An antibacterial core-spun yarn and its preparation method

Abstract

This invention discloses an antibacterial core-spun yarn and its preparation method, belonging to the field of core-spun yarn technology. The preparation steps are as follows: polyurethane particles, tetrahydrofuran, and N,N-dimethylformamide are mixed and stirred at 50°C for 24 hours. An antibacterial agent based on graphene oxide is added, and stirring is continued for 0.5-1 hours to obtain an antibacterial spinning solution. Viscose staple fibers are prepared into viscose slivers according to the opening process. The viscose slivers are combed to obtain a viscose web. Antibacterial nanofibers obtained by electrospinning the antibacterial spinning solution are sprayed onto the viscose web and bundled through a trumpet-shaped opening to obtain a viscose sliver. The viscose sliver is fed into an air-jet vortex spinning machine after two drawing passes. Nylon filaments are fed into the machine through the gap between the first and second rollers via a guide device. Vortex spinning yields a core-spun yarn with nylon filaments as the core and viscose fibers and antibacterial nanofibers as the outer fibers, exhibiting excellent antibacterial properties, flame retardant properties, and washability.

Description

Technical Field

[0001] This invention belongs to the field of core-spun yarn technology, specifically relating to an antibacterial core-spun yarn and its preparation method. Background Technology

[0002] Core-spun yarn, also known as core-spun yarn, is a type of yarn in which one fiber is used as the core and another fiber is used as the sheath. Compared to antibacterial finishing techniques for fabrics that are prone to contamination and have poor durability, electrospun core-spun yarn technology can coat the surface of the yarn with submicron fibers carrying antibacterial functions during the traditional spinning process and then process it. Compared to electrostatic antibacterial yarn, electrostatic core-spun yarn has both the mechanical properties of the core yarn, meeting the requirements of machine manufacturing, and the surface effects and rich physicochemical properties brought by the super-scale of submicron fibers. However, currently, electrospun core-spun yarn is prone to bacterial growth, which can be harmful to the human body. Most of these methods impart antibacterial properties by applying an antibacterial coating to the finished product. Although this method is efficient and provides good antibacterial performance in a short time, the adhesion between the coating and the finished yarn is weak. After several washes, the coating will peel off, resulting in the loss of antibacterial properties. Therefore, it is necessary to provide a wash-resistant antibacterial core-spun yarn and its preparation method. Summary of the Invention

[0003] The purpose of this invention is to provide an antibacterial core-spun yarn and its preparation method, so as to solve the problem of poor antibacterial properties and washability of existing core-spun yarns.

[0004] The objective of this invention can be achieved through the following technical solutions:

[0005] A method for preparing an antibacterial core-spun yarn includes the following steps:

[0006] Step 1: Mix polyurethane particles, tetrahydrofuran and N,N-dimethylformamide, stir at 50℃ and 250 r / min for 24 h, then add graphene oxide-based antibacterial agent and continue stirring for 0.5-1 h to obtain antibacterial spinning solution;

[0007] The second step involves preparing viscose slivers from viscose staple fibers using the opening process. These slivers are then combed to form a viscose web, which is placed on a web conveyor. Antibacterial nanofibers are obtained by electrospinning with an antibacterial spinning solution. The resulting antibacterial nanofibers are then sprayed onto the viscose web, causing them to deposit onto the web. The web is then bundled through a trumpet-shaped opening to obtain a viscose sliver. This sliver is then fed into an air-jet vortex spinning machine after two drawing passes. Nylon filaments are fed into the machine through a guide device from the gap between the first and second rollers. The machine is then vortex-spun to obtain an antibacterial core-spun yarn.

[0008] Furthermore, in the first step, the ratio of polyurethane particles, tetrahydrofuran, N,N-dimethylformamide, and graphene oxide-based antibacterial agent is 8-15g: 42.5-46mL: 42.5-46mL: 2-6g.

[0009] Furthermore, in the second step, the fineness of the nylon filament is 50-150D, the filament feed ratio is 0.95-1.01, the mass ratio of viscose cotton web to antibacterial nanofiber is 1:1-3, and the mass ratio of viscose sliver to nylon filament is 4:1.

[0010] Furthermore, the core yarn of the antibacterial core-spun yarn is made of nylon filament, and the outer fibers are viscose fiber and antibacterial nanofiber.

[0011] Furthermore, the graphene oxide-based antibacterial agent is prepared through the following steps:

[0012] Graphene-Schiff base ligands were dispersed in anhydrous ethanol, and an aqueous solution of copper chloride was added. The reaction was carried out at 50-70℃ for 8-12 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered, and the filter cake was washed with deionized water until the washing liquid was free of chloride ions. The cake was then dried at 60℃ to constant weight to obtain an oxide-based antibacterial agent. The ratio of graphene-Schiff base ligands, anhydrous ethanol, and copper chloride was 5g:50-100mL:1.8-2.5g. The aqueous solution of copper chloride consisted of copper chloride and deionized water at a ratio of 1g:5-10mL. Using graphene-Schiff base ligands and copper chloride as raw materials, the oxide-based antibacterial agent was obtained by utilizing the coordination reaction between Schiff bases and copper ions.

[0013] Furthermore, the graphene-Schiff base ligand is prepared via the following steps:

[0014] Step S1: Add aminated graphene oxide and anhydrous methanol to a three-necked flask, and add anhydrous methanol solution of 4-aminobenzaldehyde dropwise while stirring. After the addition is complete, stir and react at 60°C for 4-6 hours under a nitrogen atmosphere. After the reaction is complete, filter the mixture, wash the filter cake with deionized water and dry it in a vacuum drying oven at 60°C for 12 hours to obtain the intermediate product.

[0015] Step S2: Add 4-carboxybutyltriphenylphosphine bromide and DMSO to a flask, stir at room temperature for 10-20 min, then add EDC·HCl and NHS, stir for 0.5 h, then add the intermediate product, stir at room temperature for 24 h, after the reaction is complete, filter, wash the filter cake with deionized water and dry it in a vacuum drying oven at 60℃ for 12 h to obtain graphene-Schiff base ligand.

[0016] Using aminated graphene oxide and 4-aminobenzaldehyde as raw materials, an intermediate product containing a Schiff base structure and abundant amino groups is obtained through a condensation reaction between amino and aldehyde groups. Then, the amino group of the intermediate product and the carboxyl group of 4-carboxybutyltriphenylphosphine bromide are used to enter the quaternary phosphate salt structure through an amide reaction to obtain the graphene-Schiff base ligand.

[0017] Furthermore, in step S1, the mass ratio of aminated graphene oxide to 4-aminobenzaldehyde is 4:1-1.5.

[0018] Further, in step S2, the ratio of 4-carboxybutyltriphenylphosphine bromide, DMSO, EDC·HCl, NHS and intermediate product is 5g:100mL:0.96g:0.56g:2.7-3.5g, where EDC·HCl is 1-ethyl-(3-dimethylamino)carbodiimide hydrochloride and NHS is N-hydroxysuccinimide.

[0019] Furthermore, aminated graphene oxide is prepared through the following steps:

[0020] Graphene oxide was dispersed in DMF and sonicated for 1 hour. Then, silane coupling agent KH-550 and deionized water were added. The mixture was stirred at 60-80℃ for 0.5-1 hour. After cooling to room temperature, the mixture was filtered. The filter cake was washed with anhydrous ethanol and dried in a vacuum oven at 60℃ to constant weight to obtain aminated graphene oxide. The ratio of graphene oxide, DMF, silane coupling agent KH-550 and deionized water was 0.1g:100mL:0.1-0.2g:5-10mL. By modifying graphene oxide with silane coupling agent KH-550, abundant amino and silicon-oxygen-silicon structures were introduced onto the surface of graphene oxide.

[0021] Furthermore, the length of the viscose cotton roll is 30-32m, and the basis weight is 260-300g / m.

[0022] Furthermore, the parameters for the electrospinning process are: spinning temperature 20-25℃, relative humidity 30-60%, voltage 16-21kV, and receiving distance 15-20cm.

[0023] Furthermore, the adhesive strips are combined in two processes using six adhesive strips.

[0024] Furthermore, the process parameters for vortex spinning are: total draft ratio of 120-260 times, and main drafting speed of 21-35 times.

[0025] Furthermore, an antibacterial core-spun yarn is prepared by the above-described method.

[0026] The beneficial effects of this invention are:

[0027] This invention provides an antibacterial core-spun yarn and its preparation method. Using nylon filament as the core and viscose fiber and antibacterial nanofibers as the outer fibers, it is obtained through eddy spinning. The yarn possesses excellent physical and mechanical properties and antibacterial properties. The antibacterial properties are mainly manifested in the antibacterial nanofibers. These nanofibers are obtained by electrospinning with polyurethane particles as the main material and graphene oxide-based antibacterial agents as additives. The graphene oxide-based antibacterial agent contains organic modifiers and amide groups on its surface, exhibiting high compatibility with polyurethane and good dispersibility in the spinning solution. Furthermore, the graphene oxide antibacterial agent contains copper ions and quaternary phosphate structures. Copper ions are loaded onto the graphene oxide surface through Schiff base coordination, and the quaternary phosphate structures are loaded onto the graphene oxide surface through chemical bonds, both exhibiting high stability. Copper ions sterilize bacteria by killing bacterial cells, disrupting cell membranes, and inhibiting bacterial protein synthesis. Quaternary phosphates have a highly efficient and broad-spectrum bactericidal effect. Combined with the antibacterial effect of graphene oxide, the obtained antibacterial nanofibers possess stable and highly efficient antibacterial properties.

[0028] Furthermore, during combustion, the graphene oxide-based antibacterial agent exhibits strong interfacial adhesion to polyurethane, forming a dense char layer that inhibits the diffusion of volatiles into the flame, effectively protecting the polymer chains and reducing the impact of oxygen and heat. The graphene oxide-based antibacterial agent also contains N, P, and Si flame-retardant elements, which can exert a synergistic flame-retardant effect to further improve the flame retardancy of the fiber. More notably, copper ions can catalyze the char formation of the fiber in the condensed phase, and copper ions can also generate oxides to assist in reinforcing the char layer, further improving the flame retardant performance of the fiber. Moreover, compared to using existing organic or inorganic flame retardants, the resulting fiber exhibits better washability.

[0029] In summary, the antibacterial core-spun yarn obtained by this invention not only has good mechanical properties and antibacterial properties, but also has high flame retardant properties. Detailed Implementation

[0030] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0031] The polyurethane granules used in the following examples and comparative examples, with a hardness of 90 and a molecular weight of 200,000, were purchased from Dongguan Huangjiang Shengbang Plastic Raw Material Co., Ltd.; the viscose staple fibers, with a length of 5mm, were purchased from Nangong Yingyue Velvet Co., Ltd.; and other raw materials and equipment were all commercially available.

[0032] Example 1

[0033] A graphene oxide-based antibacterial agent is prepared through the following steps:

[0034] 5g of graphene-Schiff base ligand was dispersed in 50mL of anhydrous ethanol, and a solution consisting of 1.8g of copper chloride and 9mL of deionized water was added. The mixture was reacted at 50℃ for 8h, cooled to room temperature, filtered, and the filter cake was washed with deionized water until the washing liquid was free of chloride ions. The cake was dried at 60℃ to constant weight to obtain graphene oxide-based antibacterial agent.

[0035] Graphene-Schiff base ligands are prepared through the following steps:

[0036] Step S1: Add 4g of aminated graphene oxide and 40mL of anhydrous methanol to a three-necked flask. While stirring, add dropwise a solution consisting of 1g of 4-aminobenzaldehyde and 10mL of anhydrous methanol. After the addition is complete, stir the reaction at 60℃ for 4h under a nitrogen atmosphere. Filter the mixture, wash the filter cake with deionized water, and dry it in a vacuum drying oven at 60℃ for 12h to obtain the intermediate product.

[0037] Step S2: Add 5g of 4-carboxybutyltriphenylphosphine bromide and 100mL of DMSO to a flask, stir at room temperature for 10min, then add 0.96g of EDC·HCl and 0.56g of NHS, stir for 0.5h, then add 2.7g of intermediate product, stir at room temperature for 24h, filter, wash the filter cake with deionized water and dry it in a vacuum drying oven at 60℃ for 12h to obtain graphene-Schiff base ligand.

[0038] Aminated graphene oxide is prepared through the following steps:

[0039] 0.1 g of graphene oxide was dispersed in 100 mL of DMF and sonicated for 1 h. Then, 0.1 g of silane coupling agent KH-550 and 5 mL of deionized water were added. The mixture was stirred at 60 °C for 0.5 h. After cooling to room temperature, the mixture was filtered. The filter cake was washed with anhydrous ethanol and then dried in a vacuum oven at 60 °C to constant weight to obtain aminated graphene oxide.

[0040] Example 2

[0041] A graphene oxide-based antibacterial agent is prepared through the following steps:

[0042] 5g of graphene-Schiff base ligand was dispersed in 100mL of anhydrous ethanol, and a solution consisting of 2.5g of copper chloride and 25mL of deionized water was added. The mixture was reacted at 70℃ for 12h. After the reaction was completed, the mixture was cooled to room temperature, filtered, and the filter cake was washed with deionized water until the washing liquid was free of chloride ions. The cake was dried at 60℃ to constant weight to obtain graphene oxide-based antibacterial agent.

[0043] Graphene-Schiff base ligands are prepared through the following steps:

[0044] Step S1: Add 4g of aminated graphene oxide and 60mL of anhydrous methanol to a three-necked flask. While stirring, add dropwise a solution consisting of 1.5g of 4-aminobenzaldehyde and 20mL of anhydrous methanol. After the addition is complete, stir the reaction at 60℃ for 6h under a nitrogen atmosphere. Filter the mixture, wash the filter cake with deionized water, and dry it in a vacuum drying oven at 60℃ for 12h to obtain the intermediate product.

[0045] Step S2: Add 5g of 4-carboxybutyltriphenylphosphine bromide and 100mL of DMSO to a flask, stir at room temperature for 20min, then add 0.96g of EDC·HCl and 0.56g of NHS, stir for 0.5h, then add 3.5g of intermediate product, stir at room temperature for 24h, filter, wash the filter cake with deionized water and dry it in a vacuum drying oven at 60℃ for 12h to obtain graphene-Schiff base ligand.

[0046] Aminated graphene oxide is prepared through the following steps:

[0047] 0.1 g of graphene oxide was dispersed in 100 mL of DMF and sonicated for 1 h. Then, 0.2 g of silane coupling agent KH-550 and 10 mL of deionized water were added. The mixture was stirred at 80 °C for 1 h. After cooling to room temperature, the mixture was filtered. The filter cake was washed with anhydrous ethanol and then dried in a vacuum oven at 60 °C to constant weight to obtain aminated graphene oxide.

[0048] Comparative Example 1

[0049] This comparative example is the graphene-Schiff base ligand from Example 1.

[0050] Comparative Example 2

[0051] This comparative example is the aminated graphene oxide from Example 1.

[0052] Example 3

[0053] A method for preparing an antibacterial core-spun yarn includes the following steps:

[0054] Step 1: Mix 8 kg of polyurethane particles, 42.5 L of tetrahydrofuran and 42.5 L of N,N-dimethylformamide, stir at 50°C and 250 r / min for 24 h, then add 2 kg of graphene oxide-based antibacterial agent from Example 1, and continue stirring for 0.5 h to obtain antibacterial spinning solution;

[0055] The second step involves preparing viscose slivers from viscose staple fibers using the opening process. The viscose slivers are then combed to obtain a viscose web, which is placed on a web conveying device. Antibacterial nanofibers are obtained by electrospinning with an antibacterial spinning solution. The obtained antibacterial nanofibers are sprayed onto the viscose web and bundled through a trumpet-shaped opening to obtain a viscose sliver. The viscose sliver is then fed into an air-jet vortex spinning machine after two drawing passes. Nylon filaments are fed into the machine through a guide device from the gap between the first and second rollers. Vortex spinning is then performed to obtain an antibacterial core-spun yarn with nylon filaments as the core and viscose and antibacterial nanofibers as the outer sheath fibers.

[0056] The viscose cotton roll is 30m long and has a basis weight of 260g / m. The fineness of the nylon filament is 50D, the filament feed ratio is 0.95, the mass ratio of viscose cotton web to antibacterial nanofiber is 1:1, and the mass ratio of viscose sliver to nylon filament is 4:1.

[0057] In the carding process of viscose cotton laps, the cylinder speed is 200 r / min, the licker-in speed is 440 r / min, the doffer speed is 16 r / min, the flats speed is 55 mm / min, the cylinder-flats five-point spacing is 0.28 mm, 0.25 mm, 0.25 mm, 0.25 mm, 0.28 mm, the cylinder-doffer spacing is 0.2 mm, the feed plate-licker-in spacing is 0.2 mm, and the sliver weight is 16 g / 5 m.

[0058] The parameters for the electrospinning process are: spinning temperature 20℃, relative humidity 30%, voltage 16kV, and receiving distance 15cm.

[0059] The adhesive strips are made by combining six adhesive strips in two processes.

[0060] The process parameters for vortex spinning are: total draft ratio of 150 and main draft ratio of 25.

[0061] Example 4

[0062] A method for preparing an antibacterial core-spun yarn includes the following steps:

[0063] Step 1: Mix 10 kg of polyurethane particles, 44 L of tetrahydrofuran and 46 L of N,N-dimethylformamide, stir at 50°C and 250 r / min for 24 h, then add 4 kg of graphene oxide-based antibacterial agent from Example 2, and continue stirring for 0.8 h to obtain antibacterial spinning solution.

[0064] The second step involves preparing viscose slivers from viscose staple fibers using the opening process. The viscose slivers are then combed to obtain a viscose web, which is placed on a web conveying device. Antibacterial nanofibers are obtained by electrospinning with an antibacterial spinning solution. The obtained antibacterial nanofibers are sprayed onto the viscose web and bundled through a trumpet-shaped opening to obtain a viscose sliver. The viscose sliver is then fed into an air-jet vortex spinning machine after two drawing passes. Nylon filaments are fed into the machine through a guide device from the gap between the first and second rollers. Vortex spinning is then performed to obtain an antibacterial core-spun yarn with nylon filaments as the core and viscose and antibacterial nanofibers as the outer sheath fibers.

[0065] The fineness of the nylon filament is 50D, the filament feed ratio is 0.95, the mass ratio of viscose cotton web to antibacterial nanofiber is 1:2, and the mass ratio of viscose sliver to nylon filament is 4:1.

[0066] The viscose cotton roll is 31m long and has a basis weight of 280g / m.

[0067] In the carding process of viscose cotton laps, the cylinder speed is 200 r / min, the licker-in speed is 440 r / min, the doffer speed is 16 r / min, the flats speed is 55 mm / min, the cylinder-flats five-point spacing is 0.28 mm, 0.25 mm, 0.25 mm, 0.25 mm, 0.28 mm, the cylinder-doffer spacing is 0.25 mm, the feed plate-licker-in spacing is 0.24 mm, and the sliver weight is 17 g / 5 m.

[0068] The parameters for the electrospinning process are: spinning temperature 24℃, relative humidity 40%, voltage 18kV, and receiving distance 18cm.

[0069] The adhesive strips are made by combining six adhesive strips in two processes.

[0070] The process parameters for vortex spinning are: total draft ratio of 150 and main draft ratio of 25.

[0071] Example 5

[0072] A method for preparing an antibacterial core-spun yarn includes the following steps:

[0073] Step 1: Mix 15 kg of polyurethane particles, 46 L of tetrahydrofuran and 46 L of N,N-dimethylformamide, stir at 50°C and 250 r / min for 24 h, then add 6 kg of graphene oxide-based antibacterial agent from Example 2, and continue stirring for 1 h to obtain antibacterial spinning solution.

[0074] The second step involves preparing viscose slivers from viscose staple fibers using the opening process. The viscose slivers are then combed to obtain a viscose web, which is placed on a web conveying device. Antibacterial nanofibers are obtained by electrospinning with an antibacterial spinning solution. The obtained antibacterial nanofibers are sprayed onto the viscose web and bundled through a trumpet-shaped opening to obtain a viscose sliver. The viscose sliver is then fed into an air-jet vortex spinning machine after two drawing passes. Nylon filaments are fed into the machine through a guide device from the gap between the first and second rollers. Vortex spinning is then performed to obtain an antibacterial core-spun yarn with nylon filaments as the core and viscose and antibacterial nanofibers as the outer sheath fibers.

[0075] The fineness of the nylon filament is 50D, the filament feed ratio is 0.95, the mass ratio of viscose cotton web to antibacterial nanofiber is 1:3, and the mass ratio of viscose sliver to nylon filament is 4:1.

[0076] The viscose cotton roll is 32m long and has a basis weight of 300g / m.

[0077] In the carding process of viscose cotton laps, the cylinder speed is 210 r / min, the licker-in speed is 460 r / min, the doffer speed is 18 r / min, the flats speed is 65 mm / min, the cylinder-flats five-point spacing is 0.28 mm, 0.25 mm, 0.25 mm, 0.25 mm, 0.28 mm, the cylinder-doffer spacing is 0.28 mm, the feed plate-licker-in spacing is 0.28 mm, and the sliver weight is 18 g / 5 m.

[0078] The parameters for the electrospinning process are: spinning temperature 25℃, relative humidity 60%, voltage 21kV, and receiving distance 20cm.

[0079] The adhesive strips are made by combining six adhesive strips in two processes.

[0080] The process parameters for vortex spinning are: total draft ratio of 150 and main draft ratio of 25.

[0081] Comparative Example 3

[0082] Compared with Example 3, the graphene oxide-based antibacterial agent in Example 3 was replaced with the substance in Comparative Example 1, while the other raw materials and preparation process were the same as in Example 3.

[0083] Comparative Example 4

[0084] Compared with Example 3, the graphene oxide-based antibacterial agent in Example 3 was replaced with the substance in Comparative Example 2, while the other raw materials and preparation process were the same as in Example 3.

[0085] The antibacterial core-spun yarns obtained in Examples 3-5 and Comparative Examples 3-4 were tested. The inhibition rate of the core-spun yarns against Staphylococcus aureus and Escherichia coli was tested according to GB / T20994.3-2008 "Evaluation of antibacterial properties of textiles - Part 3: Oscillation method". The limiting oxygen index was tested according to GB / T5454-1997 standard. The yarns were washed 100 times using a wash fastness tester. The antibacterial properties and limiting oxygen index of the yarns after washing were tested. The results are shown in Table 1.

[0086] Table 1

[0087]

[0088] As can be seen from Table 1, compared with Comparative Examples 3 and 4, the core-spun yarns prepared in Examples 3-5 have better antibacterial properties, flame retardancy, and washability.

[0089] It should be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article, or apparatus.

[0090] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A method for producing an antibacterial core spun yarn, characterized by, The method comprises the following steps: The first step is to disperse the graphene-Schiff base ligand in anhydrous ethanol, add an aqueous solution of copper chloride, and react at 50-70 DEG C for 8-12 h, cool, filter, wash and dry the filter cake to obtain the graphene-based antibacterial agent; The second step is to mix polyurethane particles, tetrahydrofuran and N,N-dimethylformamide, stir at 50 DEG C for 24 h, add the graphene-based antibacterial agent, and continue to stir for 0.5-1 h to obtain the antibacterial spinning solution; The third step is to prepare viscose cotton lap according to the opening cotton process, card the viscose cotton lap to obtain a viscose cotton web, spray the antibacterial nanofiber obtained by electrospinning the antibacterial spinning solution onto the viscose cotton web, bundle through a horn mouth, obtain a viscose sliver, feed the viscose sliver into a jet vortex spinning machine after two-drawing, feed the polyamide filament from the first roller and the second roller through the interval distance, vortex spinning, and obtain the antibacterial core-spun yarn; The graphene-Schiff base ligand is prepared by the following steps: Step S1: add amino-functionalized graphene oxide and anhydrous methanol into a three-necked flask, drop 4-aminobenzaldehyde anhydrous methanol solution under stirring, after the dropping is completed, stir at 60 DEG C for 4-6 h under nitrogen atmosphere to obtain an intermediate product; Step S2: add 4-carboxybutyltriphenylphosphonium bromide and DMSO into a flask, stir at room temperature for 10-20 min, add EDC·HCl and NHS, stir for 0.5 h, add the intermediate product, and stir at room temperature for 24 h to obtain the graphene-Schiff base ligand.

2. A process for the production of an antimicrobial core spun yarn as claimed in claim 1, wherein, The amount ratio of the graphene-Schiff base ligand, anhydrous ethanol and copper chloride in the first step is 5 g: 50-100 mL: 1.8-2.5 g, and the aqueous solution of copper chloride is composed of copper chloride and deionized water according to 1 g: 5-10 mL.

3. A process for the preparation of an antimicrobial core spun yarn as claimed in claim 1, wherein, The amount ratio of the polyurethane particles, tetrahydrofuran, N,N-dimethylformamide and graphene-based antibacterial agent in the second step is 8-15 g: 42.5-46 mL: 42.5-46 mL: 2-6 g.

4. A process for the preparation of an antimicrobial core spun yarn as claimed in claim 1, wherein, The mass ratio of the viscose cotton web and the antibacterial nanofiber in the third step is 1: 1-3, and the mass ratio of the viscose sliver and the polyamide filament is 4:

1.

5. A process for the preparation of an antimicrobial core spun yarn as claimed in claim 1, wherein, The mass ratio of the amino-functionalized graphene oxide and 4-aminobenzaldehyde in step S1 is 4: 1-1.

5.

6. A process for the preparation of an antimicrobial core spun yarn as claimed in claim 1, wherein, The amount ratio of 4-carboxybutyltriphenylphosphonium bromide, DMSO, EDC·HCl, NHS and the intermediate product in step S2 is 5 g: 100 mL: 0.96 g: 0.56 g: 2.7-3.5 g.

7. A process for the preparation of an antimicrobial core spun yarn as claimed in claim 1, wherein, The parameters of the electrospinning process are as follows: the spinning temperature is 20-25 DEG C, the relative humidity is 30-60%, the voltage is 16-21 kV, and the receiving distance is 15-20 cm.

8. An antimicrobial core spun yarn, characterized by, The graphene-Schiff base ligand is prepared by the method according to any one of claims 1-7.

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