Antibacterial polyamide fiber material and preparation method thereof

Abstract

The invention discloses an antibacterial polyamide fiber material and a preparation method thereof, and relates to the field of polyamide fiber materials, and the polyamide fiber material is prepared from 2, 5-furandicarbonyl chloride, lithium hydroxide, DMAC, m-phenylenediamine, modified EVA, and a light stabilizing auxiliary agent. The modified EVA is obtained by introducing conjugated double bonds, ether bonds, pyrimidine and amido bonds into EVA, and the polyamide fiber is endowed with more excellent notch impact strength and antibacterial property. The light stabilizing aid is an aid which contains ferrocene, diphenylamine, acylamino and hydroxyl and has a hyperbranched structure, so that the light stability and the antistatic property of the polyamide fiber material are improved.

Description

Technical Field

[0001] This invention relates to the field of polyamide fiber materials, specifically to an antibacterial polyamide fiber material and its preparation method. Background Technology

[0002] Polyamide (PA), commonly known as nylon, is the most widely used of the five major engineering plastics and an important synthetic fiber material. Polyamide possesses excellent mechanical properties, heat resistance, wear resistance, chemical resistance, and self-lubricating properties, and its products are widely used in numerous fields such as automobiles, textiles, instruments, machinery, food packaging, and daily consumer goods.

[0003] However, in automotive interiors, tire cords, sporting goods (such as ropes, tennis racket strings, parachutes, etc.), and structural components requiring high strength and durability, polyamide fiber materials may be subjected to significant impact forces and break or fracture, thus requiring sufficient notched impact strength. EVA (ethylene-vinyl acetate copolymer) has been used as an impact modifier for PA toughening; however, EVA has poor compatibility with polyamide fiber materials and cannot effectively improve the notched impact strength of polyamide fibers.

[0004] Polyamide fiber products are highly susceptible to bacterial growth in humid and hot environments, which not only affects the quality and safety of the products themselves, but may also pose a threat to people's health. Silver-containing polyamide mesh is woven from polyamide fibers coated with silver ions. However, silver ion antibacterial agents are expensive and not water-resistant. Therefore, the development of polyamide fibers with long-lasting antibacterial properties has become an urgent need for industry upgrading.

[0005] Under prolonged exposure to sunlight and ultraviolet (UV) radiation, the UV-sensitive amide bonds in the molecular structure of polyamide fibers are prone to breakage, and the benzene rings are susceptible to photochemical reactions, leading to structural damage, reduced strength, and a tendency to yellow. Silicone-coated nylon, obtained by coating polyamide fibers with silicone rubber, enhances UV resistance; however, frequent friction, impacts, or improper folding and compression can damage silicone-coated nylon, affecting the durability of the polyamide fiber material. Therefore, more suitable modification methods are needed to improve the UV resistance of polyamide fiber materials.

[0006] Based on this, the present invention provides a modification method that improves the compatibility between EVA and polyamide fiber, and imparts antibacterial properties to EVA, thereby enhancing the notched impact strength and antibacterial properties of the polyamide fiber material; at the same time, it enhances the UV resistance of the polyamide fiber material, resulting in a polyamide fiber material with superior notched impact strength, antibacterial properties, and UV resistance. Summary of the Invention

[0007] To address the aforementioned technical problems, this invention provides an antibacterial polyamide fiber material and its preparation method.

[0008] The objective of this invention can be achieved through the following technical solutions:

[0009] An antibacterial polyamide fiber material comprises the following raw materials: 2,5-furandicarboxylic acid chloride, lithium hydroxide, DMAC, m-phenylenediamine, modified EVA, and light stabilizer;

[0010] The preparation of the antibacterial polyamide fiber material includes the following steps:

[0011] Step S1: In a nitrogen atmosphere, mix and stir DMAC and m-phenylenediamine for 10-12 min, then cool to -5±1℃, add 2,5-furandicarboxyl chloride, control the temperature at 18-20℃, stir and react for 30-35 min, add lithium hydroxide, and continue stirring for 3-3.5 h to obtain resin mixture.

[0012] Furthermore, the ratio of DMAC, m-phenylenediamine, 2,5-furandicarboxyl chloride, and lithium hydroxide is 500-520 mL : 32.4-33.0 g : 58-59 g : 13-13.5 g;

[0013] Step S2: Stir and mix the resin mixture, modified EVA, and light stabilizer at 165-175℃ for 2-2.5h, then desalt and degas the mixture before dry-jet wet spinning to obtain antibacterial polyamide fiber material.

[0014] Furthermore, the ratio of resin mixture, modified EVA, and light stabilizer is 61.5-62.5 mL: 2.2-2.4 g: 0.5-0.7 g; during the dry-jet wet spinning process, the spinning solution temperature is 19-21℃, the air bath height is maintained at 12-18 mm, the coagulation bath is a 40-42% DMAC aqueous solution at a temperature of 24-26℃, the water washing coagulation bath uses pure water at a temperature of 80-85℃, the hot stretching temperature is 300-305℃, the heat setting temperature is 280-285℃, and the setting time is 70-80 s.

[0015] The modified EVA is prepared by the following steps:

[0016] Step A1: Add vanillin acetone and sodium hydroxide to deionized water and stir for 20-25 min to obtain solution 1; then add chloroacetic acid to deionized water and stir for 10-12 min, then add sodium hydroxide and stir for 5-7 min to obtain solution 2; add solution 2 to solution 1, stir at 95-100℃ and control the pH at 11-13 for 8-8.5 h, then adjust the pH to 3-4 with dilute hydrochloric acid, filter, wash with acetone and water three times each, and dry to obtain reaction product 1;

[0017] Furthermore, the ratio of vanillin acetal, sodium hydroxide, and deionized water in solution 1 is 9.6-9.7g: 4.0-4.2g: 50-55mL; the ratio of chloroacetic acid, deionized water, and sodium hydroxide in solution 2 is 9.45-9.50g: 4.0-4.2g: 50-55mL; the ratio of solution 2 to solution 1 is 64-68mL: 66-70mL; and the mass fraction of dilute hydrochloric acid is 13-15%.

[0018] In step A1, the phenolic hydroxyl group in vanillin acetal reacts with chloroacetic acid under alkaline conditions to dehydrochlorinate, and then undergoes acidification to obtain reaction product 1 containing carboxyl groups, ether bonds, double bonds and ketone carbonyl groups.

[0019] Step A2: In a protective gas atmosphere, reaction product 1 and methylenetriphenylphosphine are added to anhydrous tetrahydrofuran and refluxed and stirred at 50-60℃ for 8-8.5h to obtain reaction product 2; reaction product 2 is added to DMF, and thionyl chloride is added with stirring, and the mixture is refluxed and stirred at 50-55℃ for 4-5h to obtain reaction product 3.

[0020] Furthermore, the ratio of reaction product 1, methylenetriphenylphosphine, and anhydrous tetrahydrofuran is 28.7-29.0 g : 27.7-28.0 g : 120-130 mL; the ratio of reaction product 2, DMF, and thionyl chloride is 30-31 g : 80-90 mL : 11.5-12 g.

[0021] In step A2, the ketone carbonyl group of reaction product 1 reacts with methylenetriphenylphosphine to form a carbon-carbon double bond, which then forms a conjugated double bond with the double bond of reaction product 1, resulting in reaction product 2 containing a conjugated double bond, a carboxyl group, and an ether bond. The carboxyl group of reaction product 2 reacts with thionyl chloride to generate reaction product 3 containing an acyl chloride, an ether bond, and a conjugated double bond.

[0022] Step A3: Mix 2-amino-5-nitropyrimidine, potassium carbonate and dimethyl sulfoxide to obtain mixture 1; then mix acryloyl chloride and dimethyl sulfoxide to obtain mixture 2; add mixture 2 dropwise to mixture 1 in an ice-water bath, heat to 45-50℃, stir and react for 9-9.5h to obtain reaction product 4;

[0023] Furthermore, in mixture 1, the ratio of 2-amino-5-nitropyrimidine, potassium carbonate, and dimethyl sulfoxide is 14-14.5g: 2.3-2.5g: 40-50mL; in mixture 2, the ratio of acryloyl chloride to dimethyl sulfoxide is 9-9.5g: 18-20mL; and the ratio of mixture 1 to mixture 2 is 60-70mL: 30-35mL.

[0024] In step A3, acryloyl chloride reacts with the amino group of 2-amino-5-nitropyrimidine to give reaction product 4, which contains a terminal carbon-carbon double bond, pyrimidine, and nitro group.

[0025] Step A4: Mix reaction product 4, dicumyl peroxide, and acetone and stir for 10-15 min. Then add EVA and continue stirring for 20-25 min. Melt extrude the mixture on a twin-screw extruder at 205-210℃ and a screw speed of 60-70 r / min. Then vacuum dry at 50-60℃ for 9-9.5 h to obtain reaction product 5. Add reaction product 5 to toluene, heat to 45-50℃, add sodium dithionite, and reflux and stir for 1.5-2 h to obtain reaction product 6.

[0026] Furthermore, the ratio of reaction product 4, dicumyl peroxide, acetone, and EVA is 23-24g: 0.1-0.15g: 50-60mL: 100-105g; the ratio of reaction product 5, toluene, and sodium dithionite is 12-14g: 30-35mL: 2-2.2g.

[0027] During step A4, reaction product 4 is melt-grafted with EVA to obtain EVA containing pyrimidine and nitro groups, i.e., reaction product 5; the nitro groups of reaction product 5 are reduced to amino groups to obtain reaction product 6.

[0028] Step A5: Mix reaction product 6, potassium carbonate and dimethyl sulfoxide to obtain mixture 3; then mix reaction product 3 and dimethyl sulfoxide to obtain mixture 4; add mixture 4 dropwise to mixture 3 in an ice-water bath, heat to 45-50℃, stir and react for 12-14 hours to obtain modified EVA.

[0029] Furthermore, in mixture 3, the ratio of reaction product 6, potassium carbonate, and dimethyl sulfoxide is 120-122g: 5.4-5.6g: 260-270mL; in mixture 4, the ratio of reaction product 3 and dimethyl sulfoxide is 33-35g: 70-75mL; and the ratio of mixture 3 to mixture 4 is 490-500mL: 105-110mL.

[0030] In step A5, the acyl chloride of reaction product 3 reacts with the amino group of reaction product 6 to obtain an EVA product containing conjugated double bonds, ether bonds, pyrimidine bonds and amide bonds, i.e., modified EVA.

[0031] The light-stabilizing agent is prepared by the following steps:

[0032] Step B1: Add epichlorohydrin, ferrocene methylamine, and tetrabutylammonium bromide to toluene, reflux and stir at 100-105℃ for 4-4.5h, cool to room temperature, add alkaline solution, and stir for 2-2.5h to obtain reaction product a;

[0033] Furthermore, the ratio of epichlorohydrin, ferrocene, tetrabutylammonium bromide, toluene, and alkaline solution is 19-21g: 21-22g: 3.2-3.4g: 100-110mL: 20-25mL, and the alkaline solution is a sodium hydroxide solution with a mass fraction of 40-45%.

[0034] In step B1, epichlorohydrin undergoes ring opening and then ring closing with the amino group of ferrocene methylamine to obtain reaction product a containing ferrocene and diepoxy groups.

[0035] Step B2: Under a protective gas atmosphere, ethyl 3-(phenylamino)benzoate is heated to 100-110℃ under reflux and stirring for 35-40 min, then cooled to 50-55℃ and methanol and N-methyl-2,4,6-trinitroaniline are added, followed by sodium methoxide. The mixture is stirred for 24-25 h to obtain reaction product b.

[0036] Furthermore, the ratio of ethyl 3-(phenylamino)benzoate, methanol, N-methyl-2,4,6-trinitroaniline, and sodium methoxide is 28.5-29 g : 115-125 mL : 24.5-25 g : 0.2-0.3 g;

[0037] In step B2, the ester group of ethyl 3-(phenylamino)benzoate reacts with the secondary amino group of N-methyl-2,4,6-trinitroaniline to generate reaction product b, which is a trinitro group and a diphenylamine.

[0038] Step B3: Add reaction product b to toluene, heat to 45-50℃, add sodium dithionite, reflux and stir for 1.5-2 hours to obtain reaction product c; add reaction product c and reaction product a to dimethyl sulfoxide, stir at 55-60℃ for 25-26 hours to obtain photostable additive.

[0039] Furthermore, the ratio of reaction product b, toluene, and sodium dithionite is 54-55g: 160-180mL: 23-25g; the ratio of reaction product c, reaction product a, and dimethyl sulfoxide is 50-52g: 41-43g: 185-195mL.

[0040] In step B3, the nitro group of reaction product b is reduced to an amino group, yielding reaction product c containing three primary amino groups and diphenylamine. The three primary amino groups of reaction product c undergo a ring-opening reaction with the diepoxy group of reaction product a to generate a light-stabilizing agent with a hyperbranched structure containing ferrocene, diphenylamine, amide, and hydroxyl groups.

[0041] Beneficial effects of the present invention: The present invention discloses an antibacterial polyamide fiber material, which is prepared from the following raw materials: 2,5-furandicarboxylic acid chloride, lithium hydroxide, DMAC, m-phenylenediamine, modified EVA and light stabilizer.

[0042] The modified EVA is obtained by introducing conjugated double bonds, ether bonds, pyrimidine bonds, and amide bonds into EVA. The amide bonds significantly improve the compatibility of the modified EVA with polyaniline resins obtained by reacting modified EVA with 2,5-furandicarboxylic acid chloride and m-phenylenediamine, which is more conducive to the toughening of polyamide fiber materials by modified EVA, thereby improving notched impact strength. Pyrimidines interfere with the synthesis process of microbial cell walls, causing the cell walls to lose their integrity, damaging the cell membrane, and interfering with the normal life activities of microorganisms, thus endowing modified EVA with antibacterial properties. The conjugated double bonds in modified EVA can bind with thiol groups in microbial enzyme systems, interfering with the normal operation of enzyme systems, inhibiting the growth and reproduction of microorganisms, thus synergistically inhibiting bacteria with pyrimidines. The introduction of ether bonds in modified EVA improves the processing performance of polyamide resin, thereby endowing polyamide fibers with superior notched impact strength and antibacterial properties.

[0043] The synthesized light-stabilizing agent is a hyperbranched agent containing ferrocene, diphenylamine, amide groups, and hydroxyl groups. After forming the hyperbranched structure containing amide groups, the compatibility and dispersion of the small-molecule ferrocene and diphenylamine with polyamide in the matrix are enhanced, resulting in improved stability and reduced susceptibility to blooming failure. Ferrocene has a strong ability to absorb ultraviolet light, protecting the matrix from UV radiation damage. Simultaneously, the ferrocene molecule possesses certain charge transfer and electron cloud orbital overlap, giving it a certain degree of conductivity, thereby improving the UV resistance and antistatic properties of the polyamide fiber material. Diphenylamine can capture peroxide free radicals generated by light and UV irradiation in the polyamide fiber material to inhibit chain initiation and propagation reactions, thus synergistically enhancing the light stability of the polyamide fiber material intramolecularly with ferrocene. Furthermore, the hydroxyl groups in the light-stabilizing agent form a denser hydrogen-bonded cross-linking network with the amide bonds in the matrix, which is beneficial for improving the water resistance of the polyamide fiber material.

[0044] In summary, the antibacterial polyamide fiber material of the present invention has excellent antibacterial properties, notched impact strength, light stability and antistatic properties, and is worthy of widespread use.

[0045] Detailed implementation methods include

[0046] The technical solutions in the embodiments of the present invention will be clearly and completely described below. 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 skilled in the art without creative effort are within the scope of protection of the present invention.

[0047] Example 1

[0048] A modified EVA, the preparation of which includes the following steps:

[0049] Step A1: Vanillin acetone and sodium hydroxide were added to deionized water and stirred for 20 min to obtain solution 1; chloroacetic acid was then added to deionized water and stirred for 10 min, followed by the addition of sodium hydroxide and stirring for 5 min to obtain solution 2; solution 2 was added to solution 1 and stirred at 95℃ with pH controlled at 11 for 8 h, then the pH was adjusted to 3 with dilute hydrochloric acid, filtered, washed three times with acetone and three times with water, and dried to obtain reaction product 1; the ratio of vanillin acetone, sodium hydroxide, and deionized water in solution 1 was 9.6 g: 4.0 g: 50 mL; the ratio of chloroacetic acid, deionized water, and sodium hydroxide in solution 2 was 9.45 g: 4.0 g: 50 mL; the ratio of solution 2 to solution 1 was 64 mL: 66 mL; the mass fraction of dilute hydrochloric acid was 13%;

[0050] Step A2: Under a nitrogen atmosphere, reaction product 1 and methylenetriphenylphosphine were added to anhydrous tetrahydrofuran and refluxed at 50°C for 8 hours to obtain reaction product 2; reaction product 2 was added to DMF, and thionyl chloride was added with stirring, and the mixture was refluxed at 50°C for 4 hours to obtain reaction product 3; the ratio of reaction product 1, methylenetriphenylphosphine, and anhydrous tetrahydrofuran was 28.7 g: 27.7 g: 120 mL; the ratio of reaction product 2, DMF, and thionyl chloride was 30 g: 80 mL: 11.5 g.

[0051] Step A3: Mix 2-amino-5-nitropyrimidine, potassium carbonate, and dimethyl sulfoxide to obtain mixture 1; then mix acryloyl chloride and dimethyl sulfoxide to obtain mixture 2; add mixture 2 dropwise to mixture 1 in an ice-water bath, heat to 45℃, and stir for 9 hours to obtain reaction product 4; the ratio of 2-amino-5-nitropyrimidine, potassium carbonate, and dimethyl sulfoxide in mixture 1 is 14g:2.3g:40mL, the ratio of acryloyl chloride and dimethyl sulfoxide in mixture 2 is 9g:18mL, and the ratio of mixture 1 to mixture 2 is 60mL:30mL.

[0052] Step A4: Mix reaction product 4, dicumyl peroxide, and acetone, and stir for 10 minutes. Then add EVA (supplier: Shanghai Oushuo Plastics Co., Ltd.) and continue stirring for 20 minutes. Then melt-extrude the mixture on a twin-screw extruder at 205°C and a screw speed of 60 r / min. Finally, vacuum dry the mixture at 50°C for 9 hours to obtain reaction product 5. Add reaction product 5 to toluene, heat to 45°C, add sodium dithionite, and reflux and stir for 1.5 hours to obtain reaction product 6. The ratio of reaction product 4, dicumyl peroxide, acetone, and EVA is 23 g: 0.1 g: 50 mL: 100 g. The ratio of reaction product 5, toluene, and sodium dithionite is 12 g: 30 mL: 2 g.

[0053] Step A5: Mix reaction product 6, potassium carbonate, and dimethyl sulfoxide to obtain mixture 3; then mix reaction product 3 and dimethyl sulfoxide to obtain mixture 4; add mixture 4 dropwise to mixture 3 in an ice-water bath, heat to 45℃, and stir for 12 hours to obtain modified EVA; the ratio of reaction product 6, potassium carbonate, and dimethyl sulfoxide in mixture 3 is 120g:5.4g:260mL, the ratio of reaction product 3 and dimethyl sulfoxide in mixture 4 is 33g:70mL, and the ratio of mixture 3 to mixture 4 is 490mL:105mL.

[0054] Example 2

[0055] A modified EVA, the preparation of which includes the following steps:

[0056] Step A1: Vanillin acetone and sodium hydroxide were added to deionized water and stirred for 23 min to obtain solution 1; chloroacetic acid was then added to deionized water and stirred for 11 min, followed by the addition of sodium hydroxide and stirring for 6 min to obtain solution 2; solution 2 was added to solution 1 and stirred at 95℃ with pH controlled at 12 for 8.3 h, then the pH was adjusted to 3.5 with dilute hydrochloric acid, filtered, washed three times with acetone and three times with water, and dried to obtain reaction product 1; the ratio of vanillin acetone, sodium hydroxide, and deionized water in solution 1 was 9.65 g: 4.1 g: 53 mL; the ratio of chloroacetic acid, deionized water, and sodium hydroxide in solution 2 was 9.48 g: 4.1 g: 53 mL; the ratio of solution 2 to solution 1 was 66 mL: 68 mL; the mass fraction of dilute hydrochloric acid was 14%;

[0057] Step A2: Under a nitrogen atmosphere, reaction product 1 and methylenetriphenylphosphine were added to anhydrous tetrahydrofuran and refluxed at 55°C for 8.3 h to obtain reaction product 2; reaction product 2 was added to DMF, and thionyl chloride was added with stirring, and the mixture was refluxed at 53°C for 4.5 h to obtain reaction product 3; the ratio of reaction product 1, methylenetriphenylphosphine, and anhydrous tetrahydrofuran was 28.8 g: 27.8 g: 125 mL; the ratio of reaction product 2, DMF, and thionyl chloride was 30.5 g: 85 mL: 11.8 g.

[0058] Step A3: Mix 2-amino-5-nitropyrimidine, potassium carbonate, and dimethyl sulfoxide to obtain mixture 1; then mix acryloyl chloride and dimethyl sulfoxide to obtain mixture 2; add mixture 2 dropwise to mixture 1 in an ice-water bath, heat to 48℃, and stir for 9.3 h to obtain reaction product 4; the ratio of 2-amino-5-nitropyrimidine, potassium carbonate, and dimethyl sulfoxide in mixture 1 is 14.3 g: 2.4 g: 45 mL, the ratio of acryloyl chloride and dimethyl sulfoxide in mixture 2 is 9.3 g: 19 mL, and the ratio of mixture 1 to mixture 2 is 65 mL: 33 mL;

[0059] Step A4: Mix reaction product 4, dicumyl peroxide, and acetone, and stir for 13 minutes. Then add EVA (supplier: Shanghai Oushuo Plastics Co., Ltd.) and continue stirring for 23 minutes. Then melt-extrude the mixture on a twin-screw extruder at 205°C and a screw speed of 60 r / min. Finally, vacuum dry the mixture at 55°C for 9.2 hours to obtain reaction product 5. Add reaction product 5 to toluene, heat to 48°C, add sodium dithionite, and reflux and stir for 1.8 hours to obtain reaction product 6. The ratio of reaction product 4, dicumyl peroxide, acetone, and EVA is 23.5 g: 0.13 g: 55 mL: 103 g; the ratio of reaction product 5, toluene, and sodium dithionite is 13 g: 33 mL: 2.1 g.

[0060] Step A5: Mix reaction product 6, potassium carbonate, and dimethyl sulfoxide to obtain mixture 3; then mix reaction product 3 and dimethyl sulfoxide to obtain mixture 4; add mixture 4 dropwise to mixture 3 in an ice-water bath, heat to 48℃, and stir for 13 hours to obtain modified EVA; the ratio of reaction product 6, potassium carbonate, and dimethyl sulfoxide in mixture 3 is 121g:5.5g:265mL, the ratio of reaction product 3 and dimethyl sulfoxide in mixture 4 is 34g:73mL, and the ratio of mixture 3 to mixture 4 is 495mL:108mL.

[0061] Example 3

[0062] A modified EVA, the preparation of which includes the following steps:

[0063] Step A1: Vanillin acetone and sodium hydroxide were added to deionized water and stirred for 25 min to obtain solution 1; chloroacetic acid was then added to deionized water and stirred for 12 min, followed by the addition of sodium hydroxide and stirring for 7 min to obtain solution 2; solution 2 was added to solution 1 and stirred at 95℃ with pH controlled at 13 for 8.5 h, then the pH was adjusted to 4 with dilute hydrochloric acid, filtered, washed three times with acetone and three times with water, and dried to obtain reaction product 1; the ratio of vanillin acetone, sodium hydroxide, and deionized water in solution 1 was 9.7 g: 4.2 g: 55 mL; the ratio of chloroacetic acid, deionized water, and sodium hydroxide in solution 2 was 9.50 g: 4.2 g: 55 mL; the ratio of solution 2 to solution 1 was 68 mL: 70 mL; the mass fraction of dilute hydrochloric acid was 15%;

[0064] Step A2: Under a nitrogen atmosphere, reaction product 1 and methylenetriphenylphosphine were added to anhydrous tetrahydrofuran and refluxed at 60°C for 8.5 h to obtain reaction product 2; reaction product 2 was added to DMF, and thionyl chloride was added with stirring, and the mixture was refluxed at 55°C for 5 h to obtain reaction product 3; the ratio of reaction product 1, methylenetriphenylphosphine, and anhydrous tetrahydrofuran was 29.0 g: 28.0 g: 130 mL; the ratio of reaction product 2, DMF, and thionyl chloride was 31 g: 90 mL: 12 g.

[0065] Step A3: Mix 2-amino-5-nitropyrimidine, potassium carbonate, and dimethyl sulfoxide to obtain mixture 1; then mix acryloyl chloride and dimethyl sulfoxide to obtain mixture 2; add mixture 2 dropwise to mixture 1 in an ice-water bath, heat to 50℃, and stir for 9.5 h to obtain reaction product 4; the ratio of 2-amino-5-nitropyrimidine, potassium carbonate, and dimethyl sulfoxide in mixture 1 is 14.5 g: 2.5 g: 50 mL, the ratio of acryloyl chloride and dimethyl sulfoxide in mixture 2 is 9.5 g: 20 mL, and the ratio of mixture 1 to mixture 2 is 70 mL: 35 mL.

[0066] Step A4: Mix reaction product 4, dicumyl peroxide, and acetone, and stir for 15 minutes. Then add EVA (supplier: Shanghai Oushuo Plastics Co., Ltd.) and continue stirring for 25 minutes. Then melt-extrude the mixture on a twin-screw extruder at 205°C and a screw speed of 60 r / min. Finally, vacuum dry the mixture at 60°C for 9.5 hours to obtain reaction product 5. Add reaction product 5 to toluene, heat to 50°C, add sodium dithionite, and reflux and stir for 2 hours to obtain reaction product 6. The ratio of reaction product 4, dicumyl peroxide, acetone, and EVA is 24 g: 0.15 g: 60 mL: 105 g; the ratio of reaction product 5, toluene, and sodium dithionite is 14 g: 35 mL: 2.2 g.

[0067] Step A5: Mix reaction product 6, potassium carbonate, and dimethyl sulfoxide to obtain mixture 3; then mix reaction product 3 and dimethyl sulfoxide to obtain mixture 4; add mixture 4 dropwise to mixture 3 in an ice-water bath, heat to 50℃, and stir for 14 hours to obtain modified EVA; the ratio of reaction product 6, potassium carbonate, and dimethyl sulfoxide in mixture 3 is 122g:5.6g:270mL, the ratio of reaction product 3 and dimethyl sulfoxide in mixture 4 is 35g:75mL, and the ratio of mixture 3 to mixture 4 is 500mL:110mL.

[0068] Example 4

[0069] A light-stabilizing agent, the preparation of which includes the following steps:

[0070] Step B1: Epichlorohydrin, ferrocene methylamine, and tetrabutylammonium bromide are added to toluene and refluxed at 100°C with stirring for 4 hours. After cooling to room temperature, an alkaline solution is added and stirred for 2 hours to obtain reaction product a. The ratio of the amount of epichlorohydrin, ferrocene methylamine, tetrabutylammonium bromide, toluene, and alkaline solution is 19g:21g:3.2g:100mL:20mL. The alkaline solution is a 40% sodium hydroxide solution.

[0071] Step B2: Under a nitrogen atmosphere, ethyl 3-(phenylamino)benzoate was heated to 100°C under reflux and stirred for 35 min, then cooled to 50°C and methanol and N-methyl-2,4,6-trinitroaniline (CAS: 1022-07-7, supplier: Dayang Chem (Hangzhou) Co., Ltd.) were added, followed by sodium methoxide. The reaction was stirred for 24 h to obtain reaction product b. The ratio of ethyl 3-(phenylamino)benzoate, methanol, N-methyl-2,4,6-trinitroaniline, and sodium methoxide was 28.5 g: 115 mL: 24.5 g: 0.2 g.

[0072] Step B3: Add reaction product b to toluene, heat to 45°C, add sodium dithionite, reflux and stir for 1.5 h to obtain reaction product c; add reaction product c and reaction product a to dimethyl sulfoxide, stir and react at 55°C for 25 h to obtain a light stabilizer; the ratio of reaction product b, toluene, and sodium dithionite is 54 g: 160 mL: 23 g; the ratio of reaction product c, reaction product a, and dimethyl sulfoxide is 50 g: 41 g: 185 mL.

[0073] Example 5

[0074] A light-stabilizing agent, the preparation of which includes the following steps:

[0075] Step B1: Epichlorohydrin, ferrocene methylamine, and tetrabutylammonium bromide are added to toluene and refluxed at 103°C for 4.3 h. After cooling to room temperature, an alkaline solution is added and stirred for 2.3 h to obtain reaction product a. The ratio of epichlorohydrin, ferrocene methylamine, tetrabutylammonium bromide, toluene, and alkaline solution is 20 g: 21.5 g: 3.3 g: 105 mL: 23 mL. The alkaline solution is a 43% sodium hydroxide solution.

[0076] Step B2: Under a nitrogen atmosphere, ethyl 3-(phenylamino)benzoate was heated to 105°C under reflux and stirred for 38 min, then cooled to 53°C and methanol and N-methyl-2,4,6-trinitroaniline (CAS: 1022-07-7, supplier: Dayang Chem (Hangzhou) Co., Ltd.) were added, followed by sodium methoxide. The reaction was stirred for 24.5 h to obtain reaction product b. The ratio of ethyl 3-(phenylamino)benzoate, methanol, N-methyl-2,4,6-trinitroaniline, and sodium methoxide was 28.8 g: 120 mL: 24.8 g: 0.25 g.

[0077] Step B3: Add reaction product b to toluene, heat to 47°C, add sodium dithionite, reflux and stir for 1.8 h to obtain reaction product c; add reaction product c and reaction product a to dimethyl sulfoxide, stir at 58°C for 25.5 h to obtain a photostable additive; the ratio of reaction product b, toluene, and sodium dithionite is 54.5 g: 170 mL: 24 g; the ratio of reaction product c, reaction product a, and dimethyl sulfoxide is 51 g: 42 g: 190 mL.

[0078] Example 6

[0079] A light-stabilizing agent, the preparation of which includes the following steps:

[0080] Step B1: Epichlorohydrin, ferrocene methylamine, and tetrabutylammonium bromide are added to toluene and refluxed at 105°C with stirring for 4.5 h. After cooling to room temperature, an alkaline solution is added and stirred for 2.5 h to obtain reaction product a. The ratio of the amount of epichlorohydrin, ferrocene methylamine, tetrabutylammonium bromide, toluene, and alkaline solution is 21 g: 22 g: 3.4 g: 110 mL: 25 mL. The alkaline solution is a 45% sodium hydroxide solution.

[0081] Step B2: Under a nitrogen atmosphere, ethyl 3-(phenylamino)benzoate was heated to 110°C under reflux and stirred for 40 min, then cooled to 55°C and methanol and N-methyl-2,4,6-trinitroaniline (CAS: 1022-07-7, supplier: Dayang Chem (Hangzhou) Co., Ltd.) were added, followed by sodium methoxide. The mixture was stirred for 25 h to obtain reaction product b. The ratio of ethyl 3-(phenylamino)benzoate, methanol, N-methyl-2,4,6-trinitroaniline, and sodium methoxide was 29 g: 125 mL: 25 g: 0.3 g.

[0082] Step B3: Add reaction product b to toluene, heat to 50°C, add sodium dithionite, reflux and stir for 2 hours to obtain reaction product c; add reaction product c and reaction product a to dimethyl sulfoxide, stir and react at 60°C for 26 hours to obtain a light stabilizer; the ratio of reaction product b, toluene, and sodium dithionite is 55g:180mL:25g; the ratio of reaction product c, reaction product a, and dimethyl sulfoxide is 52g:43g:195mL.

[0083] Example 7

[0084] An antibacterial polyamide fiber material comprises the following raw materials: 2,5-furandicarboxylic acid chloride, lithium hydroxide, DMAC, m-phenylenediamine, modified EVA, and light stabilizer;

[0085] The preparation of the antibacterial polyamide fiber material includes the following steps:

[0086] Step S1: Under a nitrogen atmosphere, DMAC and m-phenylenediamine are mixed and stirred for 10 min, then cooled to -5℃, and 2,5-furandicarboxylic acid chloride is added. The temperature is controlled at 18℃, and the mixture is stirred for 30 min. Lithium hydroxide is added, and stirring is continued for 3 h to obtain a resin mixture. The ratio of DMAC, m-phenylenediamine, 2,5-furandicarboxylic acid chloride, and lithium hydroxide is 500 mL: 32.4 g: 58 g: 13 g.

[0087] Step S2: The resin mixture, the modified EVA obtained in Example 1, and the light stabilizer obtained in Example 4 are stirred and mixed at 165°C for 2 hours. After desalting and degassing, the mixture is then dry-spun and wet-spun to obtain antibacterial polyamide fiber material. The ratio of resin mixture, modified EVA, and light stabilizer is 61.5 mL: 2.2 g: 0.5 g. During the dry-spun and wet-spun process, the spinning solution temperature is 19°C, the air bath height is maintained at 16 mm, the coagulation bath is a 40% DMAC aqueous solution at 24°C, the water washing coagulation bath is pure water at 80°C, the hot stretching temperature is 300°C, the heat setting temperature is 280°C, and the setting time is 70 s.

[0088] Example 8

[0089] An antibacterial polyamide fiber material comprises the following raw materials: 2,5-furandicarboxylic acid chloride, lithium hydroxide, DMAC, m-phenylenediamine, modified EVA, and light stabilizer;

[0090] The preparation of the antibacterial polyamide fiber material includes the following steps:

[0091] Step S1: Under a nitrogen atmosphere, DMAC and m-phenylenediamine were mixed and stirred for 11 min, then cooled to -5℃, and 2,5-furandicarboxylic acid chloride was added. The temperature was controlled at 19℃, and the mixture was stirred for 33 min. Lithium hydroxide was added, and stirring was continued for 3.3 h to obtain a resin mixture. The ratio of DMAC, m-phenylenediamine, 2,5-furandicarboxylic acid chloride, and lithium hydroxide was 510 mL: 32.7 g: 58.5 g: 13.3 g.

[0092] Step S2: The resin mixture, the modified EVA obtained in Example 2, and the light stabilizer obtained in Example 5 are stirred and mixed at 170°C for 2.3 hours. After desalting and degassing, the mixture is then dry-spun and wet-spun to obtain antibacterial polyamide fiber material. The ratio of resin mixture, modified EVA, and light stabilizer is 62.0 mL: 2.5 g: 0.6 g. During the dry-spun and wet-spun process, the spinning solution temperature is 20°C, the air bath height is maintained at 16 mm, the coagulation bath is a 41% DMAC aqueous solution at 25°C, the water washing coagulation bath is pure water at 83°C, the hot stretching temperature is 303°C, the heat setting temperature is 283°C, and the setting time is 75 s.

[0093] Example 9

[0094] An antibacterial polyamide fiber material comprises the following raw materials: 2,5-furandicarboxylic acid chloride, lithium hydroxide, DMAC, m-phenylenediamine, modified EVA, and light stabilizer;

[0095] The preparation of the antibacterial polyamide fiber material includes the following steps:

[0096] Step S1: Under a nitrogen atmosphere, DMAC and m-phenylenediamine were mixed and stirred for 12 min, then cooled to -5℃, and 2,5-furandicarboxylic acid chloride was added. The temperature was controlled at 20℃, and the mixture was stirred for 35 min. Lithium hydroxide was added, and stirring was continued for 3.5 h to obtain a resin mixture. The ratio of DMAC, m-phenylenediamine, 2,5-furandicarboxylic acid chloride, and lithium hydroxide was 520 mL: 33.0 g: 59 g: 13.5 g.

[0097] Step S2: The resin mixture, the modified EVA obtained in Example 3, and the light stabilizer obtained in Example 6 are stirred and mixed at 175°C for 2.5 hours. After desalting and degassing, the mixture is then dry-spun and wet-spun to obtain antibacterial polyamide fiber material. The ratio of resin mixture, modified EVA, and light stabilizer is 62.5 mL: 2.4 g: 0.7 g. During the dry-spun and wet-spun process, the spinning solution temperature is 21°C, the air bath height is maintained at 16 mm, the coagulation bath is a 42% DMAC aqueous solution at 26°C, the water washing coagulation bath is pure water at 85°C, the hot stretching temperature is 305°C, the heat setting temperature is 285°C, and the setting time is 80 s.

[0098] Comparative Example 1

[0099] Compared with Example 9, the reaction product 2 in the modified EVA preparation process was replaced with 2,4-hexadienoic acid, and the rest was exactly the same as in Example 9, to obtain antibacterial polyamide fiber material.

[0100] Comparative Example 2

[0101] Compared with Example 9, the reaction product 4 in the modified EVA preparation process was replaced with 2-nitro-5-vinylpyridine, and the rest was exactly the same as in Example 9, to obtain antibacterial polyamide fiber material.

[0102] Comparative Example 3

[0103] Compared with Example 9, the ferrocene methylamine in the light stabilizer preparation process was replaced with nano-hydroxy iron oxide with surface amino modification, and the rest was completely the same as in Example 9, to obtain antibacterial polyamide fiber material;

[0104] Preparation of amino-modified nano-ferric hydroxide: KH550 and anhydrous ethanol were ultrasonically dispersed at 60℃ for 3.5h, and then nano-ferric hydroxide (supplier: Xi'an Qiyue Biotechnology Co., Ltd.) was added. The temperature was raised to 80℃ and the mixture was refluxed and stirred for 8.5h to obtain amino-modified nano-ferric hydroxide. The ratio of KH550, anhydrous ethanol and nano-ferric hydroxide was 8g:235mL:2.5g.

[0105] Comparative Example 4

[0106] Compared with Example 9, ethyl 3-(phenylamino)benzoate in the light stabilizer preparation process was replaced with ethyl 3-(2-methoxybenzoyl)benzoate, and the rest was exactly the same as in Example 9, to obtain antibacterial polyamide fiber material.

[0107] The antibacterial polyamide fiber material prepared by the present invention was further tested below, and the test results are as follows.

[0108] Notched impact strength: Tested according to GB / T1043-2008;

[0109] Antibacterial activity: The antibacterial rate was tested using Escherichia coli, Staphylococcus aureus, and Candida albicans as test bacteria.

[0110] Light stability: The obtained polyamide fiber material was placed under ultraviolet light with an intensity of 0.89 W / m 2 The fracture strength retention rate was determined by aging at 50℃ for 500 hours, with reference to GB / T14337-2022.

[0111] Antistatic properties: The conductivity of the polyamide fiber material was measured using a ZC36 high-resistivity microammeter;

[0112] The results are recorded in Table 1;

[0113] Table 1: Test Results

[0114]

[0115]

[0116] According to the data in Table 1, the antibacterial polyamide fiber of the present invention exhibits excellent notched impact strength, antibacterial properties, photostability, and antistatic properties. Comparing Example 9 with Comparative Example 1, it can be seen that replacing reaction product 2 with 2,4-hexadienoic acid only introduces conjugated double bonds into the modified EVA, without ether bonds, thus failing to improve the processing performance of the polyamide fiber. Reaction product 2 has higher antibacterial properties than 2,4-hexadienoic acid, resulting in a decrease in both the notched impact strength and antibacterial properties of the antibacterial polyamide fiber. Comparing Example 9 with Comparative Example 2, it can be seen that replacing reaction product 4 in the EVA preparation process with 2-nitro-5-vinylpyridine reduces the ability of pyridine to enhance the antibacterial properties of the polyamide fiber compared to pyrimidine, thus leading to a decrease in the antibacterial properties of the antibacterial polyamide fiber. Comparing Example 9 with Comparative Example 3, it can be seen that replacing ferrocene methylamine in the light stabilizer preparation process with surface-amino-modified nano-ferric hydroxide results in decreased conductivity and UV absorption of nano-ferric hydroxide compared to ferrocene, and a decreased synergistic UV resistance with diphenylamine, thus leading to a decrease in the light stability and antistatic properties of the antibacterial polyamide fiber material. Comparing Example 9 with Comparative Example 4, it can be seen that replacing ethyl 3-(phenylamino)benzoate in the light stabilizer preparation process with ethyl 3-(2-methoxybenzoyl)benzoate results in a decreased synergistic light stability enhancement between benzophenone and ferrocene compared to the synergistic effect of diphenylamine and ferrocene, thus leading to a decrease in the light stability of the antibacterial polyamide fiber material.

[0117] The above description is merely an example and illustration of the concept of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described or use similar methods to replace them, as long as they do not deviate from the concept of the invention or exceed the scope defined in the claims, they should all fall within the protection scope of the present invention.

Claims

1. An antibacterial polyamide fiber material, characterized in that: The raw materials include: 2,5-furandicarboxylic acid chloride, lithium hydroxide, DMAC, m-phenylenediamine, modified EVA, and light stabilizers; The modified EVA is prepared by the following steps: Step A1: Add vanillin acetone and sodium hydroxide to deionized water and stir to obtain solution 1; then add chloroacetic acid to deionized water and stir, then add sodium hydroxide and stir to obtain solution 2; add solution 2 to solution 1, stir to react, adjust the pH with dilute hydrochloric acid, and then post-process to obtain reaction product 1; Step A2: Under a protective gas atmosphere, reaction product 1 and methylenetriphenylphosphine are added to anhydrous tetrahydrofuran and stirred under reflux to obtain reaction product 2; reaction product 2 is added to DMF, and thionyl chloride is added under stirring and stirred under reflux to obtain reaction product 3. Step A3: Mix 2-amino-5-nitropyrimidine, potassium carbonate and dimethyl sulfoxide to obtain mixture 1; then mix acryloyl chloride and dimethyl sulfoxide to obtain mixture 2; add mixture 2 dropwise to mixture 1 in an ice-water bath and stir the reaction to obtain reaction product 4; Step A4: Mix reaction product 4, dicumyl peroxide, and acetone, then add EVA and melt-extrude on a twin-screw extruder to obtain reaction product 5; add reaction product 5 to toluene, then add sodium dithionite, and reflux and stir to obtain reaction product 6. Step A5: Mix reaction product 6, potassium carbonate and dimethyl sulfoxide to obtain mixture 3; then mix reaction product 3 and dimethyl sulfoxide to obtain mixture 4; add mixture 4 dropwise to mixture 3 in an ice-water bath and stir to obtain modified EVA.

2. The antibacterial polyamide fiber material according to claim 1, characterized in that: In step A1, the ratio of vanillin acetal, sodium hydroxide, and deionized water in solution 1 is 9.6-9.7g: 4.0-4.2g: 50-55mL; the ratio of chloroacetic acid, deionized water, and sodium hydroxide in solution 2 is 9.45-9.50g: 4.0-4.2g: 50-55mL; the ratio of solution 2 to solution 1 is 64-68mL: 66-70mL; and the mass fraction of dilute hydrochloric acid is 13-15%.

3. The antibacterial polyamide fiber material according to claim 1, characterized in that: In step A2, the ratio of reaction product 1, methylenetriphenylphosphine, and anhydrous tetrahydrofuran is 28.7-29.0g: 27.7-28.0g: 120-130mL; the ratio of reaction product 2, DMF, and thionyl chloride is 30-31g: 80-90mL: 11.5-12g.

4. The antibacterial polyamide fiber material according to claim 1, characterized in that: In step A3, the ratio of 2-amino-5-nitropyrimidine, potassium carbonate, and dimethyl sulfoxide in mixture 1 is 14-14.5g: 2.3-2.5g: 40-50mL; the ratio of acryloyl chloride and dimethyl sulfoxide in mixture 2 is 9-9.5g: 18-20mL; and the ratio of mixture 1 to mixture 2 is 60-70mL: 30-35mL.

5. The antibacterial polyamide fiber material according to claim 1, characterized in that: In step A4, the ratio of reaction product 4, dicumyl peroxide, acetone, and EVA is 23-24g: 0.1-0.15g: 50-60mL: 100-105g; the ratio of reaction product 5, toluene, and sodium dithionite is 12-14g: 30-35mL: 2-2.2g.

6. The antibacterial polyamide fiber material according to claim 1, characterized in that: In step A5, the ratio of reaction product 6, potassium carbonate, and dimethyl sulfoxide in mixture 3 is 120-122 g. 5.4-5.6g: 260-270mL, the ratio of reaction product 3 to dimethyl sulfoxide in mixture 4 is 33-35g: 70-75mL; the ratio of mixture 3 to mixture 4 is 490-500mL: 105-110mL.

7. The antibacterial polyamide fiber material according to claim 1, characterized in that: The light-stabilizing agent is prepared by the following steps: Step B1: Add epichlorohydrin, ferrocene methylamine, and tetrabutylammonium bromide to toluene, reflux and stir at 100-105℃ for 4-4.5h, cool to room temperature, add alkaline solution, and stir for 2-2.5h to obtain reaction product a; Step B2: Under a protective gas atmosphere, ethyl 3-(phenylamino)benzoate is heated to 100-110℃ under reflux and stirring for 35-40 min, then cooled to 50-55℃ and methanol and N-methyl-2,4,6-trinitroaniline are added, followed by sodium methoxide. The mixture is stirred for 24-25 h to obtain reaction product b. Step B3: Add reaction product b to toluene, heat to 45-50℃, add sodium dithionite, reflux and stir for 1.5-2 hours to obtain reaction product c; add reaction product c and reaction product a to dimethyl sulfoxide, stir and react at 55-60℃ for 25-26 hours to obtain the light stabilizer.

8. The antibacterial polyamide fiber material according to claim 7, characterized in that: In step B1, the ratio of epichlorohydrin, ferrocene, tetrabutylammonium bromide, toluene, and alkaline solution is 19-21g: 21-22g: 3.2-3.4g: 100-110mL: 20-25mL, and the alkaline solution is a sodium hydroxide solution with a mass fraction of 40-45%.

9. The antibacterial polyamide fiber material according to claim 7, characterized in that: In step B2, the ratio of ethyl 3-(phenylamino)benzoate, methanol, N-methyl-2,4,6-trinitroaniline, and sodium methoxide is 28.5-29 g: 115-125 mL: 24.5-25 g: 0.2-0.3 g; in step B3, the ratio of reaction product b, toluene, and sodium dithionite is 54-55 g: 160-180 mL: 23-25 ​​g, and the ratio of reaction product c, reaction product a, and dimethyl sulfoxide is 50-52 g: 41-43 g: 185-195 mL.

10. A method for preparing an antibacterial polyamide fiber material according to any one of claims 1-9, characterized in that: Includes the following steps: Step S1: Under a nitrogen atmosphere, mix and stir DMAC and m-phenylenediamine for 10-12 min, then cool to -5±1℃, add 2,5-furandicarboxylic acid chloride, control the temperature at 18-20℃, stir and react for 30-35 min, add lithium hydroxide, and continue stirring for 3-3.5 h to obtain a resin mixture; the ratio of DMAC, m-phenylenediamine, 2,5-furandicarboxylic acid chloride, and lithium hydroxide is 500-520 mL : 32.4-33.0 g : 58-59 g : 13-13.5 g; Step S2: Stir the resin mixture, modified EVA, and light stabilizer at 165-175℃ for 2-2.5 hours, then desalinate and degas before dry-jet wet spinning to obtain antibacterial polyamide fiber material. The ratio of resin mixture, modified EVA, and light stabilizer is 61.5-62.5 mL: 2.2-2.4 g: 0.5-0.7 g. During the dry-jet wet spinning process, the spinning solution temperature is 19-21℃, the air bath height is maintained at 12-18 mm, the coagulation bath is a 40-42% DMAC aqueous solution at 24-26℃, the water washing coagulation bath uses pure water at 80-85℃, the hot stretching temperature is 300-305℃, the heat setting temperature is 280-285℃, and the setting time is 70-80 seconds.

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