CN113789581A

CN113789581A - Preparation method of novel antibacterial fiber

Info

Publication number: CN113789581A
Application number: CN202111104446.5A
Authority: CN
Inventors: 杨家龙; 殷明; 陈晓苏
Original assignee: Dongbuwan Yangzhou Biological New Material Co ltd
Current assignee: Dongbuwan Yangzhou Biological New Material Co ltd
Priority date: 2021-09-18
Filing date: 2021-09-18
Publication date: 2021-12-14

Abstract

The invention discloses a preparation method of novel antibacterial fiber in the technical field of antibacterial fiber, which comprises the following steps: (1) dispersing ZnO in deionized water, then carrying out ultrasonic treatment for 30min-2h, and then adjusting the pH value to 8.5; then adding dopamine into the solution, and continuously stirring for 4-12h at room temperature; finally, sequentially filtering, washing and drying to obtain a product PDA-ZnO; (2) dispersing PDA-ZnO and hexadecyl trimethyl imidazole bromide in deionized water, stirring at 70-90 ℃ for 12-24 h, and sequentially washing, centrifuging and drying the product to obtain QP-ZnO; (3) uniformly mixing QP-ZnO, PP, an antioxidant 1010, a heat stabilizer 168 and silicone powder, and performing extrusion molding to obtain antibacterial PP resin; (4) and carrying out melt spinning on the antibacterial PP resin to obtain the antibacterial fiber A. The method utilizes dopamine to modify the surface of ZnO, is beneficial to loading quaternary ammonium salt on the surface of ZnO, improves the thermal stability of the quaternary ammonium salt, and is more beneficial to the smooth spinning process.

Description

Preparation method of novel antibacterial fiber

Technical Field

The invention relates to the technical field of antibacterial fibers, and particularly relates to a preparation method of a novel antibacterial fiber.

Background

In daily life, people use a large number of fiber products, such as clothes, masks, personal care products and the like. After long-term use, the fiber products can breed a large number of bacteria, such as escherichia coli, penicillium, staphylococcus aureus and the like, and once the harmful bacteria enter the human body, the harmful bacteria can bring certain harm. With the increasing health consciousness of people, higher requirements are provided for the safety performance of fiber fabrics, certain antibacterial performance is required while no toxicity and no harm are required, and antibacterial fiber products with antibacterial functions gradually appear in the market according to the requirements of users.

Currently, most antimicrobial fibers require the surface of the fiber to be coated or smeared with an antimicrobial solution to impart antimicrobial properties. However, the antibacterial coating coated on the surface has poor elution resistance, and the antibacterial performance of the antibacterial coating is remarkably reduced after washing for a plurality of times; the eluted antibacterial agent easily enters water to cause pollution. In addition, the main component of the existing antibacterial agent is silver ions, and the silver-containing inorganic antibacterial agent has the advantage of high antibacterial activity, is effectively applied to many fields, and has remarkable effect. However, the cost cannot be reduced because the used active ingredient is silver, which hinders the large-scale application of the antibacterial agent; the product added with the silver-containing antibacterial agent under the conditions of illumination and the like is discolored due to silver, and the antibacterial product loses commercial value; in the processing process of the product, if the temperature is too high, the effective components of the silver-based antibacterial agent are changed into silver oxide, and the antibacterial effect is greatly weakened. Moreover, most of the silver-based antibacterial agents have certain toxicity (the national clear requirement on the upper limit of the content of silver ions in drinking water), and the application range of the silver-based antibacterial agents is limited.

Disclosure of Invention

The invention aims to provide a preparation method of novel efficient and durable antibacterial fiber.

In order to realize the aim, the preparation method of the novel antibacterial fiber adopts the following technical scheme:

a preparation method of novel antibacterial fiber comprises the following steps:

(1) dispersing ZnO in deionized water, then carrying out ultrasonic treatment for 30min-2h, and then adjusting the pH value to 8.5; then adding dopamine into the solution, and continuously stirring for 4-12h at room temperature; finally, sequentially filtering, washing and drying to obtain a product PDA-ZnO;

(2) dispersing PDA-ZnO and hexadecyl trimethyl imidazole bromide in deionized water, stirring at 70-90 ℃ for 12-24 h, and sequentially washing, centrifuging and drying the product to obtain QP-ZnO;

(3) uniformly mixing QP-ZnO, PP, an antioxidant 1010, a heat stabilizer 168 and silicone powder, and performing extrusion molding to obtain antibacterial PP resin;

(4) and carrying out melt spinning on the antibacterial PP resin to obtain the antibacterial fiber A.

Preferably, the QP-ZnO, the antioxidant 1010, the heat stabilizer 168 and the silicone powder are calculated according to the following weight ratio: QP-ZnO 0.5-2 wt%, antioxidant 10100.1 wt%, heat stabilizer 1680.2 wt% and silicone powder 0.5 wt%.

Preferably, the pH adjustment in step (1) is performed using a Tris buffer solution.

Preferably, the washing in step (2) is performed by deionized water washing, and the drying in step (2) is performed by freeze drying.

Preferably, the washing in the step (3) adopts deionized water and ethanol, and the drying in the step (3) is carried out for 12-24 h at the temperature of 80-100 ℃.

Preferably, the extrusion molding in the step (4) adopts a double-screw extruder, the blending temperature is 200 ℃, and the screw rotating speed is 300 rpm.

Compared with the prior art, the invention has the beneficial effects that: the invention discloses a preparation method of an antibacterial fiber, which takes zinc oxide (ZnO) and quaternary ammonium salt as main antibacterial components and polypropylene (PP) as a matrix. The antibacterial agent is added into the fiber in a melt blending mode, so that the problem of elution is avoided, and the antibacterial property is durable. Meanwhile, the antibacterial system based on zinc and quaternary ammonium salt also solves the problems of toxicity and discoloration of the silver antibacterial agent. The dopamine is used for modifying the surface of ZnO, so that the loading of quaternary ammonium salt on the surface of ZnO is facilitated, the thermal stability of the quaternary ammonium salt is improved, and the smooth spinning process is facilitated.

Detailed Description

The present invention is further illustrated by the following detailed description, which is to be construed as merely illustrative and not limitative of the remainder of the disclosure, and modifications and variations such as those ordinarily skilled in the art are intended to be included within the scope of the present invention as defined in the appended claims.

Example 1:

1g of ZnO was dispersed in 500ml of deionized water and sonicated using a 200W probe for 30 min. The Tris buffer solution was then used to adjust the pH of the system to 8.5. 1.5g of dopamine was added to the above solution and stirring was continued at room temperature for 6 hours. And filtering the solution, washing with deionized water, and freeze-drying to obtain the product PDA-ZnO. 1g of PDA-ZnO and 1g of hexadecyl trimethyl imidazole bromide are dispersed in 200ml of deionized water, the mixture is stirred for 24 hours at 90 ℃, the product is washed by the deionized water and ethanol, and the centrifuged product is dried for 24 hours at 80 ℃ to obtain QP-ZnO. QP-ZnO 1g, PP 99g, antioxidant 1010 0.1g, heat stabilizer 168 0.2g and silicone powder 0.5g are uniformly mixed, and the antibacterial PP resin is prepared in a double-screw extruder (the blending temperature is 200 ℃, and the screw rotation speed is 300 rpm). The antibacterial PP resin was melt-spun to obtain an antibacterial fiber A having a diameter of about 15 μm.

Example 2:

2g of ZnO was dispersed in 500ml of deionized water and sonicated using a 200W probe for 30 min. The Tris buffer solution was then used to adjust the pH of the system to 8.5. 4g of dopamine were added to the above solution and stirring was continued at room temperature for 6 hours. And filtering the solution, washing with deionized water, and freeze-drying to obtain the product PDA-ZnO. Dispersing 2g of PDA-ZnO and 3g of hexadecyl trimethyl ammonium chloride in 500ml of deionized water, stirring at 90 ℃ for 12h, washing a product with the deionized water and ethanol, and drying a centrifuged product at 80 ℃ for 24h to obtain QP-ZnO. QP-ZnO 2g, PP 98g, antioxidant 1010 0.1g, heat stabilizer 168 0.2g and coupling agent KH570 g are uniformly mixed, and the antibacterial PP resin is prepared in a double-screw extruder (the blending temperature is 200 ℃, and the screw rotation speed is 300 rpm). The antibacterial PP resin is subjected to melt spinning, and the diameter of the obtained antibacterial fiber B is about 16 mu m.

Example 3:

2g of ZnO was dispersed in 500ml of deionized water and sonicated using a 200W probe for 30 min. The pH of the system was then adjusted to 5 using a buffer solution. 4g of KH550 as coupling agent were added to the above solution and stirring was continued at room temperature for 6 hours. And filtering the solution, washing with deionized water, and freeze-drying to obtain the KH-ZnO product. Dispersing 2g KH-ZnO and 3g hexadecyl trimethyl imidazole bromide in 500ml deionized water, stirring at 90 ℃ for 24h, washing the product with deionized water and ethanol, and drying the centrifuged product at 80 ℃ for 24h to obtain QK-ZnO. 2g of QK-ZnO is taken to be uniformly mixed with 99g of PP, 0.1g of antioxidant 1010, 0.2g of heat stabilizer 168 and 1.0g of coupling agent KH550, and the antibacterial PP resin is prepared in a double-screw extruder (the blending temperature is 200 ℃, and the screw rotation speed is 300 rpm). The antibacterial PP resin was melt-spun to obtain an antibacterial fiber C having a diameter of about 15 μm.

And (3) performance testing:

a control group was prepared, which included control 1 and control 2.

Control 1 was prepared as follows: 1g of hexadecyl trimethyl imidazole bromide, 1g of ZnO, 99g of PP, 0.1g of antioxidant 1010, 0.2g of heat stabilizer 168 and 0.5g of silicone powder are uniformly mixed, and the antibacterial PP resin is prepared in a double-screw extruder (the blending temperature is 200 ℃, and the screw rotation speed is 300 rpm). The above PP resin was melt-spun to obtain a fiber D.

Control 2 was prepared as follows: 1g of hexadecyl trimethyl imidazole bromide, 99g of PP, 0.1g of antioxidant 1010, 0.2g of heat stabilizer 168 and 0.5g of silicone powder are uniformly mixed, and the antibacterial PP resin is prepared in a double-screw extruder (the blending temperature is 200 ℃, and the screw rotation speed is 300 rpm). The above PP resin was melt-spun to obtain a fiber E.

The control group was tested for antibacterial activity with the finished products of examples 1-3 of the present invention according to ASTM E2149-:

TABLE 1 antibacterial test tables for control group and inventive examples 1-3

The detection result shows that the quaternary ammonium salt antibacterial agent is loaded in the ZnO and then added into the PP fiber, the antibacterial effect of the product is obvious, the spinning process is smooth, and the obvious phenomenon of spinneret orifice blockage is avoided, which indicates that the carrier loaded with the antibacterial agent is uniformly dispersed in the polymer. In contrast, sample D, E, because the quaternary ammonium salt has no carrier, the quaternary ammonium salt is decomposed violently by heat during melt processing and spinning, the product is severely yellow, and the decomposition product destroys the uniformity of the product, making the spinning process more difficult. In conclusion, the PP fiber with excellent antibacterial performance can be prepared by the formula provided by the invention.

Claims

1. A preparation method of novel antibacterial fiber is characterized by comprising the following steps: the method comprises the following steps:

2. The method for preparing the novel antibacterial fiber according to claim 1, characterized in that: the QP-ZnO, the antioxidant 1010, the heat stabilizer 168 and the silicone powder are calculated according to the weight ratio as follows: QP-ZnO 0.5-2 wt%, antioxidant 10100.1 wt%, heat stabilizer 1680.2 wt% and silicone powder 0.5 wt%.

3. The method for preparing the novel antibacterial fiber according to claim 1, characterized in that: and (2) regulating the pH value in the step (1) by adopting a Tris buffer solution.

4. The method for preparing the novel antibacterial fiber according to claim 1, characterized in that: and (3) washing in the step (2) by using deionized water, and drying in the step (2) by freeze drying.

5. The method for preparing the novel antibacterial fiber according to claim 1, characterized in that: washing in the step (3) by using deionized water and ethanol, and drying in the step (3) at the temperature of 80-100 ℃ for 12-24 h.

6. The method for preparing the novel antibacterial fiber according to claim 1, characterized in that: and (4) extruding and forming by using a double-screw extruder, wherein the blending temperature is 200 ℃, and the screw rotating speed is 300 rpm.