High-strength antibacterial acrylic fiber and preparation process thereof

Abstract

The invention relates to the technical field of acrylic fiber preparation, and particularly discloses a high-strength antibacterial acrylic fiber and a preparation technology thereof.The high-strength antibacterial acrylic fiber is prepared from, by weight, 110-130 parts of modified polyacrylonitrile and 8-10 parts of antibacterial filler; the functional monomer and the antibacterial filler are added, the functional monomer contains rich active hydroxyl, a flexible long-chain alkane structure and a pyrimidine ring, not only can be chemically crosslinked with pretreated polyacrylonitrile, but also can generate hydrogen-bond interaction with the antibacterial filler, so that the overall crosslinking density of polyacrylonitrile is improved, the strength of the acrylic fiber is improved, and the antibacterial property of the acrylic fiber is improved. The hydrophilicity and the antibacterial property of the acrylic fiber are improved.

Description

Technical Field

[0001] This application relates to the technical field of acrylic fibers. More specifically, it relates to a high-strength antibacterial acrylic fiber and its preparation process. Background Art

[0002] Acrylic fiber is a fiber prepared from polyacrylonitrile as raw material through processes such as wet spinning and melt spinning. It has good fluffiness, elasticity, warmth retention, and excellent sun resistance. Under general solvent and acid-base conditions, its performance remains intact, and it is widely used in the textile and clothing industries, medical and health fields, etc.

[0003] However, the molecular chain of acrylic fiber mainly has groups such as CH2, CH, and CN. The lack of hydrophilic groups results in poor moisture absorption of polyacrylonitrile, easy generation of static electricity, and affects comfort. At the same time, it has a low breaking strength and does not have good antibacterial properties, which is not conducive to the practical application of acrylic fiber in medical and health fields.

[0004] In existing research, vinyl acetate and acrylonitrile are copolymerized to prepare fibers with good moisture absorption. However, the introduction of vinyl acetate will reduce the crystallinity of the copolymer, resulting in a decrease in the mechanical properties of the prepared fibers.

[0005] Therefore, in order to better utilize acrylic fiber, it is urgent to develop an acrylic fiber with good hydrophilicity, high strength, and excellent antibacterial properties.

[0006] Based on the above statement, this application provides a high-strength antibacterial acrylic fiber and its preparation process. Summary of the Invention

[0007] In order to solve the problems in the prior art that polyacrylonitrile has poor moisture absorption, and at the same time, its mechanical properties cannot be improved by copolymerization modification with vinyl acetate and polyacrylonitrile does not have antibacterial properties, which affects the wearing comfort, this application provides a high-strength antibacterial acrylic fiber and its preparation process.

[0008] A high-strength antibacterial acrylic fiber, comprising the following raw materials in parts by weight: 110 - 130 parts of modified polyacrylonitrile, 8 - 10 parts of antibacterial filler;

[0009] Preferably, the modified polyacrylonitrile is first obtained by treating polyacrylonitrile with an aqueous ethanol solution to obtain pretreated polyacrylonitrile, and then graft copolymerizing with a functional monomer.

[0010] Preferably, the functional monomer is first obtained by click addition reaction of 6-amino-2-mercaptopyrimidin-4-ol and acrylamide to obtain an amino monomer, then ring-opening esterification reaction with octenyl succinic anhydride to obtain an unsaturated monomer, and finally amidation reaction with tris(hydroxymethyl)aminomethane.

[0011] Preferably, the antibacterial filler is first prepared by modifying nano-zinc oxide with KH-560 to obtain epoxy-group zinc oxide, and then reacting it with α-acetamidocinnamic acid through ring-opening esterification reaction.

[0012] The preparation method of the high-strength antibacterial acrylic fiber includes the following steps:

[0013] Melting and blending the modified polyacrylonitrile and the antibacterial filler in a twin-screw extruder, extruding and granulating, and then spinning the pellets in a melt spinning machine; the obtained fiber is subjected to stretching treatment in a stretching machine to obtain the high-strength antibacterial acrylic fiber.

[0014] Preferably, the screw temperature of the twin-screw extruder is 235-245 °C, and the screw speed is set to 30-40 r / min; the melt spinning machine controls the spinning temperature at 260-280 °C, and the spinning speed is 600-800 m / min; the hot plate temperature of the stretching machine is controlled at 82-90 °C, and the draw ratio is controlled at 2.8-3.2 times.

[0015] Preferably, the modified polyacrylonitrile is prepared by the following steps:

[0016] Step A1: Add polyacrylonitrile to an ethanol aqueous solution, heat it to reflux, stir for 2-4 h, take it out, wash and dry it to obtain pretreated polyacrylonitrile, wherein the mass ratio of polyacrylonitrile to the ethanol aqueous solution is 2-4:65-75, and the mass fraction of the ethanol aqueous solution is 20-30%;

[0017] Step A2: Add the pretreated polyacrylonitrile, the functional monomer and benzophenone to anhydrous ethanol, stir evenly, irradiate with ultraviolet light for 25-35 min, control the irradiation temperature at 55-65 °C, and then perform Soxhlet extraction, washing and drying to obtain the modified polyacrylonitrile, wherein the mass ratio of the pretreated polyacrylonitrile, the functional monomer, benzophenone and anhydrous ethanol is 1.8-2.2:0.6-0.8:0.02-0.04:50-60. In the above reaction process, anhydrous ethanol is used as the solvent and benzophenone is used as the photoinitiator. The cyano group on the pretreated polyacrylonitrile can undergo graft copolymerization with the amino group on the functional monomer to obtain the modified polyacrylonitrile.

[0018] Preferably, the functional monomer is prepared by the following steps:

[0019] Step B1: 6-Amino-2-mercaptopyrimidin-4-ol, acrylamide and a photoinitiator are added to anhydrous DMF, stirred evenly, and the rotation speed is maintained unchanged. While stirring, it is placed under ultraviolet irradiation for 12 - 26 min, and the irradiation temperature is controlled at 75 - 85 °C to obtain an amino monomer. Among them, the mass ratio of 6-amino-2-mercaptopyrimidin-4-ol, acrylamide, photoinitiator and anhydrous DMF is 4 - 6:1.8 - 2.6:0.02 - 0.04:60 - 80. The photoinitiator is composed of 2,2-dimethoxy-2-phenylacetophenone and azobisisobutyronitrile mixed in a mass ratio of 1.8:3 - 5. During the above reaction process, using anhydrous DMF as a solvent, the mercapto group on 6-amino-2-mercaptopyrimidin-4-ol undergoes a click addition reaction with the unsaturated double bond on acrylamide to obtain the amino monomer;

[0020] Step B2: The amino monomer is added to anhydrous DMF, stirred evenly, the pH value is adjusted to 8 - 9, and a mixed solution a of octenyl succinic anhydride and isopropanol is added dropwise, controlled to be added dropwise within 10 min. After dropping, the temperature is raised to 74 - 78 °C, and stirring and reacting continue for 6 - 12 h. The pH value is adjusted to 6.8 - 7.2, washed, and dried to obtain an unsaturated monomer. Among them, the mass ratio of the amino monomer, anhydrous DMF and the mixed solution b is 3 - 5:75 - 85:26 - 32. In the mixed solution a, the mass ratio of octenyl succinic anhydride and isopropanol is 2.2 - 4.6:30. During the above reaction process, using anhydrous DMF as a solvent, the active amino group on the amino monomer undergoes a ring-opening esterification reaction with the anhydride group on octenyl succinic anhydride to obtain the unsaturated monomer;

[0021] Step B3: The unsaturated monomer and tris(hydroxymethyl)aminomethane are added to anhydrous DMF, stirred evenly, and a mixed solution b of N,N'-dicyclohexylcarbodiimide, 4-dimethylaminopyridine and anhydrous DMF is added dropwise while stirring. After dropping, the temperature is raised to 74 - 78 °C, and stirring and reacting continue for 5 - 6 h. After the reaction ends, it is filtered, washed and dried to obtain a functional monomer. Among them, the mass ratio of the unsaturated monomer, tris(hydroxymethyl)aminomethane, anhydrous DMF and the mixed solution b is 6 - 8:1.6 - 2.2:60 - 70:25 - 35. In the mixed solution b, the mass ratio of N,N'-dicyclohexylcarbodiimide, 4-dimethylaminopyridine and anhydrous DMF is 3.4 - 4.4:

[0022] 2.4 - 2.8:23 - 27. During the above reaction process, using anhydrous DMF as a solvent, N,N'-dicyclohexylcarbodiimide as a dehydrating agent, 4-dimethylaminopyridine as an acylating agent, the unsaturated monomer and tris(hydroxymethyl)aminomethane undergo an amidation reaction to obtain the functional monomer.

[0023] Preferably, the antibacterial filler is prepared by the following steps:

[0024] Step C1: Ultrasonically mix nano-zinc oxide, deionized water, absolute ethanol, and KH-560 for 30 - 50 min, stir and react at room temperature for 6 - 8 h, centrifuge, wash the precipitate, and dry it to obtain epoxy-group zinc oxide. Among them, the mass ratio of nano-zinc oxide, deionized water, absolute ethanol, and KH-560 is 5:10:25 - 35:0.4 - 0.6;

[0025] Step C2: Ultrasonically disperse epoxy-group zinc oxide in anhydrous DMF, dropwise add a mixed solution c of tetrabutylammonium bromide, α-acetamidocinnamic acid, and anhydrous DMF. After dropping, raise the temperature to 90 - 110 °C, stir and react for 2 - 3 h. After the reaction, centrifuge, wash several times, and dry to obtain an antibacterial filler. Among them, the mass ratio of epoxy-group zinc oxide, anhydrous DMF, and mixed solution c is 2 - 4:50 - 60:26 - 32. In the mixed solution c, the mass ratio of tetrabutylammonium bromide, α-acetamidocinnamic acid, and anhydrous DMF is 0.1:1.2 - 1.6:30. During the above reaction process, using anhydrous DMF as the solvent and tetrabutylammonium bromide as the catalyst, an open-ring esterification reaction occurs between epoxy-group zinc oxide and α-acetamidocinnamic acid to obtain an antibacterial filler.

[0026] In summary, the present application has the following beneficial effects:

[0027] In order to improve the hydrophilicity, strength, and antibacterial property of acrylic fibers, the present application starts from two aspects. One is to add modified polyacrylonitrile, which is prepared by modifying pretreated polyacrylonitrile with a functional monomer. The functional monomer contains rich active hydroxyl groups, flexible long-chain alkane structures, and pyrimidine rings. The presence of active hydroxyl groups can not only endow the modified polyacrylonitrile with good hydrophilicity, but also it can form hydrogen bond interactions with the active hydroxyl groups on the antibacterial filler to improve the strength of acrylic fibers. The presence of flexible long-chain alkane structures can entangle with the flexible chain structures in the pretreated polyacrylonitrile to further improve the strength of acrylic fibers. The presence of pyrimidine rings not only has antibacterial properties itself, but also can cooperate with the zinc oxide structure in the antibacterial filler to improve the antibacterial property of acrylic fibers. The other is to add an antibacterial filler. On the one hand, it exerts the good physical properties of nano-zinc oxide to improve the weather resistance of acrylic fibers. On the other hand, α-acetamidocinnamic acid grafted on the surface of the antibacterial filler not only has a rigid ring structure, but also has an amide group that can form hydrogen bonds with the functional monomer. Introducing it into acrylic fibers can cooperate with the functional monomer to jointly improve the strength of acrylic fibers. Specific Embodiments

[0028] To make the embodiments of the present application easier to understand, the following will detail the present application with specific examples. These examples are only illustrative and are not limited to the application scope of the present application.

[0029] The following further details the present application with examples.

[0030] The polyacrylonitrile powder (Mw = 85000 g / mol) used in the examples and comparative examples of this application was purchased from Shanghai Macklin Co., Ltd.

[0031] Preparation Examples 1-3 and Comparative Preparation Examples 1-3 provided a functional monomer.

[0032] Preparation Example 1

[0033] This preparation example provides a functional monomer, which is prepared by the following steps:

[0034] Step B1: 6-Amino-2-mercaptopyrimidin-4-ol, acrylamide, and a photoinitiator were added to anhydrous DMF. While controlling the rotation speed at 450 rpm, it was stirred for 15 min until uniform. While maintaining the rotation speed unchanged, it was irradiated with ultraviolet light with a peak wavelength of 365 nm and an intensity of 80 mw / cm 2 for 12 min, and the irradiation temperature was controlled at 75 °C to obtain an amino monomer. Among them, the mass ratio of 6-amino-2-mercaptopyrimidin-4-ol, acrylamide, the photoinitiator, and anhydrous DMF was 4:1.8:0.02:60, and the photoinitiator was a mixture of 2,2-dimethoxy-2-phenylacetophenone and azobisisobutyronitrile in a mass ratio of 1.8:3;

[0035] Step B2: The amino monomer was added to anhydrous DMF. While controlling the rotation speed at 500 rpm, it was stirred for 20 min until uniform. The pH value was adjusted to 8 with 0.6 M aqueous sodium hydroxide solution, and a mixed solution a of octenyl succinic anhydride and isopropanol was added dropwise, and the addition was controlled to be completed within 10 min. After the addition was completed, the temperature was raised to 74 °C, and while maintaining the rotation speed unchanged, the reaction was continued to stir for 6 h. The pH value was adjusted to 6.8 with 0.8 M aqueous hydrochloric acid solution, and it was washed 3 times with anhydrous ethanol and deionized water in sequence, and dried to constant weight at 55 °C to obtain an unsaturated monomer. Among them, the mass ratio of the amino monomer, anhydrous DMF, and the mixed solution b was 3:75:26. In the mixed solution a, the mass ratio of octenyl succinic anhydride and isopropanol was 2.2:30;

[0036] Step B3: The unsaturated monomer and tris(hydroxymethyl)aminomethane were added to anhydrous DMF. While controlling the rotation speed at 550 rpm, it was stirred for 22 min until uniform. While stirring, a mixed solution b of N,N'-dicyclohexylcarbodiimide, 4-dimethylaminopyridine, and anhydrous DMF was added dropwise. After the addition was completed, the temperature was raised to 74 °C, and while maintaining the rotation speed unchanged, the reaction was stirred for 5 h. After the reaction was completed, suction filtration was carried out, and the filter cake was washed 3 times with anhydrous ethanol and deionized water in sequence, and dried to constant weight at 65 °C to obtain a functional monomer. Among them, the mass ratio of the unsaturated monomer, tris(hydroxymethyl)aminomethane, anhydrous DMF, and the mixed solution b was 6:1.6:60:25. In the mixed solution b, the mass ratio of N,N'-dicyclohexylcarbodiimide, 4-dimethylaminopyridine, and anhydrous DMF was 3.4:2.4:23.

[0037] Preparation Example 2

[0038] This preparation example provides a functional monomer, which is prepared by the following steps:

[0039] Step B1: 6-Amino-2-mercaptopyrimidin-4-ol, acrylamide and a photoinitiator are added to anhydrous DMF. While controlling the rotation speed at 500 rpm, stir for 18 min until homogeneous. Keeping the rotation speed unchanged, irradiate under ultraviolet light with a peak wavelength of 365 nm and an intensity of 80 mw / cm 2 for 19 min, and control the irradiation temperature at 80 °C to obtain an amino monomer. Among them, the mass ratio of 6-amino-2-mercaptopyrimidin-4-ol, acrylamide, the photoinitiator and anhydrous DMF is 5:2.2:0.03:70, and the photoinitiator is a mixture of 2,2-dimethoxy-2-phenylacetophenone and azobisisobutyronitrile in a mass ratio of 1.8:4;

[0040] Step B2: The amino monomer is added to anhydrous DMF. While controlling the rotation speed at 550 rpm, stir for 24 min until homogeneous. Adjust the pH value to 8.5 with 0.8 M aqueous sodium hydroxide solution, and dropwise add a mixed solution a of octenyl succinic anhydride and isopropyl alcohol, and control to finish dropping within 10 min. After dropping, raise the temperature to 76 °C, keep the rotation speed unchanged, and continue to stir and react for 9 h. Adjust the pH value to 7.0 with 1.0 M aqueous hydrochloric acid solution, wash 4 times with anhydrous ethanol and deionized water in sequence, and dry at 60 °C to constant weight to obtain an unsaturated monomer. Among them, the mass ratio of the amino monomer, anhydrous DMF and the mixed solution b is 4:80:29. In the mixed solution a, the mass ratio of octenyl succinic anhydride and isopropyl alcohol is 3.4:30;

[0041] Step B3: The unsaturated monomer and tris(hydroxymethyl)aminomethane are added to anhydrous DMF. While controlling the rotation speed at 600 rpm, stir for 26 min until homogeneous. While stirring, dropwise add a mixed solution b of N,N'-dicyclohexylcarbodiimide, 4-dimethylaminopyridine and anhydrous DMF. After dropping, raise the temperature to 76 °C, keep the rotation speed unchanged, and stir and react for 5.5 h. After the reaction is completed, perform suction filtration. The filter cake is washed 4 times with anhydrous ethanol and deionized water in sequence, and dried at 70 °C to constant weight to obtain the functional monomer. Among them, the mass ratio of the unsaturated monomer, tris(hydroxymethyl)aminomethane, anhydrous DMF and the mixed solution b is 7:1.9:65:30. In the mixed solution b, the mass ratio of N,N'-dicyclohexylcarbodiimide, 4-dimethylaminopyridine and anhydrous DMF is 3.9:2.6:25.

[0042] Preparation Example 3

[0043] This preparation example provides a functional monomer, which is prepared by the following steps:

[0044] Step B1: 6-Amino-2-mercaptopyrimidin-4-ol, acrylamide, and a photoinitiator are added to anhydrous DMF. While controlling the rotation speed at 550 rpm, stir for 21 min until homogeneous. Keep the rotation speed unchanged, and irradiate with ultraviolet light for 26 min while stirring. Control the irradiation temperature at 85 °C to obtain an amino monomer. Among them, the mass ratio of 6-amino-2-mercaptopyrimidin-4-ol, acrylamide, the photoinitiator, and anhydrous DMF is 6:2.6:0.04:80. The photoinitiator is composed of 2,2-dimethoxy-2-phenylacetophenone and azobisisobutyronitrile mixed in a mass ratio of 1.8:5;

[0045] Step B2: The amino monomer is added to anhydrous DMF. While controlling the rotation speed at 600 rpm, stir for 28 min until homogeneous. Adjust the pH value to 9 with 1.0 M aqueous sodium hydroxide solution, and dropwise add a mixed solution a of octenyl succinic anhydride and isopropyl alcohol. Control to finish dropping within 10 min. After dropping, raise the temperature to 78 °C, keep the rotation speed unchanged, and continue to stir and react for 12 h. Adjust the pH value to 7.2 with 1.2 M aqueous hydrochloric acid solution, and wash 5 times with anhydrous ethanol and deionized water in sequence, and dry at 65 °C to constant weight to obtain an unsaturated monomer. Among them, the mass ratio of the amino monomer, anhydrous DMF, and the mixed solution b is 5:85:32. In the mixed solution a, the mass ratio of octenyl succinic anhydride and isopropyl alcohol is 4.6:30;

[0046] Step B3: The unsaturated monomer and tris(hydroxymethyl)aminomethane are added to anhydrous DMF. While controlling the rotation speed at 650 rpm, stir for 30 min until homogeneous. While stirring, dropwise add a mixed solution b of N,N'-dicyclohexylcarbodiimide, 4-dimethylaminopyridine, and anhydrous DMF. After dropping, raise the temperature to 78 °C, keep the rotation speed unchanged, and stir and react for 6 h. After the reaction is completed, perform suction filtration. The filter cake is washed 5 times with anhydrous ethanol and deionized water in sequence, and dried at 75 °C to constant weight to obtain a functional monomer. Among them, the mass ratio of the unsaturated monomer, tris(hydroxymethyl)aminomethane, anhydrous DMF, and the mixed solution b is 8:2.2:70:35. In the mixed solution b, the mass ratio of N,N'-dicyclohexylcarbodiimide, 4-dimethylaminopyridine, and anhydrous DMF is 4.4:2.8:27.

[0047] Comparative Preparation Example 1

[0048] This comparative preparation example provides a functional monomer, which is prepared by the following steps:

[0049] Step B1: 2,6-Diaminopyrimidin-4-ol, acrylamide, and a photoinitiator are added to anhydrous DMF. While controlling the rotation speed at 450 rpm, stir for 15 min until homogeneous. Keep the rotation speed unchanged, and place it under irradiation with a peak wavelength of 365 nm and an intensity of 80 mw / cm 2Irradiate under ultraviolet light for 12 min, control the irradiation temperature at 75 °C to obtain an amino monomer. Among them, the mass ratio of 2,6-diaminopyrimidin-4-ol, acrylamide, photoinitiator and anhydrous DMF is 4:1.8:0.02:60, and the photoinitiator is a mixture of 2,2-dimethoxy-2-phenylacetophenone and azobisisobutyronitrile in a mass ratio of 1.8:3;

[0050] Step B2: Add the amino monomer to anhydrous DMF, control the rotation speed at 500 rpm, stir for 20 min until homogeneous, adjust the pH value to 8 with 0.6 M aqueous sodium hydroxide solution, dropwise add a mixed solution a of octenyl succinic anhydride and isopropanol, control to finish dropping within 10 min, after dropping, raise the temperature to 74 °C, keep the rotation speed unchanged, continue to stir and react for 6 h, adjust the pH value to 6.8 with 0.8 M aqueous hydrochloric acid solution, wash 3 times with anhydrous ethanol and deionized water in turn, and dry at 55 °C to constant weight to obtain an unsaturated monomer. Among them, the mass ratio of the amino monomer, anhydrous DMF and mixed solution b is 3:75:26. In the mixed solution a, the mass ratio of octenyl succinic anhydride and isopropanol is 2.2:30;

[0051] Step B3: Add the unsaturated monomer and tris(hydroxymethyl)aminomethane to anhydrous DMF, control the rotation speed at 550 rpm, stir for 22 min until homogeneous, while stirring, dropwise add a mixed solution b of N,N'-dicyclohexylcarbodiimide, 4-dimethylaminopyridine and anhydrous DMF. After dropping, raise the temperature to 74 °C, keep the rotation speed unchanged, stir and react for 5 h. After the reaction is completed, filter by suction. The filter cake is washed 3 times with anhydrous ethanol and deionized water in turn, and dried at 65 °C to constant weight to obtain a functional monomer. Among them, the mass ratio of the unsaturated monomer, tris(hydroxymethyl)aminomethane, anhydrous DMF and mixed solution b is 6:1.6:60:25. In the mixed solution b, the mass ratio of N,N'-dicyclohexylcarbodiimide, 4-dimethylaminopyridine and anhydrous DMF is 3.4:2.4:23.

[0052] Comparative Preparation Example 2

[0053] This comparative preparation example provides a functional monomer, which is prepared by the following steps:

[0054] Step B1: Add 5-amino-2-mercaptobenzimidazole, acrylamide and a photoinitiator to anhydrous DMF, control the rotation speed at 450 rpm, stir for 15 min until homogeneous, keep the rotation speed unchanged, and while stirring, place it under ultraviolet light with a wavelength peak of 365 nm and an intensity of 80 mw / cm 2Irradiate under ultraviolet light with a wavelength peak of 365 nm and an intensity of 80 mw / cm² for 12 min, and control the irradiation temperature at 75 °C to obtain an amino monomer. Among them, the mass ratio of 5-amino-2-mercaptobenzimidazole, acrylamide, photoinitiator and anhydrous DMF is 4:1.8:0.02:60, and the photoinitiator is composed of 2,2-dimethoxy-2-phenylacetophenone and azobisisobutyronitrile mixed in a mass ratio of 1.8:3;

[0055] Step B2: Add the amino monomer to anhydrous DMF, control the rotation speed at 500 rpm, stir for 20 min until uniform, adjust the pH value to 8 with 0.6 M aqueous sodium hydroxide solution, dropwise add the mixed solution a of octenyl succinic anhydride and isopropanol, control to finish dropping within 10 min, after dropping, raise the temperature to 74 °C, keep the rotation speed unchanged, continue stirring and reacting for 6 h, adjust the pH value to 6.8 with 0.8 M aqueous hydrochloric acid solution, wash 3 times with anhydrous ethanol and deionized water in sequence, and dry at 55 °C to constant weight to obtain an unsaturated monomer. Among them, the mass ratio of the amino monomer, anhydrous DMF and the mixed solution b is 3:75:26, and in the mixed solution a, the mass ratio of octenyl succinic anhydride and isopropanol is 2.2:30;

[0056] Step B3: Add the unsaturated monomer and tris(hydroxymethyl)aminomethane to anhydrous DMF, control the rotation speed at 550 rpm, stir for 22 min until uniform, while stirring, dropwise add the mixed solution b of N,N'-dicyclohexylcarbodiimide, 4-dimethylaminopyridine and anhydrous DMF, after dropping, raise the temperature to 74 °C, keep the rotation speed unchanged, stir and react for 5 h, after the reaction is completed, carry out suction filtration, wash the filter cake 3 times with anhydrous ethanol and deionized water in sequence, and dry at 65 °C to constant weight to obtain a functional monomer. Among them, the mass ratio of the unsaturated monomer, tris(hydroxymethyl)aminomethane, anhydrous DMF and the mixed solution b is 6:1.6:60:25, and in the mixed solution b, the mass ratio of N,N'-dicyclohexylcarbodiimide, 4-dimethylaminopyridine and anhydrous DMF is 3.4:2.4:23.

[0057] Comparative Preparation Example 3

[0058] This comparative preparation example provides a functional monomer, which is prepared by the following steps:

[0059] Step B1: Add 6-amino-2-mercaptopyrimidin-4-ol, acrylamide and a photoinitiator to anhydrous DMF, control the rotation speed at 450 rpm, stir for 15 min until uniform, keep the rotation speed unchanged, and while stirring, place it under ultraviolet light with a wavelength peak of 365 nm and an intensity of 80 mw / cm 2Irradiate for 12 min under ultraviolet light, control the irradiation temperature at 75 °C to obtain an amino monomer. Among them, the mass ratio of 6-amino-2-mercaptopyrimidin-4-ol, acrylamide, photoinitiator and anhydrous DMF is 4:1.8:0.02:60, and the photoinitiator is composed of 2,2-dimethoxy-2-phenylacetophenone and azobisisobutyronitrile mixed according to a mass ratio of 1.8:3;

[0060] Step B2: Add the amino monomer into anhydrous DMF, stir at a controlled speed of 500 rpm for 20 min until homogeneous, adjust the pH value to 8 with 0.6 M aqueous sodium hydroxide solution, dropwise add a mixed solution a of itaconic anhydride and isopropanol, control to finish dropping within 10 min, after dropping, raise the temperature to 74 °C, maintain the rotation speed unchanged, continue to stir and react for 6 h, adjust the pH value to 6.8 with 0.8 M aqueous hydrochloric acid solution, wash 3 times with anhydrous ethanol and deionized water in sequence, and dry at 55 °C to constant weight to obtain an unsaturated monomer. Among them, the mass ratio of the amino monomer, anhydrous DMF and the mixed solution b is 3:75:26, and in the mixed solution a, the mass ratio of itaconic anhydride and isopropanol is 2.2:30;

[0061] Step B3: Add the unsaturated monomer and tris(hydroxymethyl)aminomethane into anhydrous DMF, stir at a controlled speed of 550 rpm for 22 min until homogeneous, while stirring, dropwise add a mixed solution b of N,N-dicyclohexylcarbodiimide, 4-dimethylaminopyridine and anhydrous DMF, after dropping, raise the temperature to 74 °C, maintain the rotation speed unchanged, stir and react for 5 h, after the reaction is completed, filter by suction, wash the filter cake 3 times with anhydrous ethanol and deionized water in sequence, and dry at 65 °C to constant weight to obtain a functional monomer. Among them, the mass ratio of the unsaturated monomer, tris(hydroxymethyl)aminomethane, anhydrous DMF and the mixed solution b is 6:1.6:60:25, and in the mixed solution b, the mass ratio of N,N-dicyclohexylcarbodiimide, 4-dimethylaminopyridine and anhydrous DMF is 3.4:2.4:23.

[0062] Preparation Examples 4-6 and Comparative Preparation Examples 4-6 provide a preparation method of modified polyacrylonitrile.

[0063] Preparation Example 4

[0064] This preparation example provides a modified polyacrylonitrile, which is prepared by the following steps:

[0065] Step A1: Add polyacrylonitrile into an ethanol aqueous solution, raise the temperature to reflux, stir and process at a controlled speed of 600 rpm for 2 h, take out, wash 3 times with deionized water, and dry at 65 °C to constant weight to obtain pretreated polyacrylonitrile. Among them, the mass ratio of polyacrylonitrile and the ethanol aqueous solution is 2:65, and the mass fraction of the ethanol aqueous solution is 20%;

[0066] Step A2: Add the pretreated polyacrylonitrile, the functional monomer prepared in Preparation Example 1, and benzophenone into absolute ethanol, stir at 700 rpm for 16 min until homogeneous, then place it under ultraviolet light with a peak wavelength of 365 nm and an intensity of 80 mw / cm 2 , irradiate for 25 min, control the irradiation temperature at 55 °C, then place it in a Soxhlet extractor, extract with acetone for 16 h, wash with deionized water 3 times, and dry at 65 °C to constant weight to obtain modified polyacrylonitrile. Among them, the mass ratio of the pretreated polyacrylonitrile, the functional monomer, benzophenone, and absolute ethanol is 1.8:0.6:0.02:50.

[0067] Preparation Example 5

[0068] This preparation example provides a modified polyacrylonitrile, which is prepared by the following steps:

[0069] Step A1: Add polyacrylonitrile into an ethanol aqueous solution, heat up to reflux, stir at 700 rpm for 3 h, take it out, wash with deionized water 4 times, and dry at 70 °C to constant weight to obtain pretreated polyacrylonitrile. Among them, the mass ratio of polyacrylonitrile and the ethanol aqueous solution is 3:70, and the mass fraction of the ethanol aqueous solution is 25%.

[0070] Step A2: Add the pretreated polyacrylonitrile, the functional monomer prepared in Preparation Example 2, and benzophenone into absolute ethanol, stir at 750 rpm for 20 min until homogeneous, then place it under ultraviolet light with a peak wavelength of 365 nm and an intensity of 80 mw / cm 2 , irradiate for 30 min, control the irradiation temperature at 60 °C, then place it in a Soxhlet extractor, extract with acetone for 18 h, wash with deionized water 4 times, and dry at 70 °C to constant weight to obtain modified polyacrylonitrile. Among them, the mass ratio of the pretreated polyacrylonitrile, the functional monomer, benzophenone, and absolute ethanol is 2.0:0.7:0.03:55.

[0071] Preparation Example 6

[0072] This preparation example provides a modified polyacrylonitrile, which is prepared by the following steps:

[0073] Step A1: Add polyacrylonitrile into an ethanol aqueous solution, heat up to reflux, stir at 800 rpm for 4 h, take it out, wash with deionized water 4 times, and dry at 75 °C to constant weight to obtain pretreated polyacrylonitrile. Among them, the mass ratio of polyacrylonitrile and the ethanol aqueous solution is 4:75, and the mass fraction of the ethanol aqueous solution is 30%.

[0074] Step A2: Add the pretreated polyacrylonitrile, the functional monomer prepared in Preparation Example 3, and benzophenone into absolute ethanol, stir at a rotation speed of 800 rpm for 24 min until uniform, then place it under ultraviolet light with a peak wavelength of 365 nm and an intensity of 80 mw / cm 2 for 35 min, control the irradiation temperature at 65 °C, then place it in a Soxhlet extractor, extract with acetone for 20 h, wash with deionized water 5 times, and dry at 75 °C to constant weight to obtain modified polyacrylonitrile. Among them, the mass ratio of the pretreated polyacrylonitrile, the functional monomer, benzophenone, and absolute ethanol is 2.2:0.8:0.04:60.

[0075] Comparative Preparation Example 4

[0076] This comparative preparation example provides a modified polyacrylonitrile, which is prepared by the following steps:

[0077] Step A1: Add polyacrylonitrile into an ethanol aqueous solution, heat up to reflux, stir at a rotation speed of 600 rpm for 2 h, take it out, wash with deionized water 3 times, and dry at 65 °C to constant weight to obtain pretreated polyacrylonitrile. Among them, the mass ratio of polyacrylonitrile to the ethanol aqueous solution is 2:65, and the mass fraction of the ethanol aqueous solution is 20%;

[0078] Step A2: Add the pretreated polyacrylonitrile, the functional monomer prepared in Comparative Preparation Example 1, and benzophenone into absolute ethanol, stir at a rotation speed of 700 rpm for 16 min until uniform, then place it under ultraviolet light with a peak wavelength of 365 nm and an intensity of 80 mw / cm 2 for 25 min, control the irradiation temperature at 55 °C, then place it in a Soxhlet extractor, extract with acetone for 16 h, wash with deionized water 3 times, and dry at 65 °C to constant weight to obtain modified polyacrylonitrile. Among them, the mass ratio of the pretreated polyacrylonitrile, the functional monomer, benzophenone, and absolute ethanol is 1.8:0.6:0.02:50.

[0079] Comparative Preparation Example 5

[0080] This comparative preparation example provides a modified polyacrylonitrile, which is prepared by the following steps:

[0081] Step A1: Add polyacrylonitrile into an ethanol aqueous solution, heat up to reflux, stir at a rotation speed of 600 rpm for 2 h, take it out, wash with deionized water 3 times, and dry at 65 °C to constant weight to obtain pretreated polyacrylonitrile. Among them, the mass ratio of polyacrylonitrile to the ethanol aqueous solution is 2:65, and the mass fraction of the ethanol aqueous solution is 20%;

[0082] Step A2: Add the pretreated polyacrylonitrile, the functional monomer prepared in Comparative Preparation Example 2, and benzophenone into absolute ethanol, stir at a speed of 700 rpm for 16 min until homogeneous, then place it under ultraviolet light with a peak wavelength of 365 nm and an intensity of 80 mw / cm 2 irradiate for 25 min, control the irradiation temperature at 55 °C, then place it in a Soxhlet extractor, extract with acetone for 16 h, wash with deionized water 3 times, and dry at 65 °C to constant weight to obtain modified polyacrylonitrile. Among them, the mass ratio of the pretreated polyacrylonitrile, the functional monomer, benzophenone, and absolute ethanol is 1.8:0.6:0.02:50.

[0083] Comparative Preparation Example 6

[0084] This comparative preparation example provides a modified polyacrylonitrile, which is prepared by the following steps:

[0085] Step A1: Add polyacrylonitrile into an ethanol aqueous solution, heat up to reflux, stir at a speed of 600 rpm for 2 h, take out, wash with deionized water 3 times, and dry at 65 °C to constant weight to obtain pretreated polyacrylonitrile. Among them, the mass ratio of polyacrylonitrile and the ethanol aqueous solution is 2:65, and the mass fraction of the ethanol aqueous solution is 20%;

[0086] Step A2: Add the pretreated polyacrylonitrile, the functional monomer prepared in Comparative Preparation Example 3, and benzophenone into absolute ethanol, stir at a speed of 700 rpm for 16 min until homogeneous, then place it under ultraviolet light with a peak wavelength of 365 nm and an intensity of 80 mw / cm 2 irradiate for 25 min, control the irradiation temperature at 55 °C, then place it in a Soxhlet extractor, extract with acetone for 16 h, wash with deionized water 3 times, and dry at 65 °C to constant weight to obtain modified polyacrylonitrile. Among them, the mass ratio of the pretreated polyacrylonitrile, the functional monomer, benzophenone, and absolute ethanol is 1.8:0.6:0.02:50.

[0087] Preparation Examples 7 - 9 and Comparative Preparation Examples 7 - 8 provide a preparation method of an antibacterial filler.

[0088] Preparation Example 7

[0089] This preparation example provides an antibacterial filler, which is prepared by the following steps:

[0090] Step C1: Ultrasonically mix nano-zinc oxide, deionized water, absolute ethanol, and KH-560 for 30 min. Control the ultrasonic frequency at 35 kHz and the ultrasonic power at 500 W. Then stir and react at room temperature at a rotation speed of 500 rpm for 6 h. Centrifuge, and wash the precipitate 3 times with absolute ethanol and deionized water. Dry it to constant weight at 50 °C to obtain epoxy-group zinc oxide. Among them, the mass ratio of nano-zinc oxide, deionized water, absolute ethanol, and KH-560 is 5:10:25:0.4;

[0091] Step C2: Ultrasonically disperse the epoxy-group zinc oxide in anhydrous DMF. Control the ultrasonic frequency at 35 kHz and the ultrasonic power at 500 W, and the ultrasonic time at 20 min. Dropwise add the mixed solution c of tetrabutylammonium bromide, α-acetamidocinnamic acid, and anhydrous DMF, and control the dropping to be completed within 30 min. After dropping, raise the temperature to 90 °C and stir and react for 2 h. After the reaction ends, centrifuge, and wash the precipitate 3 times with absolute ethanol and deionized water. Dry it to constant weight at 60 °C to obtain the antibacterial filler. Among them, the mass ratio of epoxy-group zinc oxide, anhydrous DMF, and the mixed solution c is 2:50:26. In the mixed solution c, the mass ratio of tetrabutylammonium bromide, α-acetamidocinnamic acid, and anhydrous DMF is 0.1:1.2:30.

[0092] Preparation Example 8

[0093] This preparation example provides an antibacterial filler, which is prepared by the following steps:

[0094] Step C1: Ultrasonically mix nano-zinc oxide, deionized water, absolute ethanol, and KH-560 for 40 min. Control the ultrasonic frequency at 40 kHz and the ultrasonic power at 550 W. Stir and react at room temperature for 7 h. Centrifuge, and wash the precipitate 4 times with absolute ethanol and deionized water. Dry it to constant weight at 55 °C to obtain epoxy-group zinc oxide. Among them, the mass ratio of nano-zinc oxide, deionized water, absolute ethanol, and KH-560 is 5:10:30:0.5;

[0095] Step C2: Ultrasonically disperse the epoxy-group zinc oxide in anhydrous DMF. Control the ultrasonic frequency at 40 kHz and the ultrasonic power at 550 W, and the ultrasonic time at 24 min. Dropwise add the mixed solution c of tetrabutylammonium bromide, α-acetamidocinnamic acid, and anhydrous DMF, and control the dropping to be completed within 30 min. After dropping, raise the temperature to 100 °C and stir and react for 2.5 h. After the reaction ends, centrifuge, and wash the precipitate 4 times with absolute ethanol and deionized water. Dry it to constant weight at 65 °C to obtain the antibacterial filler. Among them, the mass ratio of epoxy-group zinc oxide, anhydrous DMF, and the mixed solution c is 3:55:29. In the mixed solution c, the mass ratio of tetrabutylammonium bromide, α-acetamidocinnamic acid, and anhydrous DMF is 0.1:1.4:30.

[0096] Preparation Example 9

[0097] This preparation example provides an antibacterial filler, which is prepared by the following steps:

[0098] Step C1: Ultrasonically mix nano-zinc oxide, deionized water, absolute ethanol and KH-560 for 50 min, control the ultrasonic frequency at 45 kHz and the ultrasonic power at 600 w, stir and react at room temperature for 8 h, centrifuge, wash the precipitate 5 times with absolute ethanol and deionized water, and dry it to constant weight at 60 °C to obtain epoxy zinc oxide. Among them, the mass ratio of nano-zinc oxide, deionized water, absolute ethanol and KH-560 is 5:10:35:0.6;

[0099] Step C2: Ultrasonically disperse the epoxy zinc oxide in anhydrous DMF, control the ultrasonic frequency at 45 kHz and the ultrasonic power at 600 w, with an ultrasonic time of 28 min. Dropwise add the mixed solution c of tetrabutylammonium bromide, α-acetamidocinnamic acid and anhydrous DMF, and control the dropping to be completed within 30 min. After dropping, raise the temperature to 110 °C and stir and react for 3 h. After the reaction is completed, centrifuge, wash the precipitate 5 times with absolute ethanol and deionized water, and dry it to constant weight at 70 °C to obtain the antibacterial filler. Among them, the mass ratio of epoxy zinc oxide, anhydrous DMF and the mixed solution c is 4:60:32. In the mixed solution c, the mass ratio of tetrabutylammonium bromide, α-acetamidocinnamic acid and anhydrous DMF is 0.1:1.6:30.

[0100] Comparative Preparation Example 7

[0101] This comparative preparation example provides an antibacterial filler, which is prepared by the following steps:

[0102] Step C1: Ultrasonically mix nano-zinc oxide, deionized water, absolute ethanol and KH-560 for 30 min, control the ultrasonic frequency at 35 kHz and the ultrasonic power at 500 w, then stir and react at room temperature at a rotation speed of 500 rpm for 6 h, centrifuge, wash the precipitate 3 times with absolute ethanol and deionized water, and dry it to constant weight at 50 °C to obtain epoxy zinc oxide. Among them, the mass ratio of nano-zinc oxide, deionized water, absolute ethanol and KH-560 is 5:10:25:0.4;

[0103] Step C2: Ultrasonically disperse the epoxy zinc oxide in anhydrous DMF, control the ultrasonic frequency at 35 kHz and the ultrasonic power at 500 w, with an ultrasonic time of 20 min. Dropwise add the mixed solution c of tetrabutylammonium bromide, cinnamic acid and anhydrous DMF, and control the dropping to be completed within 30 min. After dropping, raise the temperature to 90 °C and stir and react for 2 h. After the reaction is completed, centrifuge, wash the precipitate 3 times with absolute ethanol and deionized water, and dry it to constant weight at 60 °C to obtain the antibacterial filler. Among them, the mass ratio of epoxy zinc oxide, anhydrous DMF and the mixed solution c is 2:50:26. In the mixed solution c, the mass ratio of tetrabutylammonium bromide, cinnamic acid and anhydrous DMF is 0.1:1.2:30.

[0104] Comparative Preparation Example 8

[0105] This comparative preparation example provides an antibacterial filler, which is prepared by the following steps:

[0106] Step C1: Ultrasonically mix nano-zinc oxide, deionized water, absolute ethanol, and KH-560 for 30 min, control the ultrasonic frequency at 35 kHz and the ultrasonic power at 500 w, then stir and react at room temperature for 6 h at a rotation speed of 500 rpm, centrifuge, wash the precipitate 3 times with absolute ethanol and deionized water, and dry to constant weight at 50 °C to obtain epoxy-group zinc oxide. Among them, the mass ratio of nano-zinc oxide, deionized water, absolute ethanol, and KH-560 is 5:10:25:0.4;

[0107] Step C2: Ultrasonically disperse the epoxy-group zinc oxide in anhydrous DMF, control the ultrasonic frequency at 35 kHz and the ultrasonic power at 500 w, with an ultrasonic time of 20 min. Dropwise add the mixed solution c of tetrabutylammonium bromide, maleic acid, and anhydrous DMF, control the dropping to be completed within 30 min. After dropping, raise the temperature to 90 °C and stir and react for 2 h. After the reaction ends, centrifuge, wash the precipitate 3 times with absolute ethanol and deionized water, and dry to constant weight at 60 °C to obtain the antibacterial filler. Among them, the mass ratio of epoxy-group zinc oxide, anhydrous DMF, and the mixed solution c is 2:50:26. In the mixed solution c, the mass ratio of tetrabutylammonium bromide, maleic acid, and anhydrous DMF is 0.1:1.2:30.

[0108] Examples 1-3 and Comparative Examples 1-5 provide a preparation method of high-strength antibacterial acrylic fibers.

[0109] Example 1

[0110] This example provides a high-strength antibacterial acrylic fiber, including the following raw materials in parts by weight: 110 parts of the modified polyacrylonitrile prepared in Preparation Example 4, and 8 parts of the antibacterial filler prepared in Preparation Example 7;

[0111] Melt and blend the modified polyacrylonitrile and the antibacterial filler in a twin-screw extruder, extrude and pelletize, then spin the pellets in a melt spinning machine; the obtained fibers are subjected to stretching treatment in a stretching machine to obtain high-strength antibacterial acrylic fibers. Among them, the screw temperature of the twin-screw extruder is 235 °C, and the screw speed is set at 30 r / min; the melt spinning machine controls the spinning temperature at 260 °C and the spinning rate at 600 m / min; the hot plate temperature of the stretching machine is controlled at 82 °C, and the drawing ratio is controlled at 2.8 times.

[0112] Example 2

[0113] This example provides a high-strength antibacterial acrylic fiber, including the following raw materials in parts by weight: 120 parts of the modified polyacrylonitrile prepared in Preparation Example 5, and 9 parts of the antibacterial filler prepared in Preparation Example 8;

[0114] The modified polyacrylonitrile and the antibacterial filler are melt-blended in a twin-screw extruder, pelletized by extrusion, and then the pellets are spun in a melt spinning machine; the obtained fibers are stretched in a stretching machine to obtain high-strength antibacterial acrylic fibers. Among them, the screw temperature of the twin-screw extruder is 240 °C, and the screw speed is set at 35 r / min; the melt spinning machine controls the spinning temperature at 270 °C and the spinning speed at 700 m / min; the hot plate temperature of the stretching machine is controlled at 86 °C, and the draw ratio is controlled at 3.0 times.

[0115] Example 3

[0116] This example provides a high-strength antibacterial acrylic fiber, which comprises the following raw materials in parts by weight: 130 parts of the modified polyacrylonitrile prepared in Preparation Example 6 and 10 parts of the antibacterial filler prepared in Preparation Example 9.

[0117] The modified polyacrylonitrile and the antibacterial filler are melt-blended in a twin-screw extruder, pelletized by extrusion, and then the pellets are spun in a melt spinning machine; the obtained fibers are stretched in a stretching machine to obtain high-strength antibacterial acrylic fibers. Among them, the screw temperature of the twin-screw extruder is 245 °C, and the screw speed is set at 40 r / min; the melt spinning machine controls the spinning temperature at 280 °C and the spinning speed at 800 m / min; the hot plate temperature of the stretching machine is controlled at 90 °C, and the draw ratio is controlled at 3.2 times.

[0118] Comparative Example 1

[0119] This comparative example provides a high-strength antibacterial acrylic fiber, which comprises the following raw materials in parts by weight: 110 parts of the modified polyacrylonitrile prepared in Comparative Preparation Example 4 and 8 parts of the antibacterial filler prepared in Preparation Example 7.

[0120] The modified polyacrylonitrile and the antibacterial filler are melt-blended in a twin-screw extruder, pelletized by extrusion, and then the pellets are spun in a melt spinning machine; the obtained fibers are stretched in a stretching machine to obtain high-strength antibacterial acrylic fibers. Among them, the screw temperature of the twin-screw extruder is 235 °C, and the screw speed is set at 30 r / min; the melt spinning machine controls the spinning temperature at 260 °C and the spinning speed at 600 m / min; the hot plate temperature of the stretching machine is controlled at 82 °C, and the draw ratio is controlled at 2.8 times.

[0121] Comparative Example 2

[0122] This comparative example provides a high-strength antibacterial acrylic fiber, which comprises the following raw materials in parts by weight: 110 parts of the modified polyacrylonitrile prepared in Comparative Preparation Example 5 and 8 parts of the antibacterial filler prepared in Preparation Example 7.

[0123] The modified polyacrylonitrile and the antibacterial filler are melt-blended in a twin-screw extruder, extruded and pelletized, and then the pellets are spun in a melt spinning machine; the obtained fibers are stretched in a stretching machine to obtain high-strength antibacterial acrylic fibers. Among them, the screw temperature of the twin-screw extruder is 235 °C, and the screw speed is set at 30 r / min; the melt spinning machine controls the spinning temperature at 260 °C and the spinning speed at 600 m / min; the hot plate temperature of the stretching machine is controlled at 82 °C, and the draw ratio is controlled at 2.8 times.

[0124] Comparative Example 3

[0125] This comparative example provides a high-strength antibacterial acrylic fiber, which comprises the following raw materials in parts by weight: 110 parts of the modified polyacrylonitrile prepared in Comparative Preparation Example 6 and 8 parts of the antibacterial filler prepared in Preparation Example 7;

[0126] The modified polyacrylonitrile and the antibacterial filler are melt-blended in a twin-screw extruder, extruded and pelletized, and then the pellets are spun in a melt spinning machine; the obtained fibers are stretched in a stretching machine to obtain high-strength antibacterial acrylic fibers. Among them, the screw temperature of the twin-screw extruder is 235 °C, and the screw speed is set at 30 r / min; the melt spinning machine controls the spinning temperature at 260 °C and the spinning speed at 600 m / min; the hot plate temperature of the stretching machine is controlled at 82 °C, and the draw ratio is controlled at 2.8 times.

[0127] Comparative Example 4

[0128] This comparative example provides a high-strength antibacterial acrylic fiber, which comprises the following raw materials in parts by weight: 110 parts of the modified polyacrylonitrile prepared in Preparation Example 4 and 8 parts of the antibacterial filler prepared in Comparative Preparation Example 7;

[0129] The modified polyacrylonitrile and the antibacterial filler are melt-blended in a twin-screw extruder, extruded and pelletized, and then the pellets are spun in a melt spinning machine; the obtained fibers are stretched in a stretching machine to obtain high-strength antibacterial acrylic fibers. Among them, the screw temperature of the twin-screw extruder is 235 °C, and the screw speed is set at 30 r / min; the melt spinning machine controls the spinning temperature at 260 °C and the spinning speed at 600 m / min; the hot plate temperature of the stretching machine is controlled at 82 °C, and the draw ratio is controlled at 2.8 times.

[0130] Comparative Example 5

[0131] This comparative example provides a high-strength antibacterial acrylic fiber, which comprises the following raw materials in parts by weight: 110 parts of the modified polyacrylonitrile prepared in Preparation Example 4 and 8 parts of the antibacterial filler prepared in Comparative Preparation Example 8;

[0132] The modified polyacrylonitrile and the antibacterial filler are melt-blended in a twin-screw extruder, extruded and pelletized, and then the pellets are spun in a melt spinning machine; the obtained fibers are stretched in a stretching machine to obtain high-strength antibacterial acrylic fibers. Among them, the screw temperature of the twin-screw extruder is 235 °C, and the screw speed is set at 30 r / min; the melt spinning machine controls the spinning temperature at 260 °C and the spinning speed at 600 m / min; the hot plate temperature of the stretching machine is controlled at 82 °C, and the draw ratio is controlled at 2.8 times.

[0133] Performance testing

[0134] Control the fineness of the acrylic fibers prepared in Examples 1-3 and Comparative Examples 1-5 to be 10.8 dtex. The high-strength antibacterial acrylic fibers prepared in Examples 1-3 and Comparative Examples 1-5 are woven using a plain weave process. The obtained woven samples are 20 cm long and 5 cm wide, and the warp and weft densities of the samples are 408 threads / 10 cm and 386 threads / 10 cm respectively. The following tests are carried out on the woven samples:

[0135] Moisture absorption: Detection is carried out according to the national standard GB / T 12704.1-2009 "Textiles - Test methods for fabric water vapor permeability - Part 1: Moisture absorption method".

[0136] Breaking strength test: The test is carried out according to the national standard GB / T 3923.1-2013 "Textiles - Tensile properties of fabrics - Part 1: Determination of breaking force and elongation at break - Strip method". The specific test results are shown in Table 1.

[0137] Table 1 Air permeability and mechanical property tests of acrylic fibers prepared in Examples 1-3 and Comparative Examples 1-5

[0138]

[0139]

[0140] As can be seen from Table 1, compared with the comparative examples, the acrylic fibers prepared in the examples of the present application not only have good hydrophilicity, but also perform excellently in terms of mechanical properties, and can meet the requirements of high-end textiles and functional clothing.

[0141] Antibacterial rate test: Antibacterial performance detection before washing and after 100 washes is carried out according to the national standard GB / T 20944.2-2007 "Evaluation of antibacterial properties of textiles - Part 2: Absorption method". The washing method refers to the regulations of GB / T 8629-2001 "Domestic washing and drying procedures for textiles used in tests". A type B agitator washing machine and washing program 8B are selected. The test results are shown in Table 2 below:

[0142] Table 2 Antibacterial performance test of acrylic fibers prepared in Examples 1-3 and Comparative Examples 1-5

[0143]

[0144] As can be seen from Table 2, compared with the comparative examples, the acrylic fibers prepared in the examples of the present application not only showed excellent antibacterial effects when first used, but also still had excellent antibacterial properties and good antibacterial persistence after being washed multiple times.

[0145] This specific embodiment is only an interpretation of the present application and not a limitation thereof. After reading this specification, those skilled in the art can make modifications to this embodiment that do not contribute creatively as needed, but as long as they are within the scope of the claims of the present application, they are protected by the patent law.

Claims

1. A high-strength antibacterial acrylic fiber, characterized in that, It comprises the following raw materials in parts by weight: 110 - 130 parts of modified polyacrylonitrile, 8 - 10 parts of antibacterial filler; The modified polyacrylonitrile is first obtained by treating polyacrylonitrile with an ethanol aqueous solution to obtain pretreated polyacrylonitrile, and then through graft copolymerization with a functional monomer; The functional monomer is first obtained by click addition reaction of 6 - amino - 2 - mercapto - 4 - pyrimidinol and acrylamide to obtain an amino monomer, then through ring - opening esterification reaction with octenyl succinic anhydride to obtain an unsaturated monomer, and finally through amidation reaction with tris(hydroxymethyl)aminomethane; The antibacterial filler is first obtained by modifying nano - zinc oxide with KH - 560 to obtain epoxy - group zinc oxide, and then through ring - opening esterification reaction with α - acetamidocinnamic acid; 2. The high-strength antibacterial acrylic fiber according to claim 1, wherein The modified polyacrylonitrile is prepared by the following steps: Step A1: Add polyacrylonitrile into an ethanol aqueous solution, heat up to reflux, stir for 2 - 4 h, take out, wash and dry to obtain pretreated polyacrylonitrile; Step A2: Add pretreated polyacrylonitrile, functional monomer and benzophenone into absolute ethanol, stir evenly, irradiate with ultraviolet light for 25 - 35 min, control the irradiation temperature at 55 - 65 °C, then perform Soxhlet extraction, washing and drying to obtain modified polyacrylonitrile.

3. The high-strength antibacterial acrylic fiber according to claim 2, wherein, In Step A1, the mass ratio of polyacrylonitrile to the ethanol aqueous solution is 2 - 4:65 - 75, and the mass fraction of the ethanol aqueous solution is 20 - 30%. In Step A2, the mass ratio of pretreated polyacrylonitrile, functional monomer, benzophenone and absolute ethanol is 1.8 - 2.2:0.6 - 0.8:0.02 - 0.04:50 - 60.

4. The high-strength antibacterial acrylic fiber according to claim 1, characterized in that, The functional monomer is prepared by the following steps: Step B1: Add 6 - amino - 2 - mercapto - 4 - pyrimidinol, acrylamide and a photoinitiator into anhydrous DMF, stir evenly, keep the rotation speed unchanged, irradiate with ultraviolet light while stirring for 12 - 26 min, control the irradiation temperature at 75 - 85 °C to obtain an amino monomer; Step B2: Add the amino monomer into anhydrous DMF, stir evenly, adjust the pH value to 8 - 9, dropwise add a mixed solution a of octenyl succinic anhydride and isopropanol, control to finish dropping within 10 min, after dropping, heat up to 74 - 78 °C, continue stirring and reacting for 6 - 12 h, adjust the pH value to 6.8 - 7.2, wash and dry to obtain an unsaturated monomer; Step B3: Add the unsaturated monomer and tris(hydroxymethyl)aminomethane into anhydrous DMF, stir evenly, dropwise add a mixed solution b of N,N - dicyclohexylcarbodiimide, 4 - dimethylaminopyridine and anhydrous DMF while stirring, after dropping, heat up to 74 - 78 °C, stir and react for 5 - 6 h, after the reaction ends, perform suction filtration, washing and drying to obtain the functional monomer.

5. The high-strength antibacterial acrylic fiber according to claim 4, characterized in that In the said step B1, the mass ratio of 6-amino-2-mercaptopyrimidin-4-ol, acrylamide, photoinitiator and anhydrous DMF is 4-6: 1.8-2.6: 0.02-0.04: 60-80. The photoinitiator is composed of 2,2-dimethoxy-2-phenylacetophenone and azobisisobutyronitrile mixed according to the mass ratio of 1.8: 3-5. In step B2, the mass ratio of amino monomer, anhydrous DMF and mixture a is 3-5: 75-85: 26-32. In mixture a, the mass ratio of octenyl succinic anhydride and isopropanol is 2.2-4.6:

30. In step B3, the mass ratio of unsaturated monomer, tris(hydroxymethyl)aminomethane, anhydrous DMF and mixture b is 6-8: 1.6-2.2: 60-70: 25-35. In mixture b, the mass ratio of N,N'-dicyclohexylcarbodiimide, 4-dimethylaminopyridine and anhydrous DMF is 3.4-4.4: 2.4-2.8: 23-27.

6. The high-strength antibacterial acrylic fiber according to claim 1, characterized in that: The said antibacterial filler is prepared by the following steps: Step C1: Ultrasonically mix nano-zinc oxide, deionized water, absolute ethanol and KH-560 for 30-50 min, stir and react at room temperature for 6-8 h, centrifuge, wash the precipitate and dry it to obtain epoxy-group zinc oxide; Step C2: Ultrasonically disperse the epoxy-group zinc oxide in anhydrous DMF, dropwise add the mixed solution c of tetrabutylammonium bromide, α-acetamidocinnamic acid and anhydrous DMF. After dropping, raise the temperature to 90-110 °C and stir and react for 2-3 h. After the reaction is completed, centrifuge, wash several times and dry to obtain the antibacterial filler.

7. The high-strength antibacterial acrylic fiber according to claim 6, wherein In the said step C1, the mass ratio of nano-zinc oxide, deionized water, absolute ethanol and KH-560 is 5: 10: 25-35: 0.4-0.

6.

8. The high-strength antibacterial acrylic fiber according to claim 6, wherein In the said step C2, the mass ratio of epoxy-group zinc oxide, anhydrous DMF and mixed solution c is 2-4: 50-60: 26-32. In mixed solution c, the mass ratio of tetrabutylammonium bromide, α-acetamidocinnamic acid and anhydrous DMF is 0.1: 1.2-1.6:

30.

9. A method for preparing the high-strength antibacterial acrylic fiber according to any one of claims 1-8, characterized in that, It includes the following steps: Melt-blend the modified polyacrylonitrile and the antibacterial filler in a twin-screw extruder, extrude and pelletize, and then spin the pellets in a melt spinning machine; stretch the obtained fibers in a stretching machine to obtain high-strength antibacterial acrylic fibers.

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