Preparation method of synergistic antibacterial and antiviral deodorant fiber

Abstract

The application relates to a preparation method of a synergistic antibacterial and antiviral deodorant fiber, wherein first, o-phenylenediamine and acid are used to prepare nanoscale nitrogen-doped carbon quantum dots through a one-step hydrothermal method; then, nanoscale elemental copper is generated on the surface of the nitrogen-doped carbon quantum dots through an in-situ reduction method; after being modified by a carboxylic acid, the polyester is introduced through in-situ polymerization to obtain high-efficiency antibacterial and antiviral deodorant polyester; and finally, the antibacterial and antiviral deodorant polyester fiber is obtained through melt spinning. The polyester fiber prepared by the application does not cause harm to the environment during use, and has the characteristics of high-efficiency and long-lasting antibacterial and antiviral properties and elimination of fabric smoke odor.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of antibacterial and antiviral fiber synthesis, in particular to a preparation method of synergistic antibacterial and antiviral deodorizing polyester fiber, and especially to a preparation method of synergistic antibacterial and antiviral deodorizing polyester fiber with high mechanical properties and good deodorizing function by nitrogen-doped carbon quantum dots and nano-copper. BACKGROUND

[0002] Pathogenic bacteria and viruses can survive on the surface of human fabric for up to 3-7 days, which seriously threatens people's health. Fiber is one of the main carriers for bacteria and viruses to parasitize and reproduce. If the fiber is endowed with antibacterial and antiviral functions, the comprehensive performance of the fiber product can be further improved, and it can be more applied to scenarios that require antibacterial and antiviral functions. In addition, there are many people who smoke in daily life, and the burning of cigarettes produces nicotine and smelly odors. This smelly odor is easily adsorbed on the surface of the fabric, affecting the wearing experience of the fabric. In recent years, antibacterial, antiviral and deodorizing composite functional textiles have gradually been favored by people, but the existing technology cannot achieve the multifunctional requirements of antibacterial, antiviral and deodorizing composite functional fibers and fabrics. Therefore, it is of great significance to study antibacterial, antiviral and deodorizing composite functional fibers.

[0003] Polyethylene terephthalate (PET) has good fiber-forming properties, mechanical properties, corrosion resistance, light transmission and electrical insulation, and is widely used in the field of fibers, such as textiles, films, industrial yarns, etc. The antibacterial modification of PET is mainly achieved by adding antibacterial agents, which are mainly divided into organic and inorganic antibacterial agents. Organic antibacterial agents have wide sources, low cost and simple process, but they are highly toxic, have poor durability, and can make microorganisms resistant. They mainly kill bacteria by entering the bacterial cell interior, destroying the protein structure and making it lose activity. Inorganic antibacterial agents are mainly divided into metal ion antibacterial agents and photocatalytic antibacterial agents. Metal ion antibacterial agents kill bacteria by dissolving heavy metal ions into the bacterial cell interior, combining with DNA and making genetic material unable to replicate, and destroying cell metabolism. However, the accumulation of heavy metal ions over a long period of time will be toxic to the human body. Photocatalytic antibacterial agents produce reactive oxygen species (ROS) such as hydroxyl radicals, singlet oxygen and peroxide radicals under light conditions. ROS has strong oxidative activity and can combine with organic matter in microorganisms to achieve antibacterial and antiviral effects.

[0004] Nano-copper is a non-dissolution type antibacterial agent. Compared with general copper-based antibacterial agents, it has the characteristics of large specific surface area, non-toxicity and stability, and can directly react with water and oxygen in the air to convert it into active oxygen radicals to kill bacteria and viruses. Nano-copper has good antibacterial performance, but it is easy to agglomerate during blending and processing, and the dispersion effect is not good. When applied to polyester fibers, there are problems of poor spinnability and poor antibacterial durability.

[0005] Nitrogen-doped carbon quantum dots (N-CQDs) are a new type of fluorescent carbon nanoparticles, which belong to photocatalytic antibacterial and antiviral agents and can only play a role under ultraviolet light. The N-CQDs have excellent optical properties, good biocompatibility and a wide range of raw material sources. Under photocatalysis, the N-CQDs can not only produce ROS to achieve antibacterial and antiviral effects, but also interact with nicotine in smoke to achieve the effect of degrading nicotine and eliminating smoke odor. However, the nanoscale size of the N-CQDs is prone to agglomeration when added to polymers, which affects the spinning performance of the polymers and the antibacterial, antiviral and deodorizing effects. SUMMARY

[0006] The purpose of the present application is to provide a preparation method of synergistic antibacterial, antiviral and deodorizing fibers to solve the problems of poor spinnability and poor antibacterial, antiviral and deodorizing effects when nanometer copper and nitrogen-doped carbon quantum dots are applied to polyester fibers. To this end, the present application adopts the following technical solutions:

[0007] A preparation method of synergistic antibacterial, antiviral and deodorizing fibers, wherein N-CQDs with a size of 3-5 nm are prepared by a one-step hydrothermal method using o-phenylenediamine and an acid, nanometer elemental copper with a size of 2-10 nm is generated on the surface of the N-CQDs by an in-situ reduction method to obtain Cu-N-CQDs, the Cu-N-CQDs are modified by a carboxylic acid to obtain CM-Cu-N-CQDs to improve the compatibility of the Cu-N-CQDs with polymers, then the Cu-N-CQDs are in-situ polymerized in a PET synthesis process to obtain antibacterial and antiviral polyester, and finally the antibacterial and antiviral polyester is melt-spun to obtain antibacterial and antiviral fibers with a cross-shaped heterostructure.

[0008] The nitrogen-doped carbon quantum dots (N-CQDs) obtained by the present application have a size of 3-5 nm. Under sunlight, the N-CQDs not only generate active oxygen free radicals to achieve high-efficiency antibacterial and antiviral functions, but also have a π-π conjugation effect with the electron-withdrawing group C=N on the surface of the nicotine to generate fluorescence resonance energy transfer. The carbon quantum dots can use more energy to degrade nicotine to achieve the effect of eliminating smoke odor. The nanometer elemental copper obtained by the present application has a size of 2-10 nm. The nanometer elemental copper with this size has higher catalytic reaction antibacterial and antiviral activity. The nanometer copper can continuously activate water and oxygen in the air to generate active oxygen free radicals (ROS). These ROS (hydroxyl radicals, superoxide radicals and hydrogen peroxide) have strong oxidizing properties and can directly or indirectly damage the structure and function of cells to cause bacteria and viruses to die. The sizes of the N-CQDs and the nanometer Cu are both nanoscale, which are prone to agglomeration during use, affecting the spinning performance of the polymers and the antibacterial, antiviral and deodorizing effects.

[0009] The application combines nano-copper and nitrogen-doped carbon quantum dots (N-CQDs) to obtain Cu-N-CQDs, and modifies the Cu-N-CQDs by carboxylic acid to obtain CM-Cu-N-CQDs to improve the dispersibility and compatibility of the Cu-N-CQDs in polyester polymerization, and develops high-efficiency antibacterial and antiviral deodorization fibers, solves the problems of poor spinnability and poor durability of antibacterial and antiviral deodorization of nano-copper and nitrogen-doped carbon quantum dots when the nano-copper and nitrogen-doped carbon quantum dots are applied to polyester fibers, and meets the higher requirements of different fields on the antibacterial and antiviral performance of fibers. The Cu-N-CQDs obtained by carboxylic acid modification not only have good compatibility with PET, but also can be uniformly and stably dispersed in the melt in PET in-situ polymerization, thereby avoiding the agglomeration of nano-scale N-CQDs and copper, and the carboxyl groups can be well combined with nano-copper to maintain the nano-copper of the Cu-N-CQDs in a reduced state, continuously release active oxygen free radicals, and play a role in antibacterial and antiviral. In addition, the nano-copper can make up for the disadvantage that the N-CQDs are difficult to play the role of antibacterial and antiviral deodorization without ultraviolet light irradiation, and play a synergistic role in high-efficiency antibacterial and antiviral deodorization. Therefore, the fibers obtained by the application have high-efficiency and durable antibacterial and antiviral deodorization effects, and have high mechanical properties, and can be used in fields with high requirements on the antibacterial and antiviral deodorization performance of fibers.

[0010] The application also provides a preparation method of the synergistic antibacterial and antiviral deodorization fiber.

[0011] (1) 2-5 parts of o-phenylenediamine are ultrasonically dispersed in 100 parts of 95% ethanol to prepare an o-phenylenediamine solution, 2-10 parts of acid are ultrasonically dispersed in 100 parts of 95% ethanol to prepare an acid solution, the o-phenylenediamine solution and the acid solution are mixed and then added to a stainless steel autoclave, reaction is carried out at 160-260 DEG C for 0.5-18 h to obtain a dark brown solution, the obtained product is washed by centrifugation with deionized water and anhydrous ethanol for 3-5 times, and finally dried to obtain nitrogen-doped carbon quantum dots (N-CQDs);

[0012] (2) 2-4 parts of N-CQDs are ultrasonically dispersed in 50 parts of deionized water to prepare an N-CQDs aqueous solution, 0.8-1.4 parts of a copper salt is dissolved in 50 parts of deionized water to prepare a copper ion aqueous solution; the N-CQDs aqueous solution and the copper ion aqueous solution are mixed in a flask, and then condensed and refluxed after mixing, and then 50 parts of a reducing agent aqueous solution is added dropwise into the flask while stirring, and stirring is carried out at 60-90 DEG C for 3-24 h to obtain a dark solution; the obtained product is separated by centrifugation with deionized water and anhydrous ethanol, and finally dried to obtain N-CQDs antibacterial agent with nano-copper on the surface (Cu-N-CQDs antibacterial agent);

[0013] (3) adding 1-3 parts of aliphatic dibasic acid, 15-20 parts of Cu-N-CQDs antibacterial agent and 0.5-2 parts of ethylene glycol into 100 parts of anhydrous ethanol, condensing and refluxing, stirring for 0.5-5 hours to obtain a Cu-N-CQDs slurry modified by carboxylic acid, then centrifuging the modified Cu-N-CQDs slurry in a centrifuge tube, removing the supernatant to obtain a precipitate, washing the precipitate with ethanol and water for 3-5 times, and drying to obtain carboxylic acid modified Cu-N-CQDs;

[0014] (4) adding 1-3 parts of carboxylic acid modified Cu-N-CQDs, 80 parts of terephthalic acid and 35-45 parts of ethylene glycol into a polymerization reactor, esterifying first, then pre-polymerizing, final polymerizing, and finally casting and cutting to obtain antibacterial and antiviral polyester chips;

[0015] (5) drying the antibacterial and antiviral polyester chips at 90-120℃ for a period of time, and adding them into a melt spinning machine to spin and obtain antibacterial and antiviral polyester fibers with cross-section structure.

[0016] The preparation method of the synergistic antibacterial and antiviral deodorizing fiber as described above, in step (1), the ultrasonic dispersion conditions of o-phenylenediamine and acid are that the time is 20-60 min and the ultrasonic frequency is 30-60 kHz.

[0017] The preparation method of the synergistic antibacterial and antiviral deodorizing fiber as described above, in step (1), the acid refers to one of benzene sulfonic acid, folic acid, boric acid, acetic acid, terephthalic acid and tartaric acid.

[0018] The preparation method of the synergistic antibacterial and antiviral deodorizing fiber as described above, in step (2), the certain conditions of ultrasonic dispersion of N-CQDs under certain conditions are that the time is 20-60 min and the ultrasonic frequency is 30-60 kHz.

[0019] The preparation method of the synergistic antibacterial and antiviral deodorizing fiber as described above, in step (2), the copper salt refers to one of copper chloride, copper sulfate and copper nitrate.

[0020] The preparation method of the synergistic antibacterial and antiviral deodorizing fiber as described above, in step (2), the aqueous solution of reducing agent refers to one of 0.1-0.5 mol / L aqueous solution of citric acid, hydrazine hydrate, sodium borohydride, ascorbic acid, sodium hypophosphite and tetrabutylammonium borohydride.

[0021] The preparation method of the synergistic antibacterial and antiviral deodorizing fiber as described above, in step (3), the aliphatic dibasic acid refers to one of adipic acid, heptanedioic acid, octanedioic acid, nonanedioic acid, decanedioic acid and dodecanedioic acid.

[0022] The preparation method of the synergistic antibacterial and antiviral deodorization fiber as described above, in step (4), the reaction conditions of esterification are that the temperature is 235-255 DEG C, the pressure is 0.3-0.4 MPa, and the time is 2-3 h.

[0023] The preparation method of the synergistic antibacterial and antiviral deodorization fiber as described above, in step (4), the reaction conditions of pre-polymerization are that the temperature is 260-270 DEG C, the pressure is -0.09 to -0.10 MPa, and the time is 0.5-1.5 h.

[0024] The preparation method of the synergistic antibacterial and antiviral deodorization fiber as described above, in step (4), the reaction conditions of final polymerization are that the temperature is 270-280 DEG C, the pressure is 20-100 Pa, and the time is 2-3 h.

[0025] The preparation method of the synergistic antibacterial and antiviral deodorization fiber as described above, in step (5), the spinneret shape during spinning is a cross-shaped spinneret hole, and the spun fiber is a cross-shaped special structure.

[0026] The preparation method of the synergistic antibacterial and antiviral deodorization fiber as described above, in step (5), the antibacterial and antiviral polyester fiber has a breaking strength of 2.0-3.5 cN / dtex, an elongation at break of 15-30%, an antibacterial effect on Staphylococcus aureus, Escherichia coli and Candida albicans of more than 99%, an antiviral effect on influenza A H1N1 virus of more than 99%, a photocatalytic degradation effect on nicotine of the antibacterial and antiviral fiber under simulated sunlight detected by ultra-performance liquid chromatography (UPLC) of more than 99% after 75 minutes of sunlight irradiation, a bacteriostatic rate on Escherichia coli and Staphylococcus aureus of more than 97% after 50 times of washing, an antiviral effect on influenza A H1N1 virus of more than 97% after 50 times of washing, a degradation effect on nicotine of more than 97% after 75 minutes of sunlight irradiation, and good washing resistance, high-efficiency antibacterial and antiviral properties and fabric smoke odor elimination.

[0027] The present application has the following advantages:

[0028] (1) Safety: the Cu-N-CQDs prepared by the present application are non-dissolved antibacterial and antiviral additives without ion overflow, which does not harm the human body and the environment, and is more safe and environmentally friendly.

[0029] (2) Persistent antibacterial: the nano copper prepared by the present application is always in a reduced state, and the nano copper continuously releases active oxygen free radicals, thereby having persistent antibacterial and antiviral effects.

[0030] (3) High efficiency antibacterial: the nano copper in the application can still play an antibacterial and antiviral effect without ultraviolet irradiation, and the combination of N-CQDs can achieve higher antibacterial and antiviral effects and eliminate the effect of fabric nicotine;

[0031] (4) High strength: the carboxylic acid modified Cu-N-CQDs prepared in the application have good dispersibility, and the antibacterial and antiviral polyester composite fibers prepared have good spinnability and high mechanical properties. DETAILED DESCRIPTION

[0032] The application will be further described in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the application and not to limit the scope of the application. In addition, it should be understood that those skilled in the art can make various modifications or changes to the application after reading the content taught by the application, and these equivalent forms also fall within the scope of the claims attached to the application.

[0033] Example 1, a preparation method of a synergistic antibacterial and antiviral deodorant fiber, the specific steps are as follows:

[0034] (1) 2.5 parts of o-phenylenediamine were dispersed in 100 parts of 95% ethanol at a frequency of 60 kHz for 20 minutes to prepare an o-phenylenediamine solution, 2 parts of terephthalic acid were dispersed in 100 parts of 95% ethanol at a frequency of 60 kHz for 20 minutes to prepare a terephthalic acid solution, and the o-phenylenediamine solution and the terephthalic acid solution were mixed and then added to a stainless steel autoclave, and reacted at 160°C for 3 hours to obtain a dark brown solution. The product was washed with deionized water and anhydrous ethanol by centrifugation for 3 times, and finally dried to obtain nitrogen-doped carbon quantum dots (N-CQDs);

[0035] (2) 2 parts of nano N-CQDs were dispersed in 50 parts of deionized water at a frequency of 60 kHz for 20 minutes to prepare an N-CQDs aqueous solution, and 0.8 parts of anhydrous copper sulfate was dissolved in 50 parts of deionized water to prepare a copper ion aqueous solution. The N-CQDs aqueous solution and the copper ion aqueous solution were mixed in a flask, and then subjected to condensation reflux at 80°C, and then stirred while 50 parts of 0.1 mol / L citric acid aqueous solution was added dropwise into the flask, and stirred at 60°C for 3 hours to obtain a dark solution. The product was separated by centrifugation with deionized water and anhydrous ethanol, and finally dried to obtain N-CQDs antibacterial agent with nano elemental copper on the surface (Cu-N-CQDs antibacterial agent);

[0036] (3) 1.5 parts of adipic acid, 15 parts of Cu-N-CQDs antibacterial agent and 0.5 parts of ethylene glycol are added to 100 parts of anhydrous ethanol, and condensation reflux and stirring are carried out at 80 DEG C for 2 hours to obtain a carboxylic acid modified Cu-N-CQDs slurry, then the carboxylic acid modified Cu-N-CQDs slurry is placed in a centrifuge tube and centrifuged, the supernatant is removed, and the obtained precipitate is washed with ethanol and water for 3 times, and dried to obtain carboxylic acid modified Cu-N-CQDs;

[0037] (4) 1.5 parts of carboxylic acid modified Cu-N-CQDs, 80 parts of terephthalic acid and 35 parts of ethylene glycol are added to a polymerization reactor, the reactor is sealed and pressurized and heated, the pressure and temperature of the reactor are controlled at 0.34 MPa and 235 DEG C respectively, esterification is carried out for 2 hours, then a vacuum pump is started, pre-polycondensation is carried out, the pressure and temperature of the reactor are-0.09 MPa and 260 DEG C respectively, and pre-polymerization is carried out for 0.5 hours, then the vacuum degree is increased to 20 Pa, the temperature is controlled at 270 DEG C, and final polymerization is carried out for 2 hours, finally, belt casting and pelletizing are carried out to obtain antibacterial and antiviral polyester chips with the function of eliminating fabric nicotine;

[0038] (5) The antibacterial and antiviral polyester chips are dried in an oven at 100 DEG C for 16 hours, and then added to melt spinning to carry out spinning, a cross-shaped jet orifice is used as a spinning plate to obtain antibacterial and antiviral polyester fibers with a cross-shaped cross section.

[0039] The breaking strength of the antibacterial and antiviral polyester fiber of the application is 3.5 cN / dtex, the breaking elongation is 30%, the antibacterial effect on Staphylococcus aureus, Escherichia coli and Candida albicans can reach 99.0%, the antiviral effect on influenza A H1N1 virus can reach 99.0%, the photocatalytic degradation effect of the antibacterial and antiviral fiber on nicotine under simulated sunlight is detected by ultra-high performance liquid chromatography (UPLC), and it is found that the degradation effect of the antibacterial and antiviral fiber on nicotine can reach more than 99.2% after 75 minutes of sunlight irradiation, the antibacterial rate of the fiber on Escherichia coli and Staphylococcus aureus still reaches more than 97% after 50 times of washing, the antiviral effect on influenza A H1N1 virus reaches 97.1%, the degradation effect on nicotine reaches more than 97.1% after 75 minutes of sunlight irradiation, and the fiber has good washing resistance, high-efficiency antibacterial and antiviral properties and fabric smoke odor elimination performance.

[0040] Example 2, a preparation method of a synergistic antibacterial and antiviral odor-eliminating fiber, the specific steps are as follows:

[0041] (1) 2.5 parts of o-phenylenediamine were dispersed in 100 parts of 95% ethanol at a frequency of 30 kHz for 60 min to prepare an o-phenylenediamine solution, 3 parts of tartaric acid were dispersed in 100 parts of 95% ethanol at a frequency of 30 kHz for 60 min to prepare a tartaric acid solution, the o-phenylenediamine solution and the tartaric acid solution were mixed, and then added to a stainless steel autoclave, reacted at 200°C for 3 h to obtain a dark brown solution, the obtained product was washed with deionized water and anhydrous ethanol by centrifugation for 4 times, and finally dried to obtain nitrogen-doped carbon quantum dots (N-CQDs);

[0042] (2) 2.5 parts of nano N-CQDs were dispersed in 50 parts of deionized water at a frequency of 30 kHz for 60 min to prepare an N-CQDs aqueous solution, 1 part of copper chloride was dissolved in 50 parts of deionized water to prepare a copper ion aqueous solution. The N-CQDs aqueous solution and the copper ion aqueous solution were mixed in a flask, then condensation reflux was carried out at 80°C, then stirring was carried out while 50 parts of 0.5 mol / L ascorbic acid aqueous solution was added dropwise into the flask, stirring was carried out at 90°C for 24 h to obtain a dark solution. The obtained product was separated by centrifugation with deionized water and anhydrous ethanol, and finally dried to obtain N-CQDs antibacterial agent with nano elemental copper on the surface (Cu-N-CQDs antibacterial agent);

[0043] (3) 2.5 parts of suberic acid, 20 parts of Cu-N-CQDs antibacterial agent and 1 part of ethylene glycol were added to 100 parts of anhydrous ethanol, condensation reflux was carried out at 80°C, and stirring was carried out for 5 h to obtain a carboxylic acid modified Cu-N-CQDs slurry, then the carboxylic acid modified Cu-N-CQDs slurry was placed in a centrifuge tube and centrifuged, the supernatant was removed to obtain a precipitate, which was washed with ethanol and water for 5 times, and dried to obtain carboxylic acid modified Cu-N-CQDs;

[0044] (4) 1.5 parts of carboxylic acid modified Cu-N-CQDs, 80 parts of terephthalic acid and 40 parts of ethylene glycol were added to a polymerization reactor, the reactor was sealed and pressurized and heated. The pressure and temperature of the reactor were controlled at 0.40 MPa and 255°C respectively, esterification was carried out for 3 h; then a vacuum pump was started, and pre-polycondensation was carried out, at this time the pressure and temperature of the reactor were-0.10 MPa and 270°C respectively, and pre-polymerization was carried out for 1.5 h; the vacuum degree was increased to 100 Pa, and the temperature was controlled at 280°C, and final polymerization was carried out for 3 h. Finally, after casting and pelletizing, an antibacterial and antiviral polyester chip with the function of eliminating fabric nicotine was obtained;

[0045] (5) The antibacterial and antiviral polyester chip was dried in an oven at 100°C for 24 h, and then added to melt spinning to perform spinning, a cross structure jet orifice was used as a spinning plate, and an antibacterial and antiviral polyester fiber with a cross section structure was obtained.

[0046] The anti-bacterial and anti-virus polyester fiber of the present application has a breaking strength of 2.8 cN / dtex, an elongation at break of 20%, an antibacterial effect of 99.3% on Staphylococcus aureus, Escherichia coli and Candida albicans, an anti-virus effect of 99.2% on influenza A H1N1 virus, and a photocatalytic degradation effect on nicotine of the anti-bacterial and anti-virus fiber under simulated sunlight detected by ultra-performance liquid chromatography (UPLC) of 99.6% or more after 75 minutes of sunlight irradiation. After 50 washes, the antibacterial rate on Escherichia coli and Staphylococcus aureus is still 97.3% or more, the anti-virus effect on influenza A H1N1 virus is 97.2%, and the degradation effect on nicotine is 97.5% or more after 75 minutes of sunlight irradiation, thus having good wash resistance, high-efficiency antibacterial and anti-virus properties and fabric smoke-eliminating properties.

[0047] Example 3, a preparation method of a synergistic antibacterial and anti-virus deodorizing fiber, the specific steps are as follows:

[0048] (1) 3.5 parts of o-phenylenediamine were dispersed in 100 parts of 95% ethanol at a frequency of 40 kHz for 40 min to prepare an o-phenylenediamine solution, 4 parts of 4-aminobenzenesulfonic acid were dispersed in 100 parts of 95% ethanol at a frequency of 40 kHz for 40 min to prepare a 4-aminobenzenesulfonic acid solution, and the o-phenylenediamine solution and the 4-aminobenzenesulfonic acid solution were mixed and then added to a stainless steel autoclave, and reacted at 220℃ for 8h to obtain a dark brown solution. The product was washed with deionized water and anhydrous ethanol by centrifugation for 3 times, and finally dried to obtain nitrogen-doped carbon quantum dots (N-CQDs);

[0049] (2) 3 parts of nano N-CQDs were dispersed in 50 parts of deionized water at a frequency of 40 kHz for 40 min to prepare an N-CQDs aqueous solution, and 1.2 parts of copper chloride was dissolved in 50 parts of deionized water to prepare a copper ion aqueous solution. The N-CQDs aqueous solution and the copper ion aqueous solution were mixed in a flask and then subjected to condensation reflux at 80℃, and then 50 parts of 0.3 mol / L ascorbic acid aqueous solution was added dropwise into the flask while stirring at 70℃ for 20h to obtain a dark solution. The product was separated by centrifugation with deionized water and anhydrous ethanol, and finally dried to obtain N-CQDs antibacterial agent with nano elemental copper on the surface (Cu-N-CQDs antibacterial agent);

[0050] (3) 2.5 parts of dodecanedioic acid, 15 parts of Cu-N-CQDs antibacterial agent and 1.5 parts of ethylene glycol are added into 100 parts of anhydrous ethanol, and condensation reflux and stirring are carried out at 80℃ for 2h to obtain a carboxylic acid modified Cu-N-CQDs slurry, then the carboxylic acid modified Cu-N-CQDs slurry is placed in a centrifugal tube and centrifuged, the supernatant is removed, and the obtained precipitate is washed with ethanol and water for 5 times, and dried to obtain carboxylic acid modified Cu-N-CQDs;

[0051] (4) 2 parts of carboxylic acid modified Cu-N-CQDs, 80 parts of terephthalic acid and 40 parts of ethylene glycol are added into a polymerization reactor, the reactor is sealed and pressurized and heated, the pressure and temperature of the reactor are controlled at 0.35 MPa and 245℃ respectively, esterification is carried out for 3h, then a vacuum pump is started, pre-polycondensation is carried out, the pressure and temperature of the reactor are-0.10 MPa and 265℃ respectively, and pre-polymerization is carried out for 1h, the vacuum degree is increased to 60 Pa, the temperature is controlled at 278℃, and final polymerization is carried out for 2.5h. Finally, through casting and granulation, an antibacterial and antiviral polyester chip with the function of eliminating fabric nicotine is obtained;

[0052] (5) The antibacterial and antiviral polyester chip is dried in an oven at 100℃ for 36h, and then added into a melt spinning machine for spinning, a cross-shaped jet orifice is used as the spinning plate, and an antibacterial and antiviral polyester fiber with a cross-shaped cross-section structure is obtained.

[0053] The breaking strength of the antibacterial and antiviral polyester fiber of the application is 3.1 cN / dtex, the breaking elongation is 24%, the antibacterial effect on Staphylococcus aureus, Escherichia coli and Candida albicans can reach 99.5%, the antiviral effect on influenza A H1N1 virus can reach 99.5%, the photocatalytic degradation effect of the antibacterial and antiviral fiber on nicotine under simulated sunlight is detected by ultra-high performance liquid chromatography (UPLC), and it is found that after 75 minutes of sunlight irradiation, the degradation effect of the antibacterial and antiviral fiber on nicotine can reach more than 99.2%, after washing the fiber for 50 times, the antibacterial rate on Escherichia coli and Staphylococcus aureus still reaches more than 97%, the antiviral effect on influenza A H1N1 virus reaches 97.1%, and the degradation effect on nicotine after 75 minutes of sunlight irradiation reaches more than 97.2%, which has good water washing resistance, high-efficiency antibacterial and antiviral properties and fabric smoke odor elimination performance.

[0054] Example 4, a preparation method of a synergistic antibacterial and antiviral odor-eliminating fiber, the specific steps are as follows:

[0055] (1) 4.5 parts of o-phenylenediamine were dispersed in 100 parts of 95% ethanol under ultrasonic dispersion at a frequency of 30 kHz for 50 min to prepare an o-phenylenediamine solution, 6 parts of folic acid were dispersed in 100 parts of 95% ethanol under ultrasonic dispersion at a frequency of 30 kHz for 50 min to prepare a folic acid solution, and the o-phenylenediamine solution and the folic acid solution were mixed and then added to a stainless steel autoclave, and reacted at 240°C for 10 h to obtain a dark brown solution, and the product was washed with deionized water and anhydrous ethanol by centrifugation for 5 times, and finally dried to obtain nitrogen-doped carbon quantum dots (N-CQDs);

[0056] (2) 4 parts of nano N-CQDs were dispersed in 50 parts of deionized water under ultrasonic dispersion at a frequency of 30 kHz for 50 min to prepare an N-CQDs aqueous solution, and 1.4 parts of copper chloride was dissolved in 50 parts of deionized water to prepare a copper ion aqueous solution. The N-CQDs aqueous solution and the copper ion aqueous solution were mixed in a flask, and then condensation reflux was carried out at 80°C, and then 50 parts of 0.4 mol / L ascorbic acid aqueous solution was added dropwise into the flask, and stirred at 80°C for 20 h to obtain a dark solution. The product was separated by centrifugation with deionized water and anhydrous ethanol, and finally dried to obtain N-CQDs antibacterial agent with nano elemental copper on the surface (Cu-N-CQDs antibacterial agent);

[0057] (3) 2.5 parts of sebacic acid, 17 parts of Cu-N-CQDs antibacterial agent, and 2 parts of ethylene glycol were added to 100 parts of anhydrous ethanol, and condensation reflux was carried out at 80°C for 3 h to obtain a carboxylic acid modified Cu-N-CQDs slurry, and then the carboxylic acid modified Cu-N-CQDs slurry was centrifuged in a centrifuge tube, and the supernatant was removed to obtain a precipitate which was washed with ethanol and water for 5 times, and dried to obtain carboxylic acid modified Cu-N-CQDs;

[0058] (4) 1.5 parts of carboxylic acid modified Cu-N-CQDs, 80 parts of terephthalic acid, and 45 parts of ethylene glycol were added to a polymerization reactor, and the reactor was sealed and pressurized and heated. The pressure and temperature of the reactor were controlled at 0.40 MPa and 245°C respectively, and esterification was carried out for 2 h; then a vacuum pump was started, and pre-polycondensation was carried out, and the pressure and temperature of the reactor were-0.08 MPa and 270°C respectively, and pre-polymerization was carried out for 1.5 h; the vacuum degree was increased to 60 Pa, and the temperature was controlled at 278°C, and final polymerization was carried out for 3 h. Finally, after casting and pelletizing, an antibacterial and antiviral polyester chip with the function of eliminating fabric nicotine was obtained;

[0059] (5) The antibacterial and antiviral polyester chip was dried in an oven at 100°C for 24 h, and then added to melt spinning to spin, and a cross-shaped jet orifice was used as the spinneret hole to obtain an antibacterial and antiviral polyester fiber with a cross-shaped cross-section structure.

[0060] The anti-bacterial and anti-virus polyester fiber of the present application has a breaking strength of 3.4 cN / dtex, an elongation at break of 20%, an antibacterial effect of 99.3% on Staphylococcus aureus, Escherichia coli and Candida albicans, an anti-virus effect of 99.1% on influenza A H1N1 virus, and a photocatalytic degradation effect on nicotine of the anti-bacterial and anti-virus fiber under simulated sunlight detected by ultra-performance liquid chromatography (UPLC) of 99.4% or more after 75 minutes of sunlight irradiation. After 50 washes, the antibacterial rate on Escherichia coli and Staphylococcus aureus is still 97.5% or more, the anti-virus effect on influenza A H1N1 virus is 97.4%, and the degradation effect on nicotine is 97.3% or more after 75 minutes of sunlight irradiation, thus having good wash resistance, high-efficiency antibacterial and anti-virus properties and fabric smoke-eliminating properties.

[0061] Example 5, a preparation method of a synergistic antibacterial and anti-virus deodorizing fiber, comprising the following specific steps:

[0062] (1) 4.5 parts of o-phenylenediamine were dispersed in 100 parts of 95% ethanol at a frequency of 50 kHz for 30 min to prepare an o-phenylenediamine solution, 8 parts of acetic acid were dispersed in 100 parts of 95% ethanol at a frequency of 50 kHz for 30 min to prepare an acetic acid solution, the o-phenylenediamine solution and the acetic acid solution were mixed and then added to a stainless steel autoclave, and a dark brown solution was obtained after reaction at 260℃ for 14 h. The product was washed with deionized water and anhydrous ethanol by centrifugation for 5 times, and finally dried to obtain nitrogen-doped carbon quantum dots (N-CQDs);

[0063] (2) 3.5 parts of nano N-CQDs were dispersed in 50 parts of deionized water at a frequency of 50 kHz for 30 min to prepare an N-CQDs aqueous solution, and 1.4 parts of copper chloride was dissolved in 50 parts of deionized water to prepare a copper ion aqueous solution. The N-CQDs aqueous solution and the copper ion aqueous solution were mixed in a flask, then condensation reflux was carried out at 80℃, and then 50 parts of 0.3 mol / L ascorbic acid aqueous solution was added dropwise into the flask while stirring at 80℃ for 22 h to obtain a dark solution. The product was separated by centrifugation with deionized water and anhydrous ethanol, and finally dried to obtain N-CQDs antibacterial agent with nano elemental copper on the surface (Cu-N-CQDs antibacterial agent);

[0064] (3) 2 parts of sebacic acid, 15 parts of Cu-N-CQDs antibacterial agent and 1.5 parts of ethylene glycol were added to 100 parts of anhydrous ethanol, and condensation reflux and stirring were carried out at 80℃ for 3 h to obtain carboxylic acid modified Cu-N-CQDs slurry. Then the slurry was centrifuged in a centrifuge tube, the supernatant was removed, and the obtained precipitate was washed with ethanol and water for 5 times, and finally dried to obtain carboxylic acid modified Cu-N-CQDs.

[0065] (4) 2.5 parts of carboxylic acid modified Cu-N-CQDs, 80 parts of terephthalic acid, and 45 parts of ethylene glycol are added into a polymerization reactor, and the reactor is sealed and pressurized and heated. The pressure and temperature of the reactor are controlled at 0.36 MPa and 245 DEG C respectively, and esterification is carried out for 3 hours. Then a vacuum pump is started, and pre-polycondensation is carried out, and the pressure and temperature of the reactor are-0.10 MPa and 265 DEG C respectively, and pre-polymerization is carried out for 0.5 hours. The vacuum degree is increased to 100 Pa, and the temperature is controlled at 280 DEG C, and final polymerization is carried out for 3 hours. Finally, the polyester chip with antibacterial and antiviral functions for eliminating fabric nicotine is obtained by casting and granulating.

[0066] (5) The antibacterial and antiviral polyester chip is dried in an oven at 100 DEG C for 36 hours, and is added into a melt spinning machine for spinning. The spinneret has a cross-shaped structure, and the antibacterial and antiviral polyester fiber with a cross-shaped cross-section structure is obtained.

[0067] The breaking strength of the antibacterial and antiviral polyester fiber of the application is 3.0 cN / dtex, the elongation at break is 21%, the antibacterial effect on Staphylococcus aureus, Escherichia coli and Candida albicans can reach 99.4%, the antiviral effect on influenza A H1N1 virus can reach 99.5%, the photocatalytic degradation effect of the antibacterial and antiviral fiber on nicotine under simulated sunlight is detected by ultra-high performance liquid chromatography (UPLC), and it is found that the degradation effect of the antibacterial and antiviral fiber on nicotine can reach more than 99.5% after 75 minutes of sunlight irradiation. After washing the fiber for 50 times, the antibacterial rate on Escherichia coli and Staphylococcus aureus still reaches more than 97.8%, the antiviral effect on influenza A H1N1 virus reaches 97.4%, the degradation effect on nicotine after 75 minutes of sunlight irradiation reaches more than 97.6%, and the fiber has good washing resistance, high-efficiency antibacterial and antiviral properties, and fabric smoke odor eliminating performance.

Claims

1. A process for the preparation of a synergistic antibacterial antiviral deodorant fiber characterized in that, The method comprises the following steps: (1) 2-5 parts of o-phenylenediamine are ultrasonically dispersed in 100 parts of 95% ethanol to prepare an o-phenylenediamine solution, 2-10 parts of acid are ultrasonically dispersed in 100 parts of 95% ethanol to prepare an acid solution, the o-phenylenediamine solution and the acid solution are mixed and then added into a stainless steel autoclave, and the mixture is reacted at 160-260°C for 0.5-18 hours to obtain a dark brown solution, the obtained product is washed by centrifugation with deionized water and anhydrous ethanol for 3-5 times, and finally dried to obtain nitrogen-doped carbon quantum dots N-CQDs; wherein the ultrasonic dispersion conditions of o-phenylenediamine and acid are that the time is 20-60 minutes and the ultrasonic frequency is 30-60 kHz; the acid refers to one of benzene sulfonic acid, folic acid, boric acid, acetic acid, terephthalic acid and tartaric acid; (2) 2-4 parts of N-CQDs are ultrasonically dispersed in 50 parts of deionized water under certain conditions to prepare an N-CQDs aqueous solution, 0.8-1.4 parts of a copper salt is dissolved in 50 parts of deionized water to prepare a copper ion aqueous solution; the N-CQDs aqueous solution and the copper ion aqueous solution are mixed in a flask, and then condensed and refluxed after mixing, and then stirred while 50 parts of a reducing agent aqueous solution is added dropwise into the flask, and the mixture is stirred at 60-90°C for 3-24 hours to obtain a dark solution; the obtained product is separated by centrifugation with deionized water and anhydrous ethanol, and finally dried to obtain a Cu-N-CQDs antibacterial agent; (3) 1-3 parts of an aliphatic dibasic acid, 15-20 parts of the Cu-N-CQDs antibacterial agent and 0.5-2 parts of ethylene glycol are added into 100 parts of anhydrous ethanol, and then condensed and refluxed and stirred for 0.5-5 hours to obtain a carboxylic acid modified Cu-N-CQDs slurry, and then the modified Cu-N-CQDs slurry is placed into a centrifuge tube and centrifuged, the supernatant is removed, and the obtained precipitate is washed with ethanol and water for 3-5 times, and finally dried to obtain carboxylic acid modified Cu-N-CQDs; (4) 1-3 parts of the carboxylic acid modified Cu-N-CQDs, 80 parts of terephthalic acid and 35-45 parts of ethylene glycol are added into a polymerization reactor, and then esterification, prepolymerization and final polymerization are carried out, and finally cast banding and pelletizing are performed to obtain an antibacterial and antiviral polyester chip; (5) The antibacterial and antiviral polyester chip is dried at 90-120°C for a period of time, and then added into a melt spinning machine to perform spinning to obtain an antibacterial and antiviral polyester fiber with a cross-section structure.

2. A method of preparing a synergistic antibacterial and antiviral deodorizing fiber according to claim 1, characterized by, In step (2), the certain conditions of ultrasonic dispersion of N-CQDs are that the time is 20-60 minutes and the ultrasonic frequency is 30-60 kHz; the copper salt refers to one of copper chloride, copper sulfate and copper nitrate; and the reducing agent aqueous solution refers to one of 0.1-0.5 mol / L of citric acid, hydrazine hydrate, sodium borohydride, ascorbic acid, sodium hypophosphite and tetrabutylammonium borohydride aqueous solution.

3. A method of preparing a synergistic antibacterial and antiviral deodorizing fiber according to claim 1, characterized by, In step (3), the aliphatic dibasic acid refers to one of adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and dodecanedioic acid.

4. A method of preparing a synergistic antibacterial and antiviral deodorizing fiber according to claim 1, characterized by, In step (4), the reaction conditions for esterification are temperature 235-255℃, pressure 0.3-0.4 MPa, and time 2-3 h; the reaction conditions for prepolymerization are temperature 260-270℃, pressure -0.09--0.10 MPa, and time 0.5-1.5 h; and the reaction conditions for final polymerization are temperature 270-280℃, pressure 20-100 Pa, and time 2-3 h.

5. A method of preparing a synergistic antibacterial and antiviral deodorizing fiber according to claim 1, characterized by, In step (5), the spinneret shape is cross-shaped spinneret hole, the prepared antibacterial and antiviral polyester fiber has breaking strength 2.0-3.5 cN / dtex and elongation at break 15-30%, the antibacterial effect on Staphylococcus aureus, Escherichia coli and Candida albicans is more than 99%, the antiviral effect on influenza A H1N1 virus is more than 99%, the photocatalytic degradation effect of the antibacterial and antiviral fiber on nicotine under simulated sunlight is detected by ultra-high performance liquid chromatography, after 75 minutes of sunlight irradiation, the degradation effect of the antibacterial and antiviral fiber on nicotine is more than 99%, after 50 times of fiber washing, the antibacterial rate on Escherichia coli and Staphylococcus aureus is still more than 97%, the antiviral effect on influenza A H1N1 virus is more than 97%, and the degradation effect on nicotine is more than 97% after 75 minutes of sunlight irradiation.