weaker antibacterial and antiviral effects, making it difficult to achieve the desired results. Conversely, when the ratio is higher than 100:5, it can easily lead to excessive pressure on the spinning equipment components, affecting fiber spinnability. Therefore, the preferred mass ratio of polymer resin chips to antibacterial and antiviral functional masterbatch is 100:5-25, thereby improving spinning performance while achieving good antibacterial and antiviral effects.

[0053] Secondly, embodiments of this application also provide antibacterial and antiviral fibers prepared by the method described in the first aspect.

[0054] The preparation method described in the first aspect enables a synergistic effect between the high molecular weight guanidine salt, cationic antibacterial agent, chloroolefin, and metal oxide. The "macromolecule" antibacterial and antiviral functional components are linked with the metal oxide to form a uniform, regular, and stable anchoring structure. Therefore, the antibacterial and antiviral fibers prepared in the embodiments of this application possess highly efficient and long-lasting antibacterial and antiviral functions.

[0055] The test results of the examples show that the antibacterial and antiviral fibers of this application have an antibacterial rate of over 99% against Escherichia coli, Staphylococcus aureus and Candida albicans, and an antiviral effect of over 99.99% against H1N1 influenza virus; after washing the fibers 50 times, the antibacterial rate against Escherichia coli, Staphylococcus aureus and Candida albicans still reaches over 90%, and the antiviral effect against H1N1 influenza virus is >99%.

[0056] Thirdly, this application also provides the application of the antibacterial and antiviral fibers described above. Specifically, it involves using the antibacterial and antiviral fibers of this application as raw materials to manufacture various textile products, environmentally friendly products, medical products, building products, and other daily necessities. Based on the highly efficient and long-lasting antibacterial and antiviral properties and effects of this antibacterial and antiviral fiber, the textile products, environmentally friendly products, medical products, building products, and other daily necessities prepared using this antibacterial and antiviral fiber possess excellent antibacterial and antiviral properties.

[0057] The technical solution of this application will be further described below with reference to specific embodiments.

[0058] Example 1

[0059] This embodiment provides a method for preparing antibacterial and antiviral fiber αMPU1, specifically including:

[0060] S101: Add 30g of polyhexamethylene guanidine hydrochloride, 12g of benzalkonium chloride and 10g of allyl chloride to 100ml of 85% vv methanol solution to form antibacterial and antiviral functional component A1.

[0061] S102: 1g titanium dioxide, 50g ethylene glycol and 10g aminopropyltriethoxysilane were ultrasonically dispersed in 500ml water and dried under vacuum at 120℃ and 0.05Mpa for 2h to obtain modified ethylene glycol α1.

[0062] S103: Add 50g of modified ethylene glycol α1, 50g of terephthalic acid, 10g of antibacterial and antiviral functional component A1 and 5g of manganese acetate to a polymerization reactor. First, perform ring-opening prepolymerization, then polycondensation, and finally cast and pelletize to form antibacterial and antiviral functional masterbatch β1.

[0063] S104: Mix 50g of functionalized masterbatch β1 and 500g of polyester resin chips, and melt spin at 285℃ with a spinning speed of 4000m / min to obtain antibacterial and antiviral fiber αMPU1.

[0064] This embodiment tested the overall appearance and cross-sectional SEM of the antibacterial and antiviral fiber αMPU1. The results are as follows: Figures 1 to 2 As shown. Among them, Figure 1 This is an overall appearance diagram of the antibacterial and antiviral fiber αMPU1; Figure 2 for Figure 1 The cross-sectional SEM image.

[0065] according to Figure 1 It can be seen that the antibacterial and antiviral fiber αMPU1 has a smooth surface and good formability, indicating that the antibacterial components are evenly dispersed in the masterbatch and the fiber has strong spinnability.

[0066] according to Figure 2 It is known that the "macromolecule" antibacterial and antiviral functional components are uniformly dispersed on the fiber surface to form a smooth film structure, which greatly ensures the antibacterial and antiviral effects and durability of the material.

[0067] Example 2

[0068] This embodiment provides a method for preparing antibacterial and antiviral fiber αMPU2, specifically including:

[0069] S201: After dissolving 30.2g of polyhexamethylene monoguanidine hydrochloride, 20.3g of benzalkonium chloride and 10g of allyl chloride in 200mL of 85% vv ethanol, an antibacterial and antiviral functional component A2 is formed.

[0070] S202: 2g zinc oxide, 30g lactic acid and 2g aminopropyltriethoxysilane were ultrasonically dispersed in 400ml water and dried under vacuum at 100℃ and 0.05Mpa for 1h to obtain modified lactic acid α2.

[0071] S203: 20g of modified lactic acid α2, 20g of lactic acid, 1.8g of antibacterial and antiviral functional component A2 and 3.6g of stannous octoate are added to the polymerization reactor. First, ring-opening prepolymerization is carried out, then polycondensation is carried out, and finally the mixture is cast and granulated to form antibacterial and antiviral functional masterbatch β2.

[0072] S204: Mix 50g of functionalized masterbatch β2 and 500g of polylactic acid chips, and melt spin at 220℃ with a spinning speed of 3200m / min to obtain antibacterial and antiviral fiber αMPU2.

[0073] Example 3

[0074] This embodiment provides a method for preparing antibacterial and antiviral fiber αMPU3, specifically including:

[0075] S301: Add 45.5g of polyhexamethylene biguanide hydrochloride, 37.6g of benzalkonium chloride and 22.4g of vinyl chloride to 120ml of 85% vv ethanol solution to form antibacterial and antiviral functional component A3;

[0076] S302: 3g titanium dioxide, 50g caprolactam and 10g aminopropylmethyldimethoxysilane were ultrasonically dispersed in 800ml water and dried under vacuum at 110℃ and 0.05Mpa for 2h to obtain modified caprolactam α3.

[0077] S303: Add 30g of modified caprolactam α3, 30g of caprolactam, 6g of antibacterial and antiviral functional component A3 and 2g of sodium caprolactam to the polymerization reactor. First, perform ring-opening prepolymerization, then perform polycondensation, and finally cast and pelletize to form antibacterial and antiviral functional masterbatch β3.

[0078] S304: Mix 50g of functionalized masterbatch β2 and 500g of polyamide 6 chips, and melt spin at 270℃ with a spinning speed of 4200m / min to obtain antibacterial and antiviral fiber αMPU3.

[0079] Example 4

[0080] This embodiment provides a method for preparing antibacterial and antiviral fiber αMPU4, specifically including:

[0081] S401: Add 55.2g of polyhexamethylene guanidine phosphate, 35.5g of chloramine salt and 26.5g of chloroprene to 120ml of 80% vv ethanol solution to form antibacterial and antiviral functional component A4;

[0082] S402: 10g manganese oxide, 25g ethylene glycol and 20g aminopropylmethyldimethoxysilane were ultrasonically dispersed in 300ml water and dried under vacuum at 130℃ and 0.05Mpa for 1.5h to obtain modified ethylene glycol α4.

[0083] S403: 18g of modified ethylene glycol α4, 180g of terephthalic acid, 4.2g of antibacterial and antiviral functional component A3 and 1.5g of manganese acetate are added to the polymerization reactor. First, ring-opening prepolymerization is carried out, then polycondensation is carried out, and finally the mixture is cast and pelletized to form antibacterial and antiviral functional masterbatch β4.

[0084] S404: Mix 30g of functionalized masterbatch β4 and 300g of polyester resin chips, and melt spin at 280℃ with a spinning speed of 3800m / min to obtain antibacterial and antiviral fiber αMPU4.

[0085] Example 5

[0086] This embodiment provides a method for preparing antibacterial and antiviral fiber αMPU5, specifically including:

[0087] S501: Add 46.2g of polyhexamethylene guanidine phosphate, 32.5g of allyl chloride and 60.2g of chloramine salt to 200ml of 70% vv ethanol solution to form antibacterial and antiviral functional component A5;

[0088] S502: 3g titanium dioxide, 40g ethylene glycol and 15g aminopropylmethyldiethoxysilane were ultrasonically dispersed in 200ml water and dried under vacuum at 100℃ and 0.05Mpa for 2.5h to obtain modified ethylene glycol α5.

[0089] S503: Add 500g of modified ethylene glycol α4, 50g of terephthalic acid, 10g of antibacterial and antiviral functional component A5 and 6g of manganese acetate to a polymerization reactor. First, perform ring-opening prepolymerization, then polycondensation, and finally cast and pelletize to form antibacterial and antiviral functional masterbatch β5.

[0090] S504: Mix 45g of functionalized masterbatch β5 and 450g of polyester resin chips, and melt spin at 280℃ with a spinning speed of 4050m / min to obtain antibacterial and antiviral fiber αMPU5.

[0091] To verify the antibacterial and antiviral properties and durability of the antibacterial and antiviral fibers αMPU1-αMPU5 prepared in the embodiments of this application, the following comparative examples 1-3 are provided in detail.

[0092] Comparative Example 1

[0093] This comparative example provides a method for preparing antibacterial and antiviral fiber βMPU1, specifically including:

[0094] S601: Add 30g of polyhexamethylene guanidine hydrochloride, 12g of benzalkonium chloride, 10g of allyl chloride and 1g of titanium dioxide to 100ml of 85% vv methanol solution to form antibacterial and antiviral functional component B1.

[0095] S602: 20g of ethylene glycol and 2g of aminopropyltriethoxysilane were ultrasonically dispersed in 500ml of water and dried under vacuum at 120℃ and 0.05Mpa for 2h to obtain modified ethylene glycol γ1.

[0096] S603: Add 50g of modified ethylene glycol γ1, 50g of terephthalic acid, 8g of antibacterial and antiviral functional component B1 and 5g of catalyst manganese acetate to a polymerization reactor. First, perform ring-opening prepolymerization, then polycondensation, and finally cast and pelletize to form antibacterial and antiviral functional masterbatch δ1.

[0097] S604: Mix 50g of functionalized masterbatch δ1 and 500g of polyester resin chips, and melt spin at 285℃ with a spinning speed of 4000m / min to obtain antibacterial and antiviral fiber βMPU1.

[0098] Comparative Example 2

[0099] This comparative example provides a method for preparing antibacterial and antiviral fiber βMPU2, specifically including:

[0100] S701: After dissolving 30.2g of polyhexamethylene monoguanidine hydrochloride and 20.3g of benzalkonium chloride in 200mL of 85% vv ethanol, antibacterial and antiviral functional component B2 is formed;

[0101] S702: 10g allyl chloride, 2g zinc oxide, 20g lactic acid and 2g aminopropyltriethoxysilane were ultrasonically dispersed in 400ml water and dried under vacuum at 100℃ and 0.05Mpa for 1h to obtain modified lactic acid γ2.

[0102] S703: 20g of modified lactic acid γ2, 20g of lactic acid, 2.5g of antibacterial and antiviral functional component B2 and 6g of catalyst stannous octoate are added to the polymerization reactor. First, ring-opening prepolymerization is carried out, then polycondensation is carried out, and finally the mixture is cast and granulated to form antibacterial and antiviral functional masterbatch δ2.

[0103] S704: Mix 50g of functionalized masterbatch δ2 and 500g of polylactic acid chips, and melt spin at 220℃ with a spinning speed of 3200m / min to obtain antibacterial and antiviral fiber βMPU2.

[0104] Comparative Example 3

[0105] This comparative example provides a method for preparing antibacterial and antiviral fiber βMPU3, specifically including:

[0106] S801: Add 45.5g of polyhexamethylene biguanide hydrochloride, 22.4g of chlorhexidine gluconate and 3g of titanium dioxide to 120ml of 85% vv ethanol solution to form antibacterial and antiviral functional component B3.

[0107] S802: 50g caprolactam and 10g aminopropylmethyldimethoxysilane were ultrasonically dispersed in 800ml water and dried under vacuum at 110℃ and 0.05Mpa for 2h to obtain modified caprolactam γ3.

[0108] S803: Add 30g of modified caprolactam γ3, 30g of caprolactam, 16g of antibacterial and antiviral functional component B3 and 10g of catalyst sodium caprolactam to a polymerization reactor. First, perform ring-opening prepolymerization, then perform polycondensation, and finally cast and pelletize to form antibacterial and antiviral functional masterbatch δ3.

[0109] S804: Mix 50g of functionalized masterbatch δ3 and 500g of polyamide 6 chips, and melt spin at 270℃ with a spinning speed of 4200m / min to obtain antibacterial and antiviral fiber βMPU3.

[0110] The antibacterial and antiviral properties of the antibacterial and antiviral fibers αMPU1-αMPU5 prepared in Examples 1-5 and the antibacterial and antiviral fibers βMPU1-βMPU3 prepared in Comparative Examples 1-3 were tested according to GB / T 20944.3-2008 "Evaluation of antibacterial properties - Part 3: Oscillation method" and ISO 18184:2014 "Textiles - Determination of antiviral activity". The test results are shown in Table 1.

[0111] Table 1: Antibacterial and antiviral performance tests of αMPU1-αMPU5 and βMPU1-βMPU3

[0112]

[0113] As shown in Table 1, the embodiments of this application first form antibacterial and antiviral functional components from polymeric guanidine salts, cationic antibacterial agents, and chloroolefins. Then, metal oxides, amine-containing monomers, and aminosilane coupling agents are reacted to form modified amine-containing monomers. Under the action of a catalyst, the modified amine-containing monomers, carboxylic acid-containing monomers, and antibacterial and antiviral functional components are blended to form antibacterial and antiviral functional masterbatches. These masterbatches are then melt-spun with polymeric resin chips to form highly efficient and durable antibacterial and antiviral fibers. This demonstrates that by first using chloroolefin-bonded polymeric guanidine salt antibacterial agents and cationic antibacterial agents, and then forming a regular and complete structure on the surface of the amine-containing monomer with metal oxides, modified amine-containing monomers are obtained. The metal oxides are then anchored and bound to novel macromolecular antibacterial agents to form a controllable and stable structure, and sufficient synergistic effects are generated between molecules, significantly improving the antibacterial and antiviral performance of the composite functional components. Meanwhile, comparing Example 1 and Comparative Example 1, it can be seen that first forming an antibacterial and antiviral functional component of chloroolefin-bonded organic antibacterial macromolecules, then forming a regular and complete structure of the amine-containing monomer with metal oxides on the surface of the amine-containing monomer, and finally mixing them to form an antibacterial and antiviral functional masterbatch is crucial for improving the antibacterial and antiviral performance of the product.

[0114] The antibacterial and antiviral durability properties of the antibacterial and antiviral fiber αMPU1 prepared in Example 1 and the antibacterial and antiviral fiber βMPU1 prepared in Comparative Example 1 were tested according to GB / T 20944.3-2008 "Evaluation of antibacterial properties - Part 3: Oscillation method", GB / T 12490-1990 "Textiles - Test methods for color fastness to domestic and commercial washing", and ISO 18184:2014 "Textiles - Determination of antiviral activity". The oscillation method was used to test the antibacterial durability properties of the fibers, and the plaque analysis method was used to test the antiviral durability properties of the fibers. The results are shown in Table 2.

[0115] Table 2: Antibacterial and antiviral properties of αMPU1 and βMPU1 under different washing cycles

[0116]

[0117] As shown in Table 2, in this embodiment, the high molecular weight guanidine salt and cationic antibacterial agent are chemically bonded to the chloroolefin molecule. During the manufacturing process of the antibacterial and antiviral functional masterbatch, the antibacterial and antiviral functional components are connected with metal oxides to form a uniform, regular, and stable material structure. The antibacterial and antiviral functional masterbatch and resin are melt-spun together, so that the antibacterial and antiviral functional molecules will not fall off from the fiber macromolecules during washing. This not only greatly improves the stability of the combination between the composite functional components and the matrix resin, but also improves the dispersibility of the composite functional components on the surface and inside of the resin, greatly improving the durability and effectiveness of the antibacterial and antiviral fiber product, and meeting the industrial requirement of 50 washes for antibacterial textiles.

[0118] The various embodiments in this specification are described in a progressive manner. The same or similar parts between the various embodiments can be referred to each other. Each embodiment focuses on describing the differences from other embodiments.

[0119] The above embodiments are only used to illustrate the technical solutions of this application, and are not intended to limit this application. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of this application.

Claims

1. A method for preparing antibacterial and antiviral fibers, characterized in that, The method includes: A mixture of high molecular weight guanidine salt, cationic antibacterial agent and chloroolefin in an organic solvent is reacted to obtain an antibacterial and antiviral functional component; Modified caprolactam was obtained by ultrasonically dispersing metal oxides, caprolactam, and aminosilane coupling agents in water and then vacuum drying. Under the action of a catalyst, the modified caprolactam, antibacterial and antiviral functional components are mixed and reacted with carboxylic acid-containing monomers, and then granulated to obtain antibacterial and antiviral functional masterbatch. The polymer resin chips are melt-spun with the antibacterial and antiviral functional masterbatch to obtain antibacterial and antiviral fibers. The polymeric guanidine salt is one or more of polyhexamethylene guanidine hydrochloride, polyhexamethylene biguanide hydrochloride, and polyhexamethylene guanidine phosphate. The cationic antibacterial agent is one or more of the following: quaternary ammonium salt antibacterial agent, chlorhexidine salt antibacterial agent, and haloamine salt antibacterial agent; The metal oxide is one or more of titanium dioxide, manganese dioxide, and zinc oxide.

2. The preparation method according to claim 1, characterized in that, The chloroolefin is one or more of vinyl chloride, propylene chloride, and chloroprene.

3. The preparation method according to claim 1, characterized in that, The aminosilane coupling agent is one or more of aminopropyltriethoxysilane, aminopropyltrimethoxysilane, aminopropylmethyldimethoxysilane, aminopropyltriethoxysilane, aminopropylmethyldiethoxysilane, phenylaminomethyltriethoxysilane, phenylaminomethyltrimethoxysilane, and aminoethyltrimethoxysilane.

4. The preparation method according to claim 1, characterized in that, The catalyst is one or more of manganese acetate, sodium caprolactam, and stannous octoate.

5. The preparation method according to claim 1, characterized in that, The polymer resin chips are one or more of polyamide, polyethylene, polypropylene, polyester, polylactic acid, polyurethane, polyimide, and polyphenylene sulfide resin chips.

6. The preparation method according to claim 1, characterized in that, When the modified caprolactam, the antibacterial and antiviral functional components are mixed and reacted with the carboxylic acid-containing monomer, the mass ratio of the modified caprolactam, the antibacterial and antiviral functional components and the carboxylic acid-containing monomer is 50:1-10:1-50.

7. The preparation method according to claim 1, characterized in that, The mass ratio of the polymer resin chips to the antibacterial and antiviral functional masterbatch is 100:5-25.

8. The antibacterial and antiviral fiber prepared by the method according to any one of claims 1-7, characterized in that, The antibacterial and antiviral fibers include fine denier monofilaments, multifilaments, and profiled fibers.

9. The use of antimicrobial and antiviral fibers produced by any one of claims 1-7 in the manufacture of antimicrobial and antiviral fiber products.

Images