CN114875521B - Preparation method of efficient antibacterial and antiviral fiber - Google Patents

Abstract

The invention relates to a preparation method of an efficient antibacterial and antiviral fiber, in particular to a preparation method of an antibacterial and antiviral polyamide 6 composite fiber prepared by loading nano Cu with TiO ₂. The invention is characterized in that nano simple substance Cu is generated on the surface of TiO ₂ by an in-situ reduction method, then TiO ₂ carboxylic acid which is used for generating nano simple substance Cu on the surface is modified, polyamide 6 is introduced by in-situ polymerization to obtain the high-efficiency antibacterial and antiviral polyamide 6, and the antibacterial and antiviral polyamide 6 composite fiber is obtained by taking the antibacterial and antiviral polyamide 6 as a skin layer and taking the conventional polyamide 6 as a core layer and carrying out composite spinning. The polyamide 6 fiber prepared by the invention does not harm the environment in the use process, and has the characteristics of high efficiency, durability, antibiosis and antivirus.

Description

A method for preparing highly effective antibacterial and antiviral fiber

Technical Field

The invention belongs to the field of antibacterial and antiviral fiber synthesis, and relates to a method for preparing antibacterial and antiviral polyamide 6 fiber, and in particular to a method for preparing antibacterial and antiviral polyamide 6 composite fiber with high mechanical properties by loading nano-copper with _TiO2 .

Background technique

Polyamide 6 (PA6) is a thermoplastic material that is usually white and translucent. It has strong crystallinity. The amide bonds on the main chain of the molecule enable hydrogen bonds to form between molecules. The intermolecular forces are strong. PA6 has high mechanical strength, wear resistance and corrosion resistance. PA6 and its fibers are widely used in textiles, industrial yarns and packaging industries. The health risks caused by pathogenic bacteria have brought severe tests to people who are caught off guard. If the antibacterial and antiviral functions of PA6 can be improved, the comprehensive performance of PA6 can be further improved, and it can be used in more scenarios that require antibacterial and anti-disease.

The antibacterial modification of PA6 is mainly achieved by adding antibacterial agents, including fabric finishing and melt-blending extrusion. Fabric finishing refers to the method of antibacterial modification by attaching antibacterial agents to formed fibers, including methods such as impregnation, coating, and spraying antibacterial agents. The fabric finishing method is simple, with less loss and less impact from other fiber forming links, but the fiber has poor washability and is not environmentally friendly. Blending extrusion utilizes the shear effect of the screw to disperse the antibacterial additives into PA6, and then obtains PA6 antibacterial fibers through melt spinning. Blending extrusion can intermittently produce masterbatches and continuously adjust the amount of additives for differentiated production. However, since it is difficult to evenly disperse the antibacterial agent by screw extrusion alone, it is necessary to add a dispersant to avoid the aggregation of the additives, resulting in poor spinnability and a significant decrease in the mechanical properties of the fiber.

Antimicrobial agents are mainly divided into two categories: organic and inorganic. Organic antimicrobial agents mainly work by affecting the activity of biological proteins. Organic antimicrobial agents are widely available, highly efficient, low-cost, and simple to process, but they are highly toxic, have poor durability, and can also cause microorganisms to develop drug resistance. Inorganic antimicrobial agents are mainly divided into metal ion antimicrobial agents and photocatalytic antimicrobial agents. Metal ion antimicrobial agents kill bacteria by dissolving heavy metal ions to destroy cell metabolism, but heavy metal ions can become toxic to the human body after long-term dissolution and accumulation. Photocatalytic antimicrobial agents produce hydroxyl radicals and peroxyl radicals under light conditions. Both radicals have strong oxidative activity and will combine with organic matter in the microorganism to kill bacteria.

Nano copper is a non-dissolving antibacterial agent. Compared with general copper-based antibacterial agents, it has the characteristics of large specific surface area, non-toxicity and stability. Nano copper particles directly react with water and oxygen in the air to generate active oxygen free radicals to play an antibacterial and antiviral role. Patent CN202110324666.2 obtains a composite antibacterial material of nano copper microcapsules encapsulating graphene by mixing and hybridizing graphene, nano copper, microporous silica and nano microcapsules, and then melt-mixes the material with polypropylene chips and extrudes and granulates to obtain nano copper antibacterial and antiviral masterbatch.

Nano-copper is prone to agglomeration due to its size, and existing technologies have rarely used nano-copper in the antibacterial application of fibers. Although _TiO2 has good antibacterial properties, its antibacterial properties can only work under ultraviolet conditions, and its dispersibility in the polymer matrix is poor. Therefore, it is of great significance to develop high-efficiency antibacterial and antiviral fibers.

Summary of the invention

The purpose of the present invention is to provide a method for preparing highly effective antibacterial and antiviral fiber, and in particular to a method for preparing antibacterial and antiviral polyamide 6 fiber by loading nano copper on TiO _2. The present invention first generates nano-element copper (Cu-TiO ₂ ) with a size of 2-10 nm on the surface of TiO ₂ by an in-situ reduction method, then modifies the Cu loaded TiO ₂ with carboxylic acid to obtain carboxylic acid-modified Cu-TiO ₂ (CM-Cu-TiO ₂ ), in-situ introduces CM-Cu-TiO ₂ during the synthesis of polyamide 6 to obtain antibacterial and antiviral polyamide 6, and finally obtains antibacterial and antiviral polyamide 6 composite fiber by composite spinning with antibacterial and antiviral polyamide 6 as the skin layer and conventional polyamide 6 as the core layer.

The nano-simple copper obtained by the present invention has a size of 2-10nm, and the nano-simple copper of this size has higher catalytic antibacterial and antiviral activity, and the nano-copper can activate water and oxygen in the air to generate active oxygen free radicals (ROS), and these ROS (hydroxyl free radicals, superoxide free radicals and hydrogen peroxide) have strong oxidizing properties, which can directly or indirectly damage the structure and function of cells, causing cell membrane rupture and bacterial death. Further, the CM-Cu- _TiO2 obtained by carboxylic acid modification not only has good compatibility with polyamide 6, but can be evenly and stably dispersed in the polyamide 6 melt in the in-situ polymerization of polyamide monomers, avoiding the agglomeration problem of nano-scale Cu loaded _TiO2 , and the carboxyl group can be well complexed with the nano-copper to maintain the nano-copper of Cu- _TiO2 in a reduced state all the time, continuously release active oxygen free radicals to play an antibacterial and antiviral role, and the complexed carboxyl group can promote the nano-copper to generate active oxygen free radicals, further improving the antibacterial and antiviral effect. In addition, nano copper can make up for the shortcoming that titanium dioxide is difficult to play an antibacterial role without ultraviolet light irradiation, and play a synergistic and efficient antibacterial and antiviral role. The present invention adopts a skin-core structure for spinning, and the high-efficiency antibacterial and antiviral polyamide 6 component of the skin layer plays an antibacterial and antiviral role, and the conventional polyamide 6 component of the core layer plays a role in supporting mechanical properties. Therefore, the fiber obtained by the present invention has a high-efficiency and lasting antibacterial and antiviral effect, and has high mechanical properties, and can be used in fields with high requirements for the antibacterial and antiviral properties of fibers.

The present invention provides a method for preparing a highly effective antibacterial and antiviral fiber, and the specific steps are as follows:

(1) By mass, 2 to 5 parts of nano titanium dioxide are ultrasonically dispersed in 50 parts of deionized water under certain conditions to prepare a _TiO2 aqueous solution, and 0.2 to 1.0 parts of copper salt are dissolved in 50 parts of deionized water to prepare a copper ion aqueous solution. The _TiO2 aqueous solution and the copper ion aqueous solution are mixed in a flask, condensed and refluxed, and then 50 parts of a reducing agent aqueous solution are added dropwise to the flask while stirring, and stirred at 60 to 90°C for 3 to 24 hours to obtain a dark solution. The obtained product is separated by centrifugation from deionized water and anhydrous ethanol, and finally dried to obtain a nano _-TiO2- loaded nano-copper composite antibacterial agent. The size of the generated nano-element copper is 2-10nm;

(2) 1-3 parts of aliphatic dibasic acid, 15-20 parts of nano- _TiO2- loaded nano-copper composite antibacterial agent ( _TiO2 -Cu) and 0.5-2 parts of caprolactam are added to 100 parts of anhydrous ethanol, condensed and refluxed, and stirred for 0.5-5 hours to obtain carboxylic acid-modified nano _-TiO2- loaded nano-copper composite antibacterial agent slurry (CM- _TiO2 -Cu slurry), and then the modified CM- _TiO2 -Cu slurry is placed in a centrifuge tube and centrifuged, the supernatant is removed, and the precipitate is washed with ethanol and water for 3-5 times, and then dried to obtain carboxylic acid-modified CM- _TiO2 -Cu (CM- _TiO2 -Cu).

(3) By weight, 1-3 parts of CM-TiO ₂ -Cu, 100 parts of caprolactam and 2-5 parts of deionized water are added into a polymerization reactor, firstly ring-opening prepolymerization is carried out, then polycondensation is carried out, and finally strip casting, pelletizing and extraction are carried out to obtain composite antibacterial and antiviral polyamide 6 slices.

(4) High-efficiency antibacterial and antiviral polyamide 6 slices and conventional polyamide 6 slices are dried at 90-120° C. for 24-36 hours, and the antibacterial and antiviral polyamide 6 and conventional polyamide 6 are added into a composite spinning machine in a certain proportion for spinning, with the antibacterial and antiviral polyamide 6 as the skin layer and the conventional polyamide 6 as the core layer, to obtain high-efficiency antibacterial and antiviral polyamide 6 composite fibers.

In the method for preparing a highly effective antibacterial and antiviral fiber as described above, in step (1), the certain conditions for ultrasonic dispersion of _TiO2 under certain conditions refer to a time of 20 to 60 minutes and an ultrasonic frequency of 30 to 60 kHz;

In the method for preparing a highly effective antibacterial and antiviral fiber as described above, in step (1), the copper salt refers to one of copper chloride, copper sulfate, and copper nitrate;

In the method for preparing a highly effective antibacterial and antiviral fiber as described above, in step (1), the reducing agent aqueous solution refers to a 0.1-0.5 mol/L aqueous solution of citric acid, hydrazine hydrate, sodium borohydride, ascorbic acid, sodium hypophosphite, or tetrabutylammonium borohydride;

In the method for preparing a highly effective antibacterial and antiviral fiber as described above, in step (2), the aliphatic dibasic acid is one of adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid;

In the method for preparing a highly effective antibacterial and antiviral fiber as described above, in step (3), the reaction conditions for the ring-opening prepolymerization are a temperature of 200 to 260° C., a pressure of 0.1 to 1.0 MPa, and a time of 2 to 5 h;

In the method for preparing a highly effective antibacterial and antiviral fiber as described above, in step (3), the polycondensation reaction conditions are a temperature of 240 to 260° C., a pressure of -0.02 to -0.10 MPa, and a time of 2 to 5 h;

In the method for preparing a high-efficiency antibacterial and antiviral fiber as described above, in step (4), the antibacterial and antiviral polyamide 6 and conventional polyamide are in a certain ratio, which means the mass ratio is (1-3):2.

In the method for preparing a high-efficiency antibacterial and antiviral fiber as described above, in step (4), the breaking strength of the antibacterial and antiviral polyamide 6 composite fiber is 3.0-4.5 cN/dtex, the breaking elongation is 15-30%, and the antibacterial and antiviral effect on Staphylococcus aureus, Escherichia coli, Candida albicans, and influenza A (H1N1) virus is more than 99%. After the fiber is washed 50 times, the antibacterial and antiviral effect on Staphylococcus aureus, Escherichia coli, Candida albicans, and influenza A (H1N1) virus is still more than 97%, and the fiber has good water wash resistance and high-efficiency antibacterial and antiviral properties.

Beneficial effects of the present invention:

(1) Safety: The present invention is a non-dissolving antibacterial and antiviral auxiliary agent, which will not cause harm to the human body and the environment, and is safer and more environmentally friendly;

(2) Stability: The nano-copper of the present invention is always in a reduced state, continuously releasing peroxyl radicals, and has a lasting antibacterial and antiviral effect;

(3) Highly effective antibacterial effect: The nano-copper in the present invention can still exert antibacterial and antiviral effects even without ultraviolet irradiation, and can achieve higher antibacterial and antiviral effects when combined with _TiO2 ;

(4) High strength: The antibacterial and antiviral polyamide 6 composite fiber of the present invention has good spinnability and high mechanical properties.

Detailed ways

The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall within the scope limited by the appended claims of the application equally.

Example 1, a method for preparing a highly effective antibacterial and antiviral fiber, the specific steps are as follows:

(1) By mass, 2 parts of nano titanium dioxide were ultrasonically dispersed in 50 parts of deionized water at a frequency of 60kHz for 20 minutes to prepare a _TiO2 aqueous solution, and 0.2 parts of anhydrous copper sulfate were dissolved in 50 parts of deionized water to prepare a copper ion aqueous solution. The _TiO2 aqueous solution and the copper ion aqueous solution were mixed in a flask, condensed and refluxed at 80°C, and then 50 parts of 0.1 mol/L citric acid aqueous solution were added dropwise to the flask while stirring, and stirred at 60°C for 3 hours to obtain a dark solution. The obtained product was centrifuged by deionized water and anhydrous ethanol, and finally dried to obtain a nano _-TiO2- loaded nano-copper composite antibacterial agent ( _TiO2 -Cu).

(2) 1 part of adipic acid, 15 parts of _TiO2 -Cu and 0.5 parts of caprolactam were added to 100 parts of anhydrous ethanol, condensed and refluxed at 80°C, and stirred for 0.5 h to obtain a carboxylic acid-modified nano- _TiO2- loaded nano-copper composite antibacterial agent slurry (CM- _TiO2 -Cu slurry). The CM- _TiO2 -Cu slurry was then placed in a centrifuge tube and centrifuged. The supernatant was removed and the obtained precipitate was washed three times with ethanol and water, and dried to obtain carboxylic acid-modified _TiO2 -Cu (CM- _TiO2 -Cu).

(3) 1 part of CM-TiO ₂ -Cu, 100 parts of caprolactam and 2 parts of deionized water were added into a polymerization reactor, and ring-opening prepolymerization was first carried out at 200°C and 0.1 MPa for 2 h, and then polycondensation was carried out at 240°C and -0.02 MPa for 2 h. Finally, high-efficiency antibacterial and antiviral polyamide 6 chips were obtained through strip casting, pelletizing and extraction.

(4) The high-efficiency antibacterial and antiviral polyamide 6 slices and the conventional polyamide 6 slices were dried at 100°C for 24 hours, and the antibacterial and antiviral polyamide 6 and the conventional polyamide 6 were added into a composite spinning machine at a mass ratio of 1:2 for spinning, with the antibacterial and antiviral polyamide 6 as the skin layer and the conventional polyamide 6 as the core layer, to obtain a high-efficiency antibacterial and antiviral polyamide 6 composite fiber.

The high-efficiency antiviral polyamide 6 fiber prepared by the present invention has a breaking strength of 4.5 cN/dtex and a breaking elongation of 30%. The antibacterial and antiviral effects on Staphylococcus aureus, Escherichia coli, Candida albicans and influenza A (H1N1) virus reach 99.1%. After the fiber is washed 50 times, the antibacterial and antiviral effects on Staphylococcus aureus, Escherichia coli, Candida albicans and influenza A (H1N1) virus still reach more than 97%, and the fiber has good water wash resistance and high-efficiency antibacterial and antiviral properties.

Example 2, a method for preparing a highly effective antibacterial and antiviral fiber, the specific steps are as follows:

(1) By mass, 5 parts of nano titanium dioxide were ultrasonically dispersed in 50 parts of deionized water at a frequency of 30kHz for 60 minutes to prepare a _TiO2 aqueous solution, and 1 part of copper chloride was dissolved in 50 parts of deionized water to prepare a copper ion aqueous solution. The _TiO2 aqueous solution and the copper ion aqueous solution were mixed in a flask, condensed and refluxed at 80°C, and then 50 parts of 0.5 mol/L ascorbic acid aqueous solution were added dropwise to the flask while stirring, and stirred at 90°C for 24 hours to obtain a dark solution. The obtained product was centrifuged by deionized water and anhydrous ethanol, and finally dried to obtain a nano _-TiO2- loaded nano-copper composite antibacterial agent ( _TiO2 -Cu).

(2) 3 parts of suberic acid, 20 parts of _TiO2 -Cu and 2 parts of caprolactam were added to 100 parts of anhydrous ethanol, condensed and refluxed at 80°C, and stirred for 5 hours to obtain a carboxylic acid-modified nano _-TiO2- loaded nano-copper composite antibacterial agent slurry (CM- _TiO2 -Cu slurry). The CM- _TiO2 -Cu slurry was then placed in a centrifuge tube and centrifuged. The supernatant was removed and the obtained precipitate was washed with ethanol and water for 5 times, and then dried to obtain carboxylic acid-modified _TiO2 -Cu (CM- _TiO2 -Cu).

(3) 3 parts of CM-TiO ₂ -Cu, 100 parts of caprolactam and 5 parts of deionized water were added into a polymerization reactor, and ring-opening prepolymerization was first carried out at 260° C. and 1.0 MPa for 5 h, and then polycondensation was carried out at 260° C. and -0.10 MPa for 5 h. Finally, high-efficiency antibacterial and antiviral polyamide 6 chips were obtained through strip casting, pelletizing and extraction.

(4) High-efficiency antibacterial and antiviral polyamide 6 slices and conventional polyamide 6 slices were dried at 100°C for 36 hours, and the antibacterial and antiviral polyamide 6 was used as the skin layer and the conventional polyamide 6 was used as the core layer. The antibacterial and antiviral polyamide 6 and conventional polyamide 6 were added into a composite spinning machine at a mass ratio of 3:2 for spinning to obtain high-efficiency antibacterial and antiviral polyamide 6 composite fibers.

The high-efficiency antiviral polyamide 6 fiber prepared by the present invention has a breaking strength of 3.0 cN/dtex and a breaking elongation of 27%. The antibacterial and antiviral effects on Staphylococcus aureus, Escherichia coli, Candida albicans and influenza A (H1N1) virus reach 99.9%. After the fiber is washed 50 times, the antibacterial and antiviral effects on Staphylococcus aureus, Escherichia coli, Candida albicans and influenza A (H1N1) virus still reach more than 97%, and the fiber has good water wash resistance and high-efficiency antibacterial and antiviral properties.

Example 3, a method for preparing a highly effective antibacterial and antiviral fiber, the specific steps are as follows:

(1) By mass, 3 parts of nano titanium dioxide were ultrasonically dispersed in 50 parts of deionized water at a frequency of 40kHz for 40 minutes to prepare a _TiO2 aqueous solution, and 0.5 parts of copper chloride were dissolved in 50 parts of deionized water to prepare a copper ion aqueous solution. The _TiO2 aqueous solution and the copper ion aqueous solution were mixed in a flask, condensed and refluxed at 80°C, and then 50 parts of 0.3 mol/L ascorbic acid aqueous solution were added dropwise to the flask while stirring, and stirred at 70°C for 20 hours to obtain a dark solution. The obtained product was centrifuged by deionized water and anhydrous ethanol, and finally dried to obtain a nano _-TiO2- loaded nano-copper composite antibacterial agent ( _TiO2 -Cu).

(2) Add 2 parts of dodecanedioic acid, 15 parts of _TiO2 -Cu and 1 part of caprolactam to 100 parts of anhydrous ethanol, condense and reflux at 80°C, and stir for 2 hours to obtain a carboxylic acid-modified nano- _TiO2- loaded nano-copper composite antibacterial agent slurry (CM- _TiO2 -Cu slurry). Then, put the CM- _TiO2 -Cu slurry into a centrifuge tube and centrifuge it. After removing the supernatant, the precipitate obtained is washed with ethanol and water for 5 times, and dried to obtain carboxylic acid-modified _TiO2 -Cu (CM- _TiO2 -Cu).

(3) 2 parts of CM-TiO ₂ -Cu, 100 parts of caprolactam and 3 parts of deionized water were added to a polymerization reactor, and ring-opening prepolymerization was first carried out at 230°C and 0.6 MPa for 4 hours, and then polycondensation was carried out at 250°C and -0.05 MPa for 4 hours. Finally, high-efficiency antibacterial and antiviral polyamide 6 chips were obtained through strip casting, pelletizing and extraction.

(4) High-efficiency antibacterial and antiviral polyamide 6 slices and conventional polyamide 6 slices were dried at 110°C for 36 hours, and the antibacterial and antiviral polyamide 6 was used as the skin layer and the conventional polyamide 6 was used as the core layer. The antibacterial and antiviral polyamide 6 and the conventional polyamide were added into a composite spinning machine at a mass ratio of 1:1 for spinning to obtain high-efficiency antibacterial and antiviral polyamide 6 composite fibers.

The high-efficiency antiviral polyamide 6 fiber prepared by the present invention has a breaking strength of 4.0 cN/dtex and a breaking elongation of 15%. The antibacterial and antiviral effects on Staphylococcus aureus, Escherichia coli, Candida albicans and influenza A (H1N1) virus reach 99.5%. After the fiber is washed 50 times, the antibacterial and antiviral effects on Staphylococcus aureus, Escherichia coli, Candida albicans and influenza A (H1N1) virus still reach more than 97%, and the fiber has good water wash resistance and high-efficiency antibacterial and antiviral properties.

Example 4, a method for preparing a highly effective antibacterial and antiviral fiber, the specific steps are as follows:

(1) By mass, 4 parts of nano titanium dioxide were ultrasonically dispersed in 50 parts of deionized water at a frequency of 30kHz for 50 minutes to prepare a _TiO2 aqueous solution, and 0.7 parts of cupric chloride were dissolved in 50 parts of deionized water to prepare a copper ion aqueous solution. The _TiO2 aqueous solution and the copper ion aqueous solution were mixed in a flask, condensed and refluxed at 80°C, and then 50 parts of 0.4 mol/L ascorbic acid aqueous solution were added dropwise to the flask while stirring, and stirred at 80°C for 20 hours to obtain a dark solution. The obtained product was centrifuged by deionized water and anhydrous ethanol, and finally dried to obtain a nano _-TiO2- loaded nano-copper composite antibacterial agent ( _TiO2 -Cu).

(2) 3 parts of sebacic acid, 16 parts of _TiO2 -Cu and 2 parts of caprolactam were added to 100 parts of anhydrous ethanol, condensed and refluxed at 80°C, and stirred for 3 hours to obtain a carboxylic acid-modified nano _-TiO2- loaded nano-copper composite antibacterial agent slurry (CM- _TiO2 -Cu slurry). The CM- _TiO2 -Cu slurry was then placed in a centrifuge tube and centrifuged. The supernatant was removed and the precipitate was washed with ethanol and water for 5 times, and then dried to obtain carboxylic acid-modified _TiO2 -Cu (CM- _TiO2 -Cu).

(3) 3 parts of CM-TiO ₂ -Cu, 100 parts of caprolactam and 4 parts of deionized water were added into a polymerization reactor, and ring-opening prepolymerization was first carried out at 250° C. and 0.5 MPa for 4 h, and then polycondensation was carried out at 240° C. and -0.06 MPa for 3 h. Finally, high-efficiency antibacterial and antiviral polyamide 6 chips were obtained through strip casting, pelletizing and extraction.

(4) The high-efficiency antibacterial and antiviral polyamide 6 slices and the conventional polyamide 6 slices were dried at 120°C for 24 hours, and the antibacterial and antiviral polyamide 6 was used as the skin layer and the conventional polyamide 6 was used as the core layer. The antibacterial and antiviral polyamide 6 and the conventional polyamide were added into a composite spinning machine at a mass ratio of 1:2 for spinning to obtain a high-efficiency antibacterial and antiviral polyamide 6 composite fiber.

The high-efficiency antiviral polyamide 6 fiber prepared by the present invention has a breaking strength of 3.5 cN/dtex and a breaking elongation of 18%. The antibacterial and antiviral effects on Staphylococcus aureus, Escherichia coli, Candida albicans and influenza A (H1N1) virus reach 99.9%. After the fiber is washed 50 times, the antibacterial and antiviral effects on Staphylococcus aureus, Escherichia coli, Candida albicans and influenza A (H1N1) virus still reach more than 97%, and the fiber has good water wash resistance and high-efficiency antibacterial and antiviral properties.

Example 5, a method for preparing a highly effective antibacterial and antiviral fiber, the specific steps are as follows:

(1) By mass, 3 parts of nano titanium dioxide were ultrasonically dispersed in 50 parts of deionized water at a frequency of 50kHz for 30 minutes to prepare a _TiO2 aqueous solution, and 0.6 parts of copper chloride were dissolved in 50 parts of deionized water to prepare a copper ion aqueous solution. The _TiO2 aqueous solution and the copper ion aqueous solution were mixed in a flask, condensed and refluxed at 80°C, and then 50 parts of 0.3 mol/L ascorbic acid aqueous solution were added dropwise to the flask while stirring, and stirred at 80°C for 22 hours to obtain a dark solution. The obtained product was centrifuged by deionized water and anhydrous ethanol, and finally dried to obtain a nano _-TiO2- loaded nano-copper composite antibacterial agent ( _TiO2 -Cu).

(2) 3 parts of sebacic acid, 16 parts of _TiO2 -Cu and 0.5 parts of caprolactam were added to 100 parts of anhydrous ethanol, condensed and refluxed at 80°C, and stirred for 3 hours to obtain a carboxylic acid-modified nano _-TiO2- loaded nano-copper composite antibacterial agent slurry (CM- _TiO2 -Cu slurry). The CM- _TiO2 -Cu slurry was then placed in a centrifuge tube and centrifuged. The supernatant was removed and the obtained precipitate was washed with ethanol and water for 5 times, and then dried to obtain carboxylic acid-modified _TiO2 -Cu (CM- _TiO2 -Cu).

(3) 1 part of CM-TiO ₂ -Cu, 100 parts of caprolactam and 2 parts of deionized water were added into a polymerization reactor, and ring-opening prepolymerization was first carried out at 240°C and 0.8 MPa for 5 h, and then polycondensation was carried out at 250°C and -0.09 MPa for 2 h. Finally, high-efficiency antibacterial and antiviral polyamide 6 chips were obtained through strip casting, pelletizing and extraction.

(4) High-efficiency antibacterial and antiviral polyamide 6 slices and conventional polyamide 6 slices were dried at 90°C for 36 hours, and the antibacterial and antiviral polyamide 6 was used as the skin layer and the conventional polyamide 6 was used as the core layer. The antibacterial and antiviral polyamide 6 and the conventional polyamide were added into a composite spinning machine at a mass ratio of 1:1 for spinning to obtain high-efficiency antibacterial and antiviral polyamide 6 composite fibers.

The high-efficiency antiviral polyamide 6 fiber prepared by the present invention has a breaking strength of 4.5 cN/dtex and a breaking elongation of 18%. The antibacterial and antiviral effects on Staphylococcus aureus, Escherichia coli, Candida albicans and influenza A (H1N1) virus reach 99.2%. After the fiber is washed 50 times, the antibacterial and antiviral effects on Staphylococcus aureus, Escherichia coli, Candida albicans and influenza A (H1N1) virus still reach more than 97%, and the fiber has good water wash resistance and high-efficiency antibacterial and antiviral properties.

Claims (6)

1. A method for preparing a highly effective antibacterial and antiviral fiber, characterized in that the method comprises the following steps: (1) By weight, 2-5 parts of _TiO2 are ultrasonically dispersed in 50 parts of deionized water under certain conditions to prepare a _TiO2 aqueous solution, and 0.2-1.0 parts of copper salt are dissolved in 50 parts of deionized water to prepare a copper ion aqueous solution; the _TiO2 aqueous solution and the copper ion aqueous solution are mixed in a flask, condensed and refluxed after mixing, and then 50 parts of a reducing agent aqueous solution are dropwise added to the flask while stirring, and stirred at 60-90°C for 3-24 hours to obtain a dark solution; the obtained product is centrifuged from deionized water and anhydrous ethanol, and finally dried to obtain Cu- _TiO2 , wherein the Cu- _TiO2 is a _TiO2 high-efficiency antibacterial agent with nano-element copper generated on the surface, and the size of the generated nano-element copper is 2-10nm; (2) Add 1-3 parts of aliphatic dibasic acid, 15-20 parts of Cu-TiO ₂ and 0.5-2 parts of caprolactam to 100 parts of anhydrous ethanol, condense and reflux, and stir for 0.5-5 hours to obtain carboxylic acid-modified Cu-TiO ₂ slurry, then put the CM-Cu-TiO ₂ slurry into a centrifuge tube for centrifugation, remove the supernatant to obtain a precipitate, wash it with ethanol and water for 3-5 times, and dry it to obtain carboxylic acid-modified Cu-TiO ₂ ; (3) adding 1-3 parts of carboxylic acid-modified Cu-TiO ₂ , 100 parts of caprolactam, and 2-5 parts of deionized water into a polymerization reactor, firstly ring-opening prepolymerization, then polycondensation, and finally strip casting, pelletizing, and extraction to obtain highly effective antibacterial and antiviral polyamide 6 chips; (4) High-efficiency antibacterial and antiviral polyamide 6 slices and conventional polyamide 6 slices are dried at 90-120°C for 24-36 hours, and the antibacterial and antiviral polyamide 6 and conventional polyamide 6 are added into a composite spinning machine in proportion for spinning, with the antibacterial and antiviral polyamide 6 as the skin layer and the conventional polyamide 6 as the core layer. The composite fibers are then stretched to obtain high-efficiency antibacterial and antiviral polyamide 6 composite fibers. 2. The method for preparing a high-efficiency antibacterial and antiviral fiber according to claim 1 is characterized in that, in step (1), the certain conditions for ultrasonic dispersion of _TiO2 under certain conditions refer to a time of 20 to 60 minutes and an ultrasonic frequency of 30 to 60 kHz; the copper salt refers to one of copper chloride, copper sulfate, and copper nitrate; the reducing agent aqueous solution refers to one of 0.1 to 0.5 mol/L citric acid, hydrazine hydrate, sodium borohydride, ascorbic acid, sodium hypophosphite, and tetrabutylammonium borohydride aqueous solution. 3. The method for preparing a high-efficiency antibacterial and antiviral fiber according to claim 1 is characterized in that in step (2), the aliphatic dibasic acid refers to one of adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid. 4. The method for preparing a high-efficiency antibacterial and antiviral fiber according to claim 1 is characterized in that in step (3), the reaction conditions of the ring-opening prepolymerization are a temperature of 200~260°C, a pressure of 0.1~1.0 MPa, and a time of 2~5 h; the reaction conditions of the condensation polymerization are a temperature of 240~260°C, a pressure of -0.02~-0.10 MPa, and a time of 2~5 h. 5. The method for preparing a high-efficiency antibacterial and antiviral fiber according to claim 1, characterized in that, in step (4), the mass ratio of antibacterial and antiviral polyamide 6 to conventional polyamide is (1~3):2. 6. The method for preparing a high-efficiency antibacterial and antiviral fiber according to claim 1 is characterized in that the antibacterial and antiviral polyamide 6 fiber has a breaking strength of 3.0-4.5 cN/dtex, an elongation at break of 15-30%, and an antibacterial and antiviral effect on Staphylococcus aureus, Escherichia coli, Candida albicans, and influenza A (H1N1) virus of more than 99%. After the fiber is washed 50 times, the antibacterial and antiviral effect on Staphylococcus aureus, Escherichia coli, Candida albicans, and influenza A (H1N1) virus is still more than 97%.