Preparation method of antibacterial black nylon 6 fiber containing Bi

Abstract

The application discloses a preparation method of Bi-containing nylon 6 antibacterial black fiber, and comprises the following steps: adding bismuth nitrate pentahydrate and ammonium metavanadate into a solvent, stirring to obtain a bismuth vanadate precursor solution; mixing the bismuth vanadate precursor solution, nylon 6 chip powder and nylon 6 chips, melt plasticizing, drawing, water tank cooling, cutting, vibration screening and vacuum constant temperature drying to obtain nylon 6 bismuth vanadate master batch; adding spinning grade nylon 6 chips into a main feeding position, adding carbon black powder and an additive into a side feeding position, melt plasticizing, drawing, water tank cooling, cutting, vibration screening and vacuum constant temperature drying to obtain nylon 6 black master batch; mixing the nylon 6 bismuth vanadate master batch, the nylon 6 black master batch and nylon 6 chips, and extruding to obtain the Bi-containing nylon 6 antibacterial black fiber; the application can generate hydroxyl radicals and superoxide radicals under photocatalysis to kill and inhibit the growth and reproduction of bacteria, and the application does not contain heavy metals, and has the characteristics of low cost, non-toxicity, simple operation and good antibacterial performance.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of chemical fibers, and particularly relates to a preparation method of Bi-containing nylon 6 antibacterial black fiber. BACKGROUND

[0002] In recent years, people's awareness of health and environmental protection has been increasing, and the technology of dope-dyed nylon 6 fiber has also been developed rapidly. In addition, people's functional requirements for clothing are also increasing, among which the antibacterial function has attracted more and more attention in the industry. At present, silver-based antibacterial agents are commonly used in antibacterial fibers. However, silver as a noble metal is not only expensive, but also its product safety has been controversial. Therefore, it has become a problem to be solved to explore a low-cost and safe antibacterial fiber.

[0003] In the research of antibacterial performance, in addition to metal ion antibacterial agents in inorganic antibacterial agents, various pollutants can also be decomposed and bacteria and viruses can be killed through photocatalytic technology to achieve the effect of antibacterial fiber. A Chinese patent with application number CN201711066288.2 discloses an antibacterial and deodorizing polyamide 6 fiber and a preparation method thereof, which is prepared from the following raw materials by weight: 0.90-1.50 parts of nano-surface coated antibacterial agent, 0.03-0.10 parts of dispersing agent, and 99.07-331.73 parts of polyamide 6 chips. The nano-surface coated antibacterial agent comprises a nano-surface coated antibacterial agent and a coating on the surface of the nano-surface coated antibacterial agent, the weight ratio of the coating to the nano-surface coated antibacterial agent is 2-5%, the nano-surface coated antibacterial agent is nano-zinc oxide or nano-titanium dioxide, and the coating is silicon dioxide or aluminum oxide. The antibacterial and deodorizing polyamide 6 fiber provided by the application has high-efficiency and long-lasting antibacterial and deodorizing functions, because the nano-zinc oxide or nano-titanium dioxide is a photocatalyst material and can realize the antibacterial and deodorizing functions through photocatalytic reaction under ultraviolet irradiation. However, the potential risks of heavy metals have not been solved in the application.

[0004] Bismuth vanadate has the characteristics of low cost, non-toxic and stable, and is an important low-carbon and environmentally friendly dye, but because the Bi salt is easy to hydrolyze, the stability of the bismuth vanadate precursor solution prepared is poor and it is difficult to store, the patent application No. CN202010146051.0 discloses a preparation method of nano copper / bismuth vanadate composite antibacterial agent, adopts bismuth vanadate as a photocatalyst, and prepares a composite antibacterial agent by loading nano copper on the bismuth vanadate photocatalyst, including the following steps: (1) accurately weighing bismuth nitrate, ammonium metavanadate and ammonia water, dissolving bismuth nitrate and ammonium metavanadate into deionized water and ammonia water solution respectively, then mixing them, and obtaining bismuth vanadate after hydrothermal treatment; (2) after ultrasonic dispersion of bismuth vanadate in deionized water, adding copper chloride, and reducing it with sodium borohydride, the obtained solid after centrifugation, drying and grinding is the nano copper / bismuth vanadate composite antibacterial agent, the invention prepares a composite antibacterial agent by loading nano copper on the bismuth vanadate photocatalyst, still contains heavy metals, and the use field is not clear, and the antibacterial performance for nylon fiber cannot be verified. SUMMARY

[0005] In order to solve the above problems, the application provides a preparation method of Bi-containing nylon 6 antibacterial black fiber.

[0006] The object of the application can be achieved by the following technical solutions:

[0007] A preparation method of Bi-containing nylon 6 antibacterial black fiber, comprising the following steps:

[0008] S1: adding bismuth nitrate pentahydrate and ammonium metavanadate into an organic solvent in sequence, stirring at room temperature for 8-10 min, and obtaining a bismuth vanadate precursor solution;

[0009] S2: uniformly mixing the bismuth vanadate precursor solution obtained in step S1, nylon 6 chip powder and nylon 6 chip in advance, and adding them to the main feeding position of a double screw extruder, melt plasticizing the above raw materials, and obtaining nylon 6 bismuth vanadate master batch through drawing, water tank cooling, particle cutting vibration screening and vacuum constant temperature drying, for standby use;

[0010] S3: adding spinning grade nylon 6 chip to the main feeding position of a double screw extruder, adding carbon black powder and additives to the side feeding position, melt plasticizing the above raw materials, and obtaining nylon 6 black master batch through drawing, water tank cooling, particle cutting vibration screening and vacuum constant temperature drying, for standby use;

[0011] S4: preparing the Bi-containing nylon 6 antibacterial black fiber by double-component simultaneous melt extrusion of the nylon 6 bismuth vanadate master batch prepared in step S2, the nylon 6 black master batch prepared in step S3 and nylon 6 chip through a master batch machine.

[0012] Further, in step S1, the organic solvent is one of ethylene glycol, acetic acid and acetylacetone.

[0013] Further, in step S1, the molar ratio of the bismuth nitrate pentahydrate and the ammonium metavanadate is 1:1.

[0014] Further, in step S1, the concentration of the bismuth vanadate precursor solution is 0.08-0.12 mol / L.

[0015] Further, in step S2, the weight ratio of the bismuth vanadate precursor solution, the nylon 6 chip powder and the nylon 6 chip is 1:2:17.

[0016] Further, in step S2, the temperature of the first section, the second section of the twin-screw extruder is 225 DEG C, the temperature of the third section, the fourth section and the fifth section is 230 DEG C, the temperature of the sixth section is 225-230 DEG C, the temperature of the seventh section is 210-215 DEG C, the temperature of the eighth section is 200-205 DEG C, the temperature of the ninth section is 195-205 DEG C, the temperature of the tenth section is 185-195 DEG C, the temperature of the eleventh section is 180-190 DEG C, and the temperature of the head section is 230-240 DEG C.

[0017] Further, in step S3, the weight ratio of the spinning grade nylon 6 chip, the carbon black powder and the auxiliary agent is 67:30:3.

[0018] Further, in step S4, the proportion of the nylon 6 bismuth vanadate master batch in the Bi-containing nylon 6 antibacterial black fiber is 5-10%, and the proportion of the nylon 6 black master batch is 5%.

[0019] Compared with the prior art, the present application has the following beneficial effects:

[0020] 1. The preparation method of the Bi-containing nylon 6 antibacterial black fiber provided by the present application uses a modified bismuth vanadate precursor solution to prepare a nylon 6 bismuth vanadate master batch, and then uses the nylon 6 bismuth vanadate master batch and a nylon 6 black master batch in a two-component manner to prepare a Bi-containing nylon 6 antibacterial black fiber.

[0021] 2、The application selects ethylene glycol or acetic acid or acetylacetone as an organic solvent, and the BiVO4 precursor solution is prepared by taking the organic solvent as a stabilizer, Bi ions form a complex with the organic solvent, are in a stable state in the solution, do not hydrolyze, are monoclinic BiVO4, have high purity, good crystallinity and good stability, are applied in the nylon 6 antibacterial black fiber, have washing resistance and durability, and can exhibit stable antibacterial performance. BRIEF DESCRIPTION OF DRAWINGS

[0022] Figure 1 A Raman spectrum of the BiVO4 solution in the preparation method of the Bi-containing nylon 6 antibacterial black fiber provided by the application. DETAILED DESCRIPTION

[0023] The application will be further described below in combination with preferred embodiments and with reference to the accompanying drawings. Figure 1 The end points and any values in the range disclosed in the application are not limited to the exact range or value, and the range or value should be understood as containing values close to the range or value; for the numerical range, the end point values of each range, the end point values of each range and the individual point values can be combined with each other to obtain one or more new numerical ranges, and the numerical ranges should be regarded as being specifically disclosed herein; the materials, reagents and the like used in the following examples are commercially available unless otherwise specified; the experimental methods in the following examples are conventional methods unless otherwise specified.

[0024] Example 1

[0025] The embodiment provides a preparation method of a Bi-containing nylon 6 antibacterial black fiber, which comprises the following steps.

[0026] S1: five bismuth nitrate hydrates and ammonium metavanadate are sequentially added to ethylene glycol, and stirring is performed at room temperature for 8 min to obtain a bismuth vanadate precursor solution; the molar ratio of the five bismuth nitrate hydrates and the ammonium metavanadate is 1:1, and the concentration of the bismuth vanadate precursor solution is 0.08 mol / L;

[0027] S2: the bismuth vanadate precursor solution obtained in step S1, nylon 6 chip powder and nylon 6 chips are uniformly premixed and added to a main feeding position of a double-screw extruder, the above raw materials are melt plasticized, and after drawing, water tank cooling, granulation vibration screening and vacuum constant-temperature drying, a nylon 6 bismuth vanadate master batch is prepared and reserved; the weight ratio of the bismuth vanadate precursor solution, the nylon 6 chip powder and the nylon 6 chips is 1:2:13;

[0028] S3: the spinning grade nylon 6 chip is added to the main feeding position of the twin-screw extruder, the carbon black powder and the additive are added to the side feeding position, the above raw materials are melt plasticized, and the nylon 6 black master batch is prepared through drawing, water tank cooling, granulation vibration screening and vacuum constant temperature drying, which is ready for use; the weight ratio of the spinning grade nylon 6 chip, the carbon black powder and the additive is 67:30:3;

[0029] S4: the nylon 6 bismuth vanadate master batch prepared in step S2 and the nylon 6 black master batch prepared in step S3 are mixed with the nylon 6 chip at an addition ratio of 5%, and the Bi-containing nylon 6 antibacterial black fiber is prepared through the double-component simultaneous melt extrusion of the master batch machine.

[0030] In step S2 of the embodiment, the temperature of the first section, the second section, the third section, the fourth section and the fifth section of the twin-screw extruder is 225℃, the temperature of the sixth section is 228℃, the temperature of the seventh section is 212℃, the temperature of the eighth section is 203℃, the temperature of the ninth section is 200℃, the temperature of the tenth section is 190℃, the temperature of the eleventh section is 185℃, and the temperature of the die head section is 235℃.

[0031] Example 2

[0032] The embodiment provides a preparation method of a Bi-containing nylon 6 antibacterial black fiber, which comprises the following steps:

[0033] S1: bismuth nitrate pentahydrate and ammonium metavanadate are sequentially added to acetic acid, and stirred at room temperature for 9 min to obtain a bismuth vanadate precursor solution; the molar ratio of the bismuth nitrate pentahydrate and the ammonium metavanadate is 1:1, and the concentration of the bismuth vanadate precursor solution is 0.1 mol / L;

[0034] S2: the bismuth vanadate precursor solution obtained in step S1, nylon 6 chip powder and nylon 6 chip are uniformly mixed in advance and added to the main feeding position of the twin-screw extruder, the above raw materials are melt plasticized, and the nylon 6 bismuth vanadate master batch is prepared through drawing, water tank cooling, granulation vibration screening and vacuum constant temperature drying, which is ready for use; the weight ratio of the bismuth vanadate precursor solution, the nylon 6 chip powder and the nylon 6 chip is 1:2:17;

[0035] S3: the spinning grade nylon 6 chip is added to the main feeding position of the twin-screw extruder, the carbon black powder and the additive are added to the side feeding position, the above raw materials are melt plasticized, and the nylon 6 black master batch is prepared through drawing, water tank cooling, granulation vibration screening and vacuum constant temperature drying, which is ready for use; the weight ratio of the spinning grade nylon 6 chip, the carbon black powder and the additive is 67:30:3;

[0036] S4: The bismuth vanadate nylon 6 master batch prepared in step S2 and the black nylon 6 master batch prepared in step S3 are mixed with nylon 6 chips at an addition ratio of 8% and 5% respectively, and a double-component simultaneous melt extrusion is performed by a master batch machine to prepare the Bi-containing nylon 6 antibacterial black fiber.

[0037] In step S2 of the embodiment, the temperature of the first section and the second section of the twin-screw extruder is 225℃, the temperature of the third section, the fourth section and the fifth section is 230℃, the temperature of the sixth section is 225℃, the temperature of the seventh section is 210℃, the temperature of the eighth section is 200℃, the temperature of the ninth section is 195℃, the temperature of the tenth section is 185℃, the temperature of the eleventh section is 180℃, and the temperature of the die section is 230℃.

[0038] Example 3

[0039] The embodiment provides a preparation method of a Bi-containing nylon 6 antibacterial black fiber, comprising the following steps:

[0040] S1: Bismuth nitrate pentahydrate and ammonium metavanadate are sequentially added to acetylacetone, and stirred at room temperature for 10 min to obtain a bismuth vanadate precursor solution; the molar ratio of the bismuth nitrate pentahydrate and the ammonium metavanadate is 1:1, and the concentration of the bismuth vanadate precursor solution is 0.12 mol / L;

[0041] S2: The bismuth vanadate precursor solution obtained in step S1, nylon 6 chip powder and nylon 6 chips are uniformly mixed in advance and added to the main feeding position of a twin-screw extruder, the above-mentioned raw materials are melt-plasticized, and then drawn, cooled in a water tank, screened by a granulator vibrating screen, and dried at a constant temperature in a vacuum to prepare a bismuth vanadate nylon 6 master batch for standby use; the weight ratio of the bismuth vanadate precursor solution, the nylon 6 chip powder and the nylon 6 chips is 1:2:21;

[0042] S3: Spinning-grade nylon 6 chips are added to the main feeding position of a twin-screw extruder, and carbon black powder and an additive are added to the side feeding position, the above-mentioned raw materials are melt-plasticized, and then drawn, cooled in a water tank, screened by a granulator vibrating screen, and dried at a constant temperature in a vacuum to prepare a black nylon 6 master batch for standby use; the weight ratio of the spinning-grade nylon 6 chips, the carbon black powder and the additive is 67:30:3;

[0043] S4: The bismuth vanadate nylon 6 master batch prepared in step S2 and the black nylon 6 master batch prepared in step S3 are mixed with nylon 6 chips at an addition ratio of 10% and 5% respectively, and a double-component simultaneous melt extrusion is performed by a master batch machine to prepare the Bi-containing nylon 6 antibacterial black fiber.

[0044] In step S2 of the embodiment, the first section, the second section of the twin-screw extruder have a temperature of 225℃, the third section, the fourth section, the fifth section have a temperature of 230℃, the sixth section has a temperature of 230℃, the seventh section has a temperature of 215℃, the eighth section has a temperature of 205℃, the ninth section has a temperature of 205℃, the tenth section has a temperature of 195℃, the eleventh section has a temperature of 190℃, and the head section has a temperature of 240℃.

[0045] Comparative Example 1

[0046] The difference between the embodiment 1 and the comparative example 1 is that:

[0047] The nylon 6 antibacterial black fiber of the comparative example does not contain the nylon 6 bismuth vanadate master batch; the comparative example provides a preparation method of a nylon 6 antibacterial black fiber, comprising the following steps:

[0048] S1: spin the nylon 6 chip into the main feeding position of the twin-screw extruder, add carbon black powder and auxiliary agent to the side feeding position, melt and plasticize the above-mentioned raw materials, pass through the draw bar, water tank cooling, cutting vibration screen selection, vacuum constant temperature drying, and prepare the nylon 6 black master batch for standby; the weight ratio of the spinny nylon 6 chip, carbon black powder and auxiliary agent is 67:30:3;

[0049] S2: use the nylon 6 black master batch prepared in step S1 to spin at an addition ratio of 5% to prepare the nylon 6 antibacterial black fiber.

[0050] Comparative Example 2

[0051] The difference between the embodiment 1 and the comparative example 2 is that:

[0052] In the preparation method provided by the comparative example, the organic solvent used in step S1 is ethanol.

[0053] Evaluation of implementation effect

[0054] The following will further illustrate the excellent effect achieved by the present application through specific tests on the nylon 6 antibacterial black fiber prepared by the embodiment 1-3 and the comparative example 1-2:

[0055] The Raman spectrum of the bismuth vanadate precursor solution prepared in the embodiment 1 is shown in the following figure: Figure 1 As can be seen from the figure, the Raman peak is mainly at 124cm -1 , 209cm -1 , 324cm -1 1, 365cm -1 1 and 824cm -1 , which corresponds to the monoclinic BiVO4, indicating that the monoclinic BiVO4 is successfully prepared in the embodiment 1, wherein 124cm -1 and 209cm -1characteristic peaks at 324 cm -1 and 365 cm -1 characteristic peaks at 824 cm -1 The peak with the highest intensity at 824 cm

[0056] The content of the nylon 6 black master batch prepared from examples 1-3 and comparative examples 1-2 and the content of the nylon 6 bismuth vanadate master batch were detected, and the results are as follows:

[0057] Table 1 Master batch content detection table

[0058]

[0059] The effective content of the nylon 6 black master batch of examples 1-3 and comparative example 1 deviates by ±0.2%, which is within the range of standard deviation ±0.5%, and the content is basically uniform. In the Bi content detection of the nylon 6 bismuth vanadate master batch in examples 1-3 and comparative examples, it is found that the Bi content of examples 1-3 is within ±0.002% of the theoretical value, which is more uniform, while comparative example 2 using ethanol appears to be layered in solution, and there is a large deviation in the detection of the content of 5 groups of nylon 6 bismuth vanadate master batch, which deviates far from the theoretical value. Therefore, from the uniformity of the bismuth vanadate solution state and the corresponding master batch, the bismuth vanadate precursor solution prepared by using ethylene glycol or acetic acid or acetylacetone as a solvent and using the organic solvent as a stabilizer is more stable, which is conducive to the application in nylon 6 master batch and subsequent yarn preparation.

[0060] Antibacterial performance test: according to the relevant provisions of GB / T 20944.3-2008, the antibacterial performance of the nylon 6 antibacterial black fiber prepared from examples 1-3 and comparative examples 1-2 was detected by "textiles-antibacterial performance evaluation-oscillation method (according to the household double barrel washing machine washing method, washing 30 times, drying)", and the detection results are shown in the following table:

[0061] Table 2 Antibacterial performance test results

[0062]

[0063] As can be seen from the above table, the Candida albicans inhibition rate of Comparative Example 1 only reaches the basic value (70%) of the national standard, and the Candida albicans antibacterial performance of Examples 1-3 is more excellent with the increase of bismuth content in the yarn, which is far better than that of Comparative Example 1, indicating that the nylon 6 antibacterial black fiber prepared by the application can effectively improve the antibacterial effect on Candida albicans; in addition, the antibacterial rate of Escherichia coli in Examples 1-3 is improved by 6%-7% compared with Comparative Example 1, indicating that the nylon 6 antibacterial black fiber prepared by the application also has an inhibitory effect on Escherichia coli, and the Bi-containing nylon 6 antibacterial black fiber provided by the application has washing resistance and durability, and can exhibit stable antibacterial performance.

[0064] The above only describes the preferred embodiments of the present application, and it should be pointed out that, for those skilled in the art, without departing from the inventive concept, several modifications and improvements can be made, which are all within the protection scope of the present application.

Claims

1. A method for preparing Bi-containing nylon 6 antibacterial black fiber, characterized in that: The following steps are involved: S1: adding bismuth nitrate pentahydrate and ammonium metavanadate to an organic solvent in sequence, and stirring at room temperature for 8-10 minutes to obtain a bismuth vanadate precursor solution; S2: The bismuth vanadate precursor solution, nylon 6 chip powder, and nylon 6 chips obtained in step S1 are pre-mixed and added to the main feeding position of a twin-screw extruder, and the above raw materials are melted and plasticized, and then subjected to strand drawing, water tank cooling, pelletizing, vibration screening, and vacuum constant temperature drying to obtain nylon 6 bismuth vanadate masterbatch for later use; S3: Add spinning-grade nylon 6 chips to the main feed position of the twin-screw extruder, add carbon black powder and additives at the side feed position, melt and plasticize the above raw materials, and then undergo stretching, water tank cooling, pelletizing, vibration screening, and vacuum constant temperature drying to obtain nylon 6 black masterbatch for later use; S4: The nylon 6 bismuth vanadate masterbatch prepared in step S2, the nylon 6 black masterbatch prepared in step S3, and the nylon 6 chips are simultaneously melt-extruded through a masterbatch machine to prepare the Bi-containing nylon 6 antibacterial black fiber; In step S1, the organic solvent is one of ethylene glycol, acetic acid, and acetylacetone.

2. The method for preparing a Bi-containing nylon 6 antibacterial black fiber according to claim 1, characterized in that: In step S1, the molar ratio of the bismuth nitrate pentahydrate to ammonium metavanadate is 1:

1.

3. The method for preparing Bi-containing nylon 6 antibacterial black fiber according to claim 1, characterized in that: In step S1, the concentration of the bismuth vanadate precursor solution is 0.08-0.12 mol / L.

4. The method for preparing Bi-containing nylon 6 antibacterial black fiber according to claim 1, characterized in that: In step S2, the weight ratio of the bismuth vanadate precursor solution, nylon 6 chip powder, and nylon 6 chip is 1:2:

17.

5. The method for preparing Bi-containing nylon 6 antibacterial black fiber according to claim 1, characterized in that: In step S2, the temperatures of the first and second temperature zones of the twin-screw extruder are both 225°C, the temperatures of the third, fourth and fifth temperature zones are all 230°C, the temperature of the sixth temperature zone is 225-230°C, the temperature of the seventh temperature zone is 210-215°C, the temperature of the eighth temperature zone is 200-205°C, the temperature of the ninth temperature zone is 195-205°C, the temperature of the tenth temperature zone is 185-195°C, the temperature of the eleventh temperature zone is 180-190°C, and the temperature of the head temperature zone is 230-240°C.

6. The method for preparing Bi-containing nylon 6 antibacterial black fiber according to claim 1, characterized in that: In step S3, the weight ratio of the spinning-grade nylon 6 chips, carbon black powder, and additives is 67:30:

3.

7. The method for preparing Bi-containing nylon 6 antibacterial black fiber according to claim 1, characterized in that: In step S4, the proportion of the nylon 6 bismuth vanadate masterbatch in the Bi-containing nylon 6 antibacterial black fiber is 5-10%, and the proportion of the nylon 6 black masterbatch is 5%.

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