Nylon yarn with slow-release antibacterial performance and preparation process thereof

Abstract

The invention belongs to the technical field of functional textiles, and particularly relates to a nylon yarn with slow-release antibacterial performance and a preparation process of the nylon yarn. The preparation technology of the nylon yarn with the slow-release antibacterial performance comprises the steps that 1-(4-isothiocyanobenzyl) vinyl diamine-N, N, N ', N'-tetraacetic acid reacts with copper salt, and chelated copper is prepared; reacting the chelated copper with nylon 66 to prepare modified nylon 66; spinning the modified nylon 66 into nylon yarns through an electrostatic spinning process; and the nylon yarn is subjected to antibacterial finishing, and the nylon yarn with the slow-release antibacterial performance is prepared. In the invention, due to the slow release property of copper ions in chelated copper, the antibacterial component silver in the antibacterial finishing agent is nano-silver, and the release rate is slow, so that the nylon yarn has good slow-release antibacterial performance.

Description

Technical Field

[0001] The present invention belongs to the technical field of functional textiles, and in particular relates to a nylon yarn with slow-release antibacterial properties and a preparation process thereof. Background Art

[0002] Nylon yarn, also known as polyamide fiber, includes nylon filament and nylon staple. Due to its good comprehensive properties, including mechanical properties, heat resistance, and wear resistance, it is widely used in textile fields such as clothing, carpets, and decorative fabrics.

[0003] However, textiles are prone to bacterial growth during use, posing a potential threat to human health when in contact with the human body. Therefore, the antibacterial properties of nylon yarns need to be improved. Furthermore, textiles generally have a long service life, requiring nylon yarns to possess sustained-release antibacterial properties to achieve long-lasting antibacterial efficacy. Chinese patent CN114672894B discloses a process for preparing antibacterial nylon yarns. This process achieves antibacterial properties by adding an antibacterial masterbatch to a conventional masterbatch. The antibacterial component in the antibacterial masterbatch is a graphene oxide / nanosilver antibacterial agent. The graphene oxide / nanosilver composite material can reduce the release rate of the nanosilver, providing a sustained-release effect and extending the duration of the antibacterial nylon yarn's action. However, the graphene oxide / nanosilver antibacterial agent suffers from poor compatibility with the PA6 carrier resin, leaving room for improvement in the antibacterial properties of the nylon yarns. Summary of the Invention

[0004] In view of the deficiencies in the prior art, the present invention provides a nylon yarn with slow-release antibacterial properties, thereby solving the problem in the prior art that the antibacterial properties of nylon yarns need to be improved.

[0005] In order to achieve the above object, the technical solution adopted by the present invention is as follows: A preparation process of nylon yarn with slow-release antibacterial properties comprises the following steps: Step 1: dissolving 1-(4-isothiocyanobenzyl)ethylenediamine-N,N,N',N'-tetraacetic acid in phosphate buffer, adding copper salt, reacting, and adjusting the pH of the reaction mixture to 8-9 after the reaction is completed. Filtering and rotary evaporation are performed to obtain chelated copper; Step 2: dissolving nylon 66 slices in a mixed solvent to obtain a nylon 66 slice solution, adding chelated copper to the nylon 66 slice solution, reacting, and after the reaction is completed, precipitating, filtering, and washing to obtain modified nylon 66; Step 3: dissolving the modified nylon 66 in a mixed solvent to obtain a spinning solution, and subjecting the spinning solution to electrospinning, stretching and shaping to obtain nylon yarn; Step 4: placing the nylon yarn in an antibacterial finishing liquid, reacting, washing, and drying after the reaction to obtain the nylon yarn with slow-release antibacterial properties; wherein the antibacterial finishing liquid comprises a mixture of a slow-release antibacterial agent, an initiator, and ethyl acetate.

[0006] Preferably, in step 1, the molar ratio of 1-(4-isothiocyanatobenzyl)ethylenediamine-N,N,N',N'-tetraacetic acid to copper salt is 1:(1.1-1.2), the amount of phosphate buffer used is 800-1000 times the mass of 1-(4-isothiocyanatobenzyl)ethylenediamine-N,N,N',N'-tetraacetic acid, and the reaction conditions are stirring at room temperature for 30-60 minutes.

[0007] Preferably, the copper salt comprises copper chloride dihydrate.

[0008] Preferably, in step 2, the mass ratio of nylon 66 chips, mixed solvent, and chelated copper is (15-20): (400-600): (0.6-0.8), and the reaction is carried out at a temperature of 70-90° C. for 6-8 hours.

[0009] Preferably, the mixed solvent is prepared by mixing benzene, m-cresol, xylene and ethylene glycol ethyl ether; the mass ratio of benzene, m-cresol, xylene and ethylene glycol ethyl ether is 30:25:25:20.

[0010] Preferably, in step three, the mass ratio of modified nylon 66 to the mixed solvent is (10-20):100; the electrospinning process conditions include: the electrospinning voltage is 12-18 kV, the height from the spinneret to the bath surface is 5-10 cm, and the winding speed is 5-7 m / min; the stretching and shaping process conditions include: the stretching temperature is 100-120 ° C, and the stretching ratio is 1-3 times.

[0011] Optionally, the bath comprises 0.4 wt% to 1.2 wt% of a Peregal O-15 aqueous solution.

[0012] Preferably, the mixed solvent is the same as the mixed solvent in step 2.

[0013] Preferably, in step 4, the bath ratio of the nylon yarn to the antibacterial finishing liquid is 1:(20-30), and the reaction conditions are 80-90° C. for 1.5-2.5 hours.

[0014] Preferably, in the step 4: when preparing the antibacterial finishing liquid, the mass ratio of the slow-release antibacterial agent, the initiator, and ethyl acetate is (5-10): (0.05-0.1): (150-250).

[0015] Preferably, the initiator comprises benzoyl peroxide.

[0016] Preferably, the sustained-release antibacterial agent is prepared by the following steps: S1. Dispersing mesoporous silica molecular sieve in hydrochloric acid, stirring, filtering, washing, and drying to obtain activated mesoporous silica molecular sieve; adding the activated mesoporous silica molecular sieve to toluene, ultrasonically dispersing, adding γ-methacryloxypropyltrimethoxysilane (silane coupling agent KH570), reacting, filtering, washing, and drying to obtain olefinated mesoporous silica molecular sieve; S2, add olefinic mesoporous silica molecular sieve to ethanol, after ultrasonic dispersion, add silver nitrate, stir, after stirring, filter, dry, to obtain loaded Ag + Alkenylated mesoporous silica molecular sieves; S3, load Ag + The olefinic mesoporous silica molecular sieve is added to ethanol, an ascorbic acid aqueous solution is added dropwise, and the mixture is stirred. After the stirring is completed, an aqueous sodium citrate solution is added and the stirring is continued. After the stirring is completed, the mixture is filtered, washed, and dried to obtain an olefinic mesoporous silica molecular sieve loaded with nanosilver particles, that is, a sustained-release antibacterial agent; preferably, in S1, the mass ratio of the mesoporous silica molecular sieve to the hydrochloric acid is 1:(12-18), and the stirring condition is stirring at room temperature for 1.5-2.5 hours.

[0017] Preferably, the concentration of the hydrochloric acid is 2 mol / L.

[0018] Preferably, in S1, the mass ratio of activated mesoporous silica molecular sieve, toluene, and γ-methacryloxypropyltrimethoxysilane is 1:(30-50):(1.5-2.5), and the reaction conditions are stirring at 80-90° C. for 10-15 hours.

[0019] Preferably, the mesoporous silica molecular sieve includes mesoporous silica molecular sieve SBA-15.

[0020] Preferably, in S2, the mass ratio of olefinated mesoporous silica molecular sieve, ethanol and silver nitrate is 60:(180-240):(6.8-8), and the stirring condition is to stir for 3-5 hours in a sealed container at room temperature in the dark.

[0021] Preferably, in said S3: load Ag + The mass ratio of the olefinated mesoporous silica molecular sieve, ethanol, ascorbic acid aqueous solution, and sodium citrate aqueous solution is 65: (200-300): (20-25): (15-20), and the stirring conditions are: stirring in a sealed container in the dark at a temperature of 35-45°C for 20-40 minutes, and the stirring conditions are continued: stirring in a sealed container in the dark at a temperature of 35-45°C for 20-40 minutes.

[0022] Preferably, the concentration of the ascorbic acid aqueous solution is 0.01 mol / L.

[0023] The concentration of the sodium citrate aqueous solution is 0.04 mol / L.

[0024] The present invention also discloses a nylon yarn with sustained-release antibacterial properties prepared by adopting the above-mentioned process for preparing nylon yarn with sustained-release antibacterial properties.

[0025] Compared with the prior art, the present invention has the following beneficial effects: 1-(4-isothiocyanobenzyl)ethylenediamine-N,N,N',N'-tetraacetic acid is used as a chelating agent to 2+ ) has a strong coordination and chelating effect, and can form a stable hexadentate ligand chelate with copper ions to obtain chelated copper, and then the isothiocyanate group contained in the 1-(4-isothiocyanobenzyl)ethylenediamine-N,N,N',N'-tetraacetic acid molecule reacts with the amino group on the nylon 66 molecule to connect the chelated copper to the nylon 66 molecule with a stable chemical bond (thiourea) to obtain modified nylon 66, which has good antibacterial stability; the nylon yarn spun from the modified nylon 66 can slowly release copper ions, thereby achieving a sustained release effect on copper ions, and the nylon yarn has a sustained release antibacterial effect; in the present invention, the antibacterial performance can be further improved by performing antibacterial finishing on the nylon yarn, wherein the effective antibacterial component of the antibacterial finishing agent is silver, and mesoporous silica molecular sieve is used as a carrier. Since the mesoporous silica molecular sieve contains a large number of pore structures, it can load a large amount of silver ions (Ag + ), has good antibacterial effect, and by reducing silver ions to form nanosilver particles, the antibacterial activity is exerted through the slow release of nanosilver particles. Compared with silver ions, the release rate of nanosilver is weakened, the antibacterial effect is more long-lasting, and it can effectively control the rapid loss of silver ions to achieve sustained-release antibacterial efficacy; because the mesoporous silica molecular sieve has been modified and olefin groups have been introduced, graft polymerization is achieved on the nylon 66 molecule under the action of the initiator, and the sustained-release antibacterial agent is connected to the nylon 66 molecule with a stable chemical bond, and the antibacterial performance is stable. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 This is a flow chart of the preparation process of the nylon yarn with sustained-release antibacterial properties of the present invention; Figure 2 This is a bar chart showing the antibacterial performance test results of nylon yarns prepared in Examples 1-5 and Comparative Examples 1-2; Figure 3 This is a bar chart showing the test results of the sustained-release antibacterial properties of the nylon yarns prepared in Examples 1-5 and Comparative Examples 1-2. DETAILED DESCRIPTION

[0027] Example 1 This embodiment discloses a preparation process of nylon yarn with sustained-release antibacterial properties, comprising the following steps: Step 1, dissolving 1-(4-isothiocyanatobenzyl)ethylenediamine-N,N,N',N'-tetraacetic acid in phosphate buffer, the amount of phosphate buffer is 800 times the mass of 1-(4-isothiocyanatobenzyl)ethylenediamine-N,N,N',N'-tetraacetic acid, adding copper chloride dihydrate, 1-(4-isothiocyanatobenzyl)ethylenediamine-N,N,N',N'-tetraacetic acid, copper chloride dihydrate The molar ratio is 1:1.1, and the reaction is stirred at room temperature at a speed of 300 r / min for 30 minutes. After the reaction is completed, the pH value of the reaction mixture is adjusted to 8 with a 1 mol / L sodium hydroxide aqueous solution, filtered, and the filtrate is rotary evaporated at 75°C to obtain chelated copper; Step 2: dissolving nylon 66 slices in a mixed solvent to obtain a nylon 66 slice solution, adding chelated copper to the nylon 66 slice solution, wherein the mass ratio of nylon 66 slices, mixed solvent, and chelated copper is 15:400:0.6, reacting at 70°C for 8 hours, and after the reaction is completed, adding deionized water twice the mass of the mixed solvent for precipitation, filtering, and washing the precipitate with ethanol three times to obtain modified nylon 66; wherein the mixed solvent is prepared by mixing benzene, m-cresol, xylene, and ethylene glycol ethyl ether in a mass ratio of 30:25:25:20; Step 3: dissolving modified nylon 66 in a mixed solvent with a mass ratio of modified nylon 66 to the mixed solvent being 10:100 to obtain a spinning solution, and subjecting the spinning solution to electrospinning and stretching to obtain nylon yarn; wherein the electrospinning process conditions include: an electrospinning voltage of 15 kV, a height from the spinneret to the bath surface of 8 cm, and a winding speed of 6 m / min; the bath is a 1 wt % aqueous solution of Peregal O-15; the stretching and setting process conditions include: a stretching temperature of 110° C. and a stretching ratio of 2.5 times; and the mixed solvent is the same as the mixed solvent in step 2; Step 4, placing the nylon yarn in the antibacterial finishing liquid, the bath ratio of the nylon yarn to the antibacterial finishing liquid is 1:20, and reacting at 80°C for 2.5 hours. After the reaction is completed, the nylon yarn is taken out from the antibacterial finishing liquid, washed with ethanol 3 times, and dried naturally to obtain a nylon yarn with slow-release antibacterial properties; wherein the antibacterial finishing liquid is prepared by mixing a slow-release antibacterial agent, benzoyl peroxide, and ethyl acetate in a mass ratio of 5:0.05:150; the slow-release antibacterial agent is prepared by the following steps: S1, dispersing mesoporous silica molecular sieve SBA-15 in 2mol / L hydrochloric acid, the mass ratio of mesoporous silica molecular sieve SBA-15 to 2mol / L hydrochloric acid is 1:15, stirring at room temperature for 2 hours, after the stirring is completed, filtering, washing with toluene 5 times, and drying in a vacuum drying oven at 60°C for 24 hours to obtain activated mesoporous silica molecular sieve; adding the activated mesoporous silica molecular sieve to toluene , after ultrasonic dispersion at a frequency of 40kHz for 30min, γ-methacryloxypropyltrimethoxysilane was added, the mass ratio of activated mesoporous silica molecular sieve, toluene, and γ-methacryloxypropyltrimethoxysilane was 1:40:2, and the mixture was stirred at a temperature of 85°C and a speed of 250r / min for 12h. After the reaction was completed, it was filtered, washed with toluene 5 times, and dried in a vacuum drying oven at 60°C for 24h to obtain olefinic mesoporous silica molecular sieve; S2, the olefinic mesoporous silica molecular sieve was added to ethanol and ultrasonically dispersed at a frequency of 40kHz for 30min, and silver nitrate was added. The mass ratio of olefinic mesoporous silica molecular sieve, ethanol, and silver nitrate was 60:220:7.5. It was sealed and stirred in the dark for 4h at room temperature with a stirring speed of 300r / min. After the stirring was completed, it was filtered and dried in a vacuum drying oven at 50°C for 24h to obtain loaded Ag. + Alkenyl mesoporous silica molecular sieve; S3, load Ag + The olefinated mesoporous silica molecular sieve was added to ethanol, and 0.01 mol / L ascorbic acid aqueous solution was added dropwise. The mixture was sealed and stirred at 40 ° C in the dark for 30 min at a stirring speed of 300 r / min. After the stirring was completed, 0.04 mol / L sodium citrate aqueous solution was added to load Ag. + The mass ratio of olefinated mesoporous silica molecular sieve, ethanol, 0.01 mol / L ascorbic acid aqueous solution and 0.04 mol / L sodium citrate aqueous solution is 65:250:22:18. The mixture is sealed and stirred in the dark at 40°C for 30 minutes at a stirring speed of 300 r / min. After stirring, it is filtered, washed with ethanol and water three times respectively, and dried in a vacuum drying oven at 50°C for 24 hours to obtain a sustained-release antibacterial agent.

[0028] Example 2 This embodiment discloses a preparation process of nylon yarn with sustained-release antibacterial properties, comprising the following steps: Step 1, dissolving 1-(4-isothiocyanatobenzyl)ethylenediamine-N,N,N',N'-tetraacetic acid in phosphate buffer, the amount of phosphate buffer is 1000 times the mass of 1-(4-isothiocyanatobenzyl)ethylenediamine-N,N,N',N'-tetraacetic acid, adding copper chloride dihydrate, 1-(4-isothiocyanatobenzyl)ethylenediamine-N,N,N',N'-tetraacetic acid, copper chloride dihydrate The molar ratio is 1:1.2, and the reaction is stirred at room temperature at a speed of 200 r / min for 60 minutes. After the reaction is completed, the pH value of the reaction mixture is adjusted to 9 with a 1 mol / L sodium hydroxide aqueous solution, filtered, and the filtrate is rotary evaporated at 75°C to obtain chelated copper; Step 2: dissolving nylon 66 slices in a mixed solvent to obtain a nylon 66 slice solution, adding chelated copper to the nylon 66 slice solution, wherein the mass ratio of nylon 66 slices, mixed solvent, and chelated copper is 20:600:0.8, reacting at 90°C for 6 hours, and after the reaction, adding deionized water twice the mass of the mixed solvent for precipitation, filtering, and washing the precipitate with ethanol three times to obtain modified nylon 66; wherein the mixed solvent is prepared by mixing benzene, m-cresol, xylene, and ethylene glycol ethyl ether in a mass ratio of 30:25:25:20; Step 3: dissolving modified nylon 66 in a mixed solvent with a mass ratio of modified nylon 66 to the mixed solvent being 20:100 to obtain a spinning solution, and the spinning solution is subjected to electrospinning and stretching to obtain nylon yarn; wherein the electrospinning process conditions include: an electrospinning voltage of 15 kV, a height from the spinneret to the bath surface of 8 cm, and a winding speed of 6 m / min; the bath is a 1 wt % aqueous solution of perepinga O-15; the stretching and setting process conditions include: a stretching temperature of 110° C. and a stretching ratio of 2.5 times; and the mixed solvent is the same as the mixed solvent in step 2; Step 4: Place the nylon yarn in an antibacterial finishing liquid with a bath ratio of nylon yarn to antibacterial finishing liquid of 1:30, react at 90°C for 1.5 hours, and after the reaction, remove the nylon yarn from the antibacterial finishing liquid, wash it three times with ethanol, and dry it naturally to obtain a nylon yarn with sustained-release antibacterial properties; wherein the antibacterial finishing liquid is prepared by mixing a sustained-release antibacterial agent, benzoyl peroxide, and ethyl acetate in a mass ratio of 10:0.1:250; the preparation method of the sustained-release antibacterial agent is the same as that in Example 1.

[0029] Example 3 This embodiment discloses a preparation process of nylon yarn with sustained-release antibacterial properties, comprising the following steps: Step 1, dissolving 1-(4-isothiocyanatobenzyl)ethylenediamine-N,N,N',N'-tetraacetic acid in phosphate buffer, the amount of phosphate buffer being 850 times the mass of 1-(4-isothiocyanatobenzyl)ethylenediamine-N,N,N',N'-tetraacetic acid, adding copper chloride dihydrate, the molar ratio of 1-(4-isothiocyanatobenzyl)ethylenediamine-N,N,N',N'-tetraacetic acid and copper chloride dihydrate being 1:1.12, stirring at room temperature at a speed of 250 r / min for 45 minutes, after the reaction is completed, adjusting the pH value of the reaction mixture to 8.5 with 1 mol / L sodium hydroxide aqueous solution, filtering, and rotary evaporating the filtrate at 75°C to obtain chelated copper; Step 2: dissolving nylon 66 slices in a mixed solvent to obtain a nylon 66 slice solution, adding chelated copper to the nylon 66 slice solution, wherein the mass ratio of nylon 66 slices, mixed solvent, and chelated copper is 16:450:0.65, reacting at 80°C for 7 hours, and after the reaction is completed, adding deionized water twice the mass of the mixed solvent for precipitation, filtering, and washing the precipitate with ethanol three times to obtain modified nylon 66; wherein the mixed solvent is prepared by mixing benzene, m-cresol, xylene, and ethylene glycol ethyl ether in a mass ratio of 30:25:25:20; Step 3: dissolving modified nylon 66 in a mixed solvent with a mass ratio of modified nylon 66 to the mixed solvent being 15:100 to obtain a spinning solution, and subjecting the spinning solution to electrospinning and stretching to obtain nylon yarn; wherein the electrospinning process conditions include: an electrospinning voltage of 15 kV, a height from the spinneret to the bath surface of 8 cm, and a winding speed of 6 m / min; the bath is a 1 wt % aqueous solution of Peregal O-15; the stretching and setting process conditions include: a stretching temperature of 110° C. and a stretching ratio of 2.5 times; and the mixed solvent is the same as the mixed solvent in step 2; Step 4: Place the nylon yarn in an antibacterial finishing liquid with a bath ratio of nylon yarn to antibacterial finishing liquid of 1:25, react at 85°C for 2 hours, and after the reaction, remove the nylon yarn from the antibacterial finishing liquid, wash it three times with ethanol, and dry it naturally to obtain a nylon yarn with sustained-release antibacterial properties; wherein the antibacterial finishing liquid is prepared by mixing a sustained-release antibacterial agent, benzoyl peroxide, and ethyl acetate in a mass ratio of 6:0.06:200; the preparation method of the sustained-release antibacterial agent is the same as that in Example 1.

[0030] Example 4 This embodiment discloses a preparation process of nylon yarn with sustained-release antibacterial properties, comprising the following steps: Step 1, dissolving 1-(4-isothiocyanatobenzyl)ethylenediamine-N,N,N',N'-tetraacetic acid in phosphate buffer, the amount of phosphate buffer is 900 times the mass of 1-(4-isothiocyanatobenzyl)ethylenediamine-N,N,N',N'-tetraacetic acid, adding copper chloride dihydrate, 1-(4-isothiocyanatobenzyl)ethylenediamine-N,N,N',N'-tetraacetic acid, copper chloride dihydrate The molar ratio is 1:1.15, and the reaction is stirred at room temperature at a speed of 250r / min for 45min. After the reaction is completed, the pH value of the reaction mixture is adjusted to 8.5 with 1mol / L sodium hydroxide aqueous solution, filtered, and the filtrate is rotary evaporated at 75°C to obtain chelated copper; Step 2: dissolving nylon 66 slices in a mixed solvent to obtain a nylon 66 slice solution, adding chelated copper to the nylon 66 slice solution, wherein the mass ratio of nylon 66 slices, mixed solvent, and chelated copper is 17.5:500:0.7, reacting at 80°C for 7 hours, and after the reaction is completed, adding deionized water twice the mass of the mixed solvent for precipitation, filtering, and washing the precipitate with ethanol three times to obtain modified nylon 66; wherein the mixed solvent is prepared by mixing benzene, m-cresol, xylene, and ethylene glycol ethyl ether in a mass ratio of 30:25:25:20; Step 3: dissolving modified nylon 66 in a mixed solvent with a mass ratio of modified nylon 66 to the mixed solvent being 15:100 to obtain a spinning solution, and subjecting the spinning solution to electrospinning and stretching to obtain nylon yarn; wherein the electrospinning process conditions include: an electrospinning voltage of 15 kV, a height from the spinneret to the bath surface of 8 cm, and a winding speed of 6 m / min; the bath is a 1 wt % aqueous solution of Peregal O-15; the stretching and setting process conditions include: a stretching temperature of 110° C. and a stretching ratio of 2.5 times; and the mixed solvent is the same as the mixed solvent in step 2; Step 4: Place the nylon yarn in an antibacterial finishing liquid with a bath ratio of nylon yarn to antibacterial finishing liquid of 1:25, react at 85°C for 2 hours, and after the reaction, remove the nylon yarn from the antibacterial finishing liquid, wash it three times with ethanol, and dry it naturally to obtain a nylon yarn with sustained-release antibacterial properties; wherein the antibacterial finishing liquid is prepared by mixing a sustained-release antibacterial agent, benzoyl peroxide, and ethyl acetate in a mass ratio of 7.5:0.08:200; the preparation method of the sustained-release antibacterial agent is the same as that in Example 1.

[0031] Example 5 This embodiment discloses a preparation process of nylon yarn with sustained-release antibacterial properties, comprising the following steps: Step 1, dissolving 1-(4-isothiocyanatobenzyl)ethylenediamine-N,N,N',N'-tetraacetic acid in phosphate buffer, the amount of phosphate buffer is 900 times the mass of 1-(4-isothiocyanatobenzyl)ethylenediamine-N,N,N',N'-tetraacetic acid, adding copper chloride dihydrate, 1-(4-isothiocyanatobenzyl)ethylenediamine-N,N,N',N'-tetraacetic acid, copper chloride dihydrate The molar ratio is 1:1.18, and the reaction is stirred at room temperature at a speed of 250r / min for 45min. After the reaction is completed, the pH value of the reaction mixture is adjusted to 8.5 with 1mol / L sodium hydroxide aqueous solution, filtered, and the filtrate is rotary evaporated at 75°C to obtain chelated copper; Step 2: dissolving nylon 66 slices in a mixed solvent to obtain a nylon 66 slice solution, adding chelated copper to the nylon 66 slice solution, wherein the mass ratio of nylon 66 slices, mixed solvent, and chelated copper is 19:550:0.75, reacting at 80°C for 7 hours, and after the reaction is completed, adding deionized water twice the mass of the mixed solvent for precipitation, filtering, and washing the precipitate with ethanol three times to obtain modified nylon 66; wherein the mixed solvent is prepared by mixing benzene, m-cresol, xylene, and ethylene glycol ethyl ether in a mass ratio of 30:25:25:20; Step 3: dissolving modified nylon 66 in a mixed solvent with a mass ratio of modified nylon 66 to the mixed solvent being 15:100 to obtain a spinning solution, and subjecting the spinning solution to electrospinning and stretching to obtain nylon yarn; wherein the electrospinning process conditions include: an electrospinning voltage of 15 kV, a height from the spinneret to the bath surface of 8 cm, and a winding speed of 6 m / min; the bath is a 1 wt % aqueous solution of Peregal O-15; the stretching and setting process conditions include: a stretching temperature of 110° C. and a stretching ratio of 2.5 times; and the mixed solvent is the same as the mixed solvent in step 2; Step 4: Place the nylon yarn in an antibacterial finishing liquid with a bath ratio of nylon yarn to antibacterial finishing liquid of 1:25, react at 85°C for 2 hours, and after the reaction, remove the nylon yarn from the antibacterial finishing liquid, wash it three times with ethanol, and dry it naturally to obtain a nylon yarn with sustained-release antibacterial properties; wherein the antibacterial finishing liquid is prepared by mixing a sustained-release antibacterial agent, benzoyl peroxide, and ethyl acetate in a mass ratio of 9:0.09:200; the preparation method of the sustained-release antibacterial agent is the same as that in Example 1.

[0032] Comparative Example 1 Step 1, dissolving nylon 66 chips in a mixed solvent to obtain a nylon 66 chip solution, adding copper chloride dihydrate to the nylon 66 chip solution, the mass ratio of nylon 66 chips, copper chloride dihydrate, and the mixed solvent is 9.83:0.17:100, stirring and mixing to obtain a spinning solution, and the spinning solution is subjected to electrostatic spinning and stretching to obtain nylon yarn; wherein the mixed solvent is prepared by mixing benzene, m-cresol, xylene, and ethylene glycol ethyl ether in a mass ratio of 30:25:25:20; the process conditions of electrostatic spinning include: the electrostatic spinning voltage is 15kV, the height from the spinneret to the bath surface is 8cm, and the winding speed is 6m / min; the bath is a 1wt% perepinga O-15 aqueous solution; the process conditions of stretching and setting include: the stretching temperature is 110°C, and the stretching ratio is 2.5 times; Step 2: Place the nylon yarn in an antibacterial finishing liquid with a bath ratio of nylon yarn to antibacterial finishing liquid of 1:20, react at 80°C for 2.5 hours, and after the reaction, remove the nylon yarn from the antibacterial finishing liquid, wash it three times with ethanol, and dry it naturally to obtain a nylon yarn with sustained-release antibacterial properties; wherein the antibacterial finishing liquid is prepared by mixing a sustained-release antibacterial agent, benzoyl peroxide, and ethyl acetate in a mass ratio of 5:0.05:150; the preparation method of the sustained-release antibacterial agent is the same as that in Example 1.

[0033] Comparative Example 2 This comparative example discloses a preparation process of nylon yarn with sustained-release antibacterial properties, comprising the following steps: Step 1, dissolving 1-(4-isothiocyanatobenzyl)ethylenediamine-N,N,N',N'-tetraacetic acid in phosphate buffer, the amount of phosphate buffer is 800 times the mass of 1-(4-isothiocyanatobenzyl)ethylenediamine-N,N,N',N'-tetraacetic acid, adding copper chloride dihydrate, 1-(4-isothiocyanatobenzyl)ethylenediamine-N,N,N',N'-tetraacetic acid, copper chloride dihydrate The molar ratio is 1:1.1, and the reaction is stirred at room temperature at a speed of 300 r / min for 30 minutes. After the reaction is completed, the pH value of the reaction mixture is adjusted to 8 with a 1 mol / L sodium hydroxide aqueous solution, filtered, and the filtrate is rotary evaporated at 75°C to obtain chelated copper; Step 2: dissolving nylon 66 slices in a mixed solvent to obtain a nylon 66 slice solution, adding chelated copper to the nylon 66 slice solution, wherein the mass ratio of nylon 66 slices, mixed solvent, and chelated copper is 15:400:0.6, reacting at 70°C for 8 hours, and after the reaction is completed, adding deionized water twice the mass of the mixed solvent for precipitation, filtering, and washing the precipitate with ethanol three times to obtain modified nylon 66; wherein the mixed solvent is prepared by mixing benzene, m-cresol, xylene, and ethylene glycol ethyl ether in a mass ratio of 30:25:25:20; Step 3: Dissolve modified nylon 66 in a mixed solvent with a mass ratio of modified nylon 66 to the mixed solvent of 10:100 to obtain a spinning solution, and the spinning solution is subjected to electrospinning and stretching to obtain a nylon yarn with sustained-release antibacterial properties; wherein the electrospinning process conditions include: an electrospinning voltage of 15 kV, a height from the spinneret to the bath surface of 8 cm, and a winding speed of 6 m / min; the bath is a 1 wt% aqueous solution of perepinga O-15; the stretching and setting process conditions include: a stretching temperature of 110° C. and a stretching ratio of 2.5 times; the mixed solvent is the same as the mixed solvent in step 2; Step 4: placing the nylon yarn in the antibacterial finishing liquid, the bath ratio of the nylon yarn to the antibacterial finishing liquid is 1:20, and reacting at 80°C for 2.5 hours. After the reaction is completed, the nylon yarn is taken out from the antibacterial finishing liquid, washed with ethanol 3 times, and dried naturally to obtain a nylon yarn with slow-release antibacterial properties; wherein the antibacterial finishing liquid is loaded with Ag + The olefinated mesoporous silica molecular sieve, benzoyl peroxide and ethyl acetate are mixed in a mass ratio of 5:0.05:150; the loaded Ag + The alkenyl mesoporous silica molecular sieve is prepared by the following steps: S1, dispersing the mesoporous silica molecular sieve SBA-15 in 2mol / L hydrochloric acid, the mass ratio of the mesoporous silica molecular sieve SBA-15 to the 2mol / L hydrochloric acid is 1:15, stirring at room temperature for 2h, filtering after the stirring is completed, washing with toluene 5 times, and drying in a vacuum drying oven at 60℃ for 24h to obtain an activated mesoporous silica molecular sieve; adding the activated mesoporous silica molecular sieve to toluene, ultrasonically dispersing at a frequency of 40kHz for 30min, adding γ-methacryloyloxypropyltrimethoxysilane, and the activated mesoporous silica molecular sieve, toluene, and γ-methacryloyloxypropyltrimethoxysilane. The mass ratio of the silane is 1:40:2, and the reaction is stirred at 85°C and 250r / min for 12h. After the reaction is completed, it is filtered, washed with toluene 5 times, and placed in a vacuum drying oven at 60°C for 24h to obtain an olefinic mesoporous silica molecular sieve; S2, the olefinic mesoporous silica molecular sieve is added to ethanol and ultrasonically dispersed at a frequency of 40kHz for 30min, and then silver nitrate is added. The mass ratio of the olefinic mesoporous silica molecular sieve, ethanol, and silver nitrate is 60:220:7.5. The mixture is sealed and stirred at room temperature in the dark for 4h at a stirring speed of 300r / min. After the stirring is completed, it is filtered and placed in a vacuum drying oven at 50°C for 24h to obtain loaded Ag. +In the above examples and comparative examples, phosphate buffer was purchased from Shanghai Yuanye Biotechnology Co., Ltd., with a pH of 7.8-80; nylon 66 chips were purchased from Jiangsu Huayang Nylon Co., Ltd., with a molecular weight of 14,300-20,000 and a melting point of 253°C; and mesoporous silica molecular sieve SBA-15 was purchased from Jiangsu Xianfeng Nanomaterials Technology Co., Ltd., with a pore size of 6-13 nm.

[0034] Test Case The performance tests were conducted on the nylon yarns with sustained-release antibacterial properties prepared in Examples 1-5 and Comparative Examples 1-2: (1) Antibacterial performance test: The initial antibacterial rate of nylon yarn against Staphylococcus aureus, Escherichia coli and Candida albicans was determined with reference to the standard GB / T20944.3-2008 "Evaluation of antibacterial properties of textiles Part 3: Oscillation method". The test results are shown in Table 1: .

[0035] As shown in Table 1, the nylon yarn produced by the present invention has good antibacterial properties. Since the antibacterial component copper ions are introduced into nylon 66 and the antibacterial component silver is grafted onto the nylon yarn spun from nylon 66, the nylon yarn has excellent antibacterial properties.

[0036] (2) Sustained-release antibacterial performance test: The antibacterial rate of nylon yarn against Staphylococcus aureus, Escherichia coli and Candida albicans after washing 30 times was determined with reference to the standard GB / T20944.3-2008 "Evaluation of antibacterial properties of textiles Part 3: Oscillation method". The results are shown in Table 2: .

[0037] Table 2 shows that the nylon yarn produced by the present invention exhibits excellent sustained-release antimicrobial properties. The antimicrobial component, copper ions, undergoes chelation with a chelating agent, resulting in a slow release effect. The antimicrobial component, silver, is reduced from its ionic state to a nanoelement, reducing its leaching rate and maintaining sustained-release antimicrobial efficacy. Compared with Example 1, in Comparative Example 1, the antimicrobial component, copper ions, are not chelated, resulting in a high leaching rate and reduced sustained-release antimicrobial performance. In Comparative Example 2, the antimicrobial component, silver ions, exhibit an increased leaching rate and a significant decrease in sustained-release antimicrobial performance.

[0038] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to these embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.

Claims

1. A process for preparing nylon yarn with sustained-release antibacterial properties, characterized in that: The following steps are involved: Step 1: dissolving 1-(4-isothiocyanobenzyl)ethylenediamine-N,N,N',N'-tetraacetic acid in phosphate buffer, adding copper salt, reacting, and adjusting the pH of the reaction mixture to 8-9 after the reaction is completed. Filtering and rotary evaporation are performed to obtain chelated copper; Step 2: dissolving nylon 66 slices in a mixed solvent to obtain a nylon 66 slice solution, adding chelated copper to the nylon 66 slice solution, reacting, and after the reaction is completed, precipitating, filtering, and washing to obtain modified nylon 66; Step 3: dissolving the modified nylon 66 in a mixed solvent to obtain a spinning solution, and subjecting the spinning solution to electrospinning, stretching and shaping to obtain nylon yarn; Step 4: placing the nylon yarn in an antibacterial finishing liquid, reacting, washing, and drying after the reaction to obtain the nylon yarn with slow-release antibacterial properties; wherein the antibacterial finishing liquid comprises a mixture of a slow-release antibacterial agent, an initiator, and ethyl acetate.

2. The process for preparing nylon yarn with sustained-release antibacterial properties according to claim 1, characterized in that: In step 1, the molar ratio of 1-(4-isothiocyanatobenzyl)ethylenediamine-N,N,N',N'-tetraacetic acid to copper salt is 1:(1.1-1.2), the amount of phosphate buffer used is 800-1000 times the mass of 1-(4-isothiocyanatobenzyl)ethylenediamine-N,N,N',N'-tetraacetic acid, and the reaction conditions are stirring at room temperature for 30-60 minutes.

3. The process for preparing nylon yarn with sustained-release antibacterial properties according to claim 1, characterized in that: In step 2, the mass ratio of nylon 66 chips, mixed solvent, and chelated copper is (15-20): (400-600): (0.6-0.8), and the reaction conditions are 70-90°C for 6-8 hours. The mixed solvent is prepared by mixing benzene, m-cresol, xylene, and ethylene glycol ethyl ether. The mass ratio of benzene, m-cresol, xylene, and ethylene glycol ethyl ether is 30:25:25:

20.

4. The process for preparing nylon yarn with sustained-release antibacterial properties according to claim 1, characterized in that: In step three, the mass ratio of modified nylon 66 to the mixed solvent is (10-20):100; the electrospinning process conditions include: the electrospinning voltage is 12-18 kV, the height from the spinneret to the bath surface is 5-10 cm, and the winding speed is 5-7 m / min; the stretching and shaping process conditions include: the stretching temperature is 100-120°C and the stretching ratio is 1-3 times.

5. The process for preparing nylon yarn with sustained-release antibacterial properties according to claim 1, characterized in that: In the step 4, the bath ratio of the nylon yarn to the antibacterial finishing liquid is 1:(20-30), and the reaction conditions are 80-90° C. for 1.5-2.5 hours.

6. The process for preparing nylon yarn with sustained-release antibacterial properties according to claim 1, characterized in that: In the fourth step, when preparing the antibacterial finishing liquid, the mass ratio of the slow-release antibacterial agent, the initiator, and ethyl acetate is (5-10): (0.05-0.1): (150-250); the initiator includes benzoyl peroxide; the slow-release antibacterial agent is prepared by the following steps: S1. Dispersing mesoporous silica molecular sieve in hydrochloric acid, stirring, filtering, washing, and drying after the stirring is completed to obtain activated mesoporous silica molecular sieve; adding the activated mesoporous silica molecular sieve to toluene, ultrasonically dispersing, adding γ-methacryloxypropyltrimethoxysilane, reacting, filtering, washing, and drying after the reaction is completed to obtain olefinated mesoporous silica molecular sieve; S2, add olefinic mesoporous silica molecular sieve into ethanol, after ultrasonic dispersion, add silver nitrate, stir, after stirring, filter, dry, and obtain loaded Ag + Alkenylated mesoporous silica molecular sieves; S3, load Ag + The olefinated mesoporous silica molecular sieve is added to ethanol, an ascorbic acid aqueous solution is added dropwise, and the mixture is stirred. After the stirring is completed, an aqueous sodium citrate solution is added and the stirring is continued. After the stirring is completed, the mixture is filtered, washed, and dried to obtain a sustained-release antibacterial agent.

7. The process for preparing nylon yarn with sustained-release antibacterial properties according to claim 6, characterized in that: In the S1, the mass ratio of the mesoporous silica molecular sieve to the hydrochloric acid is 1:(12-18), and the stirring condition is stirring at room temperature for 1.5-2.5 hours.

8. The process for preparing nylon yarn with sustained-release antibacterial properties according to claim 6, characterized in that: In the S2, the mass ratio of olefinated mesoporous silica molecular sieve, ethanol and silver nitrate is 60:(180-240):(6.8-8), and the stirring condition is to stir in a sealed manner at room temperature in the dark for 3-5 hours.

9. The process for preparing nylon yarn with sustained-release antibacterial properties according to claim 6, characterized in that: In S3: Load Ag + The mass ratio of the olefinated mesoporous silica molecular sieve, ethanol, ascorbic acid aqueous solution, and sodium citrate aqueous solution is 65: (200-300): (20-25): (15-20), and the stirring conditions are: stirring in a sealed container in the dark at a temperature of 35-45°C for 20-40 minutes, and the stirring conditions are continued: stirring in a sealed container in the dark at a temperature of 35-45°C for 20-40 minutes.

10. A nylon yarn with sustained-release antibacterial properties prepared by the process for preparing nylon yarn with sustained-release antibacterial properties according to any one of claims 1 to 9.

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