Preparation method and application of a synergistic antibacterial, antiviral and deodorizing functional masterbatch

Abstract

The present invention relates to a preparation method and application of a synergistic antibacterial, antiviral and deodorizing masterbatch. First, nano-scale nitrogen-doped carbon quantum dots are prepared by a one-step hydrothermal method using o-phenylenediamine and an acid, and then nano-scale elemental copper is coordinated and generated on the surface of the nitrogen-doped carbon quantum dots by an in-situ reduction method. After being modified with carboxylic acid, polyester is introduced by in-situ polymerization to obtain an antibacterial and antiviral masterbatch. The antibacterial and antiviral masterbatch can be melt-spun with a matrix resin in a certain proportion to obtain antibacterial and antiviral fibers. The antibacterial and antiviral masterbatch prepared by the present invention will not cause harm to the environment during use, and the antibacterial and antiviral fibers prepared therefrom have the characteristics of high-efficiency and long-lasting antibacterial and antiviral properties and eliminating the smoke odor of fabrics.

Description

Technical Field

[0001] The present invention relates to the field of preparation of polymer functional masterbatches, and relates to a preparation method and application of a synergistic antibacterial, antiviral and deodorizing functional masterbatch, in particular to a preparation method and application of a functional masterbatch that realizes antibacterial, antiviral and fabric smoke odor elimination effects through the synergy of nano copper and nitrogen-doped carbon quantum dots. Background Art

[0002] The harm caused by the breeding, reproduction and cross-infection of pathogenic bacteria and viruses to human health is inestimable. Textiles are the main carriers of pathogenic bacteria and viruses, and endowing textiles with antibacterial and antiviral functions has increasingly attracted social attention. In addition, the nicotine smoke odor generated by cigarette burning in life is also easily adsorbed on the surface of fiber fabrics, affecting the wearing experience of the fabrics. The demand for antibacterial, antiviral and deodorizing composite functional textiles by people has been increasing year by year, and the existing technologies cannot meet the urgent needs of people for antibacterial, antiviral and deodorizing composite functional fibers and fabrics. Therefore, it is of great significance to develop antibacterial, antiviral and deodorizing composite functional fibers.

[0003] Polyester materials mainly include polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), and polybutylene terephthalate (PBT), and have good fiber-forming properties, mechanical properties, corrosion resistance, light transmittance, electrical insulation properties, etc., and are widely used in the fiber field, such as textiles, films, industrial yarns, etc. If antibacterial, antiviral and deodorizing capabilities are imparted to polyester fibers, it can not only broaden the application market of polyester fibers, but also meet the needs of people for antibacterial, antiviral and deodorizing composite functional fibers.

[0004] Polyester fibers themselves do not have antibacterial, antiviral and deodorizing capabilities, and their antibacterial and antiviral modification is mainly achieved by adding antibacterial and antiviral agents. In recent years, silver- or copper-containing antibacterial and antiviral agents have often been used in combination with fibers to make antibacterial and antiviral fibers. However, silver-based antibacterial and antiviral agents are expensive and easily degraded by heat, and the use of nano-silver antibacterial and antiviral agents in textiles is restricted abroad. Copper-based antibacterial and antiviral agents are economical and practical, have a broad bactericidal spectrum, strong comprehensive treatment ability, are not easy to cause bacteria to develop drug resistance, and have good persistence, and are currently the antibacterial and antiviral agents studied more. Nano copper belongs to a non-leaching type antibacterial and antiviral agent, which can directly react with water and oxygen in the air to convert them into reactive oxygen species (ROS) to kill bacteria and viruses, and can play an antibacterial and antiviral role without specific conditions. However, the surface of nano-Cu has defects and is easily oxidized and agglomerated during use, affecting the antibacterial and antiviral effects.

[0005] As a new type of fluorescent carbon nanoparticles, nitrogen-doped carbon quantum dots (N-CQDs) have excellent optical properties and good biocompatibility. N-CQDs belong to photocatalytic antibacterial and antiviral agents and can only play a role under ultraviolet conditions. Under sunlight excitation, they can not only generate ROS for antibacterial and antiviral purposes, but also combine with nicotine in tobacco odor to play a deodorizing role. However, N-CQDs are also prone to aggregation, which affects the antibacterial, antiviral, and deodorizing effects. Summary of the Invention

[0006] The purpose of the present invention is to provide a preparation method and application of an antibacterial, antiviral, and deodorizing composite functional masterbatch, which realizes an antibacterial, antiviral, and deodorizing functional masterbatch through the synergistic effect of nano-copper and nitrogen-doped carbon quantum dots, and improves the durability of antibacterial, antiviral, and deodorizing effects.

[0007] According to the first aspect of the present invention, the present invention provides a preparation method of an antibacterial, antiviral, and deodorizing composite functional masterbatch, which adopts the following technical solutions:

[0008] 3-5 nm nitrogen-doped carbon quantum dots (N-CQDs) are prepared by one-step hydrothermal method using o-phenylenediamine and an acid, and then nano-elemental copper Cu-N-CQDs are generated on the surface of the nitrogen-doped carbon quantum dots by in-situ reduction method. CM-Cu-N-CQDs are obtained by carboxyl modification of Cu-N-CQDs, which has good compatibility with polyester and can be uniformly and stably dispersed in the polyester melt during in-situ polymerization of polyester monomers, enhancing its antibacterial, antiviral, and deodorizing durability.

[0009] The nitrogen-doped carbon quantum dots (N-CQDs) obtained in the present invention have a size of 3-5 nm and exhibit extremely high catalytic reaction antibacterial, antiviral, and deodorizing activities. Under photocatalytic conditions, N-CQDs can activate water and oxygen in the air to generate ROS, which can directly or indirectly damage cell structures, playing an antibacterial and antiviral role. Moreover, the electron-donating groups C=N or C=O on the surface of N-CQDs can also undergo π-π conjugation with the electron-donating group C=N on the surface of nicotine, resulting in fluorescence resonance energy transfer. This causes the fluorescence quenching of the donor N-CQDs and the fluorescence enhancement of the acceptor nicotine. After fluorescence quenching, N-CQDs can utilize more energy to degrade nicotine, achieving the effect of eliminating the smell of tobacco. The size of the elemental copper nanoparticles obtained in the present invention is 2-10 nm, and it has extremely high catalytic reaction antibacterial and antiviral activities. The in-situ reduction method is used to generate elemental copper nanoparticles (Cu-N-CQDs) with a size of 2-10 nm on the surface of N-CQDs, and then Cu-N-CQDs are carboxyl-modified to obtain CM-Cu-N-CQDs. The carboxyl group can better complex with the copper nanoparticles to maintain the copper nanoparticles in Cu-N-CQDs in a reduced state, continuously releasing reactive oxygen species (ROS) to play an antibacterial and antiviral role. Carboxyl modification can improve its compatibility with polyester polymerization and enhance its antibacterial, antiviral, and deodorizing persistence.

[0010] The Cu-N-CQDs obtained by carboxyl modification have good compatibility with polyester and can be uniformly and stably dispersed in the polyester melt during the in-situ polymerization of polyester monomers, solving the problem of uneven dispersion of antibacterial, antiviral, and deodorizing agents in polyester. In addition, the copper nanoparticles play an antibacterial and antiviral role without the need for light conditions, solving the defect that N-CQDs need to be excited by sunlight to play an antibacterial, antiviral, and deodorizing role. The two work together to have antibacterial, antiviral, and deodorizing effects, further expanding the application fields of antibacterial, antiviral, and deodorizing fibers.

[0011] Furthermore, a preparation method of a synergistic antibacterial, antiviral, and deodorizing functional masterbatch of the present invention includes the following steps:

[0012] (1) By mass, 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 an acid are ultrasonically dispersed in 100 parts of 95% ethanol to prepare an acid solution. After mixing the o-phenylenediamine solution and the acid solution, they are added to a stainless-steel autoclave and reacted at 160-260 °C for 0.5-18 h to obtain a dark brown solution. The obtained product is washed, centrifuged, and separated with deionized water and absolute ethanol, and finally dried to obtain nitrogen-doped carbon quantum dots (N-CQDs);

[0013] (2) Disperse 3 - 10 parts of N-CQDs in 50 parts of deionized water by ultrasonic treatment to obtain an N-CQDs aqueous solution, and dissolve 3 - 4 parts of copper salt in 50 parts of deionized water to obtain a copper ion aqueous solution; mix the N-CQDs aqueous solution and the copper ion aqueous solution in a flask, carry out condensation reflux, and while stirring, dropwise add 50 parts of the reducing agent aqueous solution into the flask, and stir at 60 - 90 °C for 3 - 20 h to obtain a dark solution; wash the obtained product with deionized water and absolute ethanol, carry out centrifugal separation, and finally dry to obtain an N-CQDs antibacterial agent with nano elemental copper loaded on its surface (Cu-N-CQDs antibacterial agent);

[0014] (3) Add 3 - 5 parts of aliphatic dicarboxylic acid, 5 - 10 parts of deionized water, and 100 - 200 parts of Cu-N-CQDs antibacterial agent to 100 parts of ethylene glycol at 80 - 90 °C, and stir for 0.5 - 5 h to obtain a carboxylic acid-modified Cu-N-CQDs polyester slurry;

[0015] (4) Add 10 - 20 parts of the carboxylic acid-modified Cu-N-CQDs polyester slurry, 80 parts of terephthalic acid, and 35 - 45 parts of ethylene glycol to a polymerization reactor, first carry out esterification, then carry out prepolymerization and final polymerization, and finally carry out casting and pelletizing to obtain an antibacterial and antiviral functional masterbatch.

[0016] For the preparation method of a synergistic antibacterial, antiviral, and deodorizing functional masterbatch as described above, in step (1), the conditions for ultrasonic dispersion of o-phenylenediamine and the acid refer to a time of 20 - 60 min and an ultrasonic frequency of 30 - 60 kHz.

[0017] For the preparation method of a synergistic antibacterial, antiviral, and deodorizing functional masterbatch as described above, in step (1), the acid refers to one of benzenesulfonic acid, folic acid, boric acid, acetic acid, terephthalic acid, and tartaric acid.

[0018] For the preparation method of a synergistic antibacterial, antiviral, and deodorizing functional masterbatch as described above, in step (2), the conditions for ultrasonic dispersion of N-CQDs refer to a time of 20 - 60 min and an ultrasonic frequency of 30 - 60 kHz.

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

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

[0021] In the preparation method of a synergistic antibacterial, antiviral and deodorizing masterbatch as described above, in step (3), the aliphatic dibasic acid refers to one of adipic acid, suberic acid, sebacic acid, and dodecanedioic acid.

[0022] In the preparation method of a synergistic antibacterial, antiviral and deodorizing masterbatch as described above, in step (4), the reaction conditions for esterification are a temperature of 235 - 255°C, a pressure of 0.3 - 0.4 MPa, and a time of 2 - 3 h.

[0023] In the preparation method of a synergistic antibacterial, antiviral and deodorizing masterbatch as described above, in step (4), the reaction conditions for prepolymerization are a temperature of 260 - 270°C, a pressure of -0.09 - -0.10 MPa, and a time of 0.5 - 1.5 h.

[0024] In the preparation method of a synergistic antibacterial, antiviral and deodorizing masterbatch as described above, in step (4), the reaction conditions for final polymerization are a temperature of 270 - 280°C, an absolute pressure of 20 - 100 Pa, and a time of 2 - 3 h.

[0025] According to the second aspect of the present invention, the present invention provides an application of a nano - copper antibacterial and antiviral masterbatch as described above, adopting the following technical solutions:

[0026] The prepared antibacterial and antiviral masterbatch and the matrix resin are dried at 90 - 120°C for a period of time, and then the two are blended in a certain proportion. After mixing evenly, they are added to a melt - spinning machine for spinning to obtain antibacterial and antiviral fibers.

[0027] In the application of a synergistic antibacterial, antiviral and deodorizing masterbatch as described above, the matrix resin is one of polyethylene terephthalate, polytrimethylene terephthalate, and polybutylene terephthalate.

[0028] In the application of a synergistic antibacterial, antiviral and deodorizing masterbatch as described above, the ratio of the antibacterial and antiviral masterbatch to the matrix resin is that the antibacterial and antiviral masterbatch accounts for 10 - 20% of the matrix resin.

[0029] The application of a synergistic antibacterial, antiviral and deodorizing masterbatch as described above. The spun fiber has a breaking strength of 2.2 - 3.5 cN / dtex and an elongation at break of 15 - 30%. The antibacterial effect against Staphylococcus aureus, Escherichia coli, and Candida albicans can reach over 99%, and the antiviral effect against the H1N1 influenza virus reaches over 99%. By detecting the photocatalytic degradation effect of the antibacterial and antiviral fiber on nicotine through ultra-high performance liquid chromatography (UPLC), it is found that after 75 minutes of sunlight irradiation, the degradation effect of the antibacterial and antiviral fiber on nicotine can reach over 99%. After the fiber is washed 50 times, the antibacterial rate against Escherichia coli and Staphylococcus aureus still reaches over 97%, the antiviral effect against the H1N1 influenza virus reaches over 97%, and after 75 minutes of sunlight irradiation, the degradation effect on nicotine reaches over 97%. It has good water-wash resistance, high-efficiency antibacterial and antiviral properties, and the ability to eliminate fabric smoke odor.

[0030] Due to the technical solution of the present invention, the present invention can achieve the following beneficial effects:

[0031] 1. The present invention uses nano-Cu as the main antibacterial and antiviral agent, without ion leakage, and will not cause harm to the environment;

[0032] 2. The N-CQDs-loaded nano-Cu antibacterial agent used in the present invention has good dispersibility and compatibility in polyester, and has little influence on the spinning performance and fiber mechanical properties of polyester;

[0033] 3. The nano-copper in the antibacterial and antiviral masterbatch of the present invention is always in a reduced state, and the nano-copper plays an antibacterial and antiviral role by continuously releasing reactive oxygen free radicals, with high-efficiency and long-lasting antibacterial and antiviral effects;

[0034] 4. The N-CQDs in the antibacterial and antiviral masterbatch of the present invention play a role in degrading nicotine by continuously releasing reactive oxygen free radicals, with high-efficiency and long-lasting effects of eliminating fabric smoke odor. Specific Embodiments

[0035] 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 not 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 also fall within the scope defined by the appended claims of this application.

[0036] Example 1, A preparation method and application of a synergistic antibacterial, antiviral and deodorizing masterbatch, the specific steps are as follows:

[0037] (1) By mass, 3.5 parts of o-phenylenediamine were ultrasonically dispersed in 100 parts of 95% ethanol for 20 min at a frequency of 60 kHz to prepare an o-phenylenediamine solution. 2 parts of terephthalic acid were ultrasonically dispersed in 100 parts of 95% ethanol for 20 min at a frequency of 60 kHz to prepare a terephthalic acid solution. 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 h to obtain a dark brown solution. The obtained product was centrifugally washed 3 times with deionized water and absolute ethanol, and finally dried to obtain nitrogen-doped carbon quantum dots (N-CQDs);

[0038] (2) 5 parts of N-CQDs were added to 50 parts of deionized water and ultrasonically treated in an ultrasonic machine with a frequency of 60 kHz for 20 min to prepare an N-CQDs aqueous solution. 3 parts of copper sulfate were dissolved in 50 parts of deionized water to prepare an aqueous copper ion solution. The N-CQDs aqueous solution and the aqueous copper ion solution were mixed in a flask, and then subjected to condensing reflux at 80 °C. While stirring, 50 parts of 0.1 mol / L citric acid aqueous solution were added dropwise to the flask, and stirred at 60 °C for 3 h to obtain a dark-colored solution. The obtained product was washed and centrifuged with deionized water and absolute ethanol respectively, and finally dried to obtain an N-CQDs antibacterial agent with nano-elemental copper loaded on the surface (Cu-N-CQDs antibacterial agent);

[0039] (3) 3 parts of suberic acid, 100 parts of Cu-N-CQDs antibacterial agent and 5 parts of deionized water were added to 100 parts of ethylene glycol at 80 °C, and stirred for 0.5 h to obtain a carboxylic acid-modified Cu-N-CQDs polyester slurry;

[0040] (4) 10 parts of the carboxylic acid-modified Cu-N-CQDs polyester slurry, 80 parts of terephthalic acid, and 35 parts of ethylene glycol were put into a polymerization reactor for esterification and polycondensation reactions. The pressure and temperature of the reactor were controlled at 0.30 MPa and 235 °C respectively, and the esterification reaction was carried out for 2 h; then the vacuum pump was turned on for pre-polycondensation. At this time, the pressure and temperature of the reactor were -0.09 MPa and 260 °C respectively, and the pre-polycondensation reaction was carried out for 0.5 h; the vacuum degree was increased to 20 Pa, and the temperature was controlled at 270 °C for the final polycondensation reaction for 2 h. Finally, through casting and pelletizing, a Cu-N-CQDs antibacterial and antiviral masterbatch was obtained;

[0041] (5) After drying the prepared Cu-N-CQDs antibacterial and antiviral masterbatch and polyethylene terephthalate at 100 °C for 24 h, the Cu-N-CQDs antibacterial and antiviral masterbatch was added to polyethylene terephthalate at a ratio of 10%, and after mixing evenly, it was added to a melt spinning machine for spinning to obtain antibacterial and antiviral fibers.

[0042] The breaking strength of the antibacterial and antiviral fiber spun from the Cu-N-CQDs antibacterial and antiviral masterbatch prepared by the present invention and polyethylene terephthalate is 3.2 cN / dtex, and the elongation at break is 15%. The antibacterial effects on Staphylococcus aureus, Escherichia coli, and Candida albicans can reach 99.5%, and the antiviral effect on influenza A virus (H1N1) reaches 99.3%. By detecting the photocatalytic degradation effect of the antibacterial and antiviral fiber on nicotine by ultra-high performance liquid chromatography (UPLC) under simulated sunlight, 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 the fiber is washed 50 times, the antibacterial rates against Escherichia coli and Staphylococcus aureus still reach more than 98%, the antiviral effect on influenza A virus (H1N1) reaches 97.7%, and after 75 minutes of sunlight irradiation, the degradation effect on nicotine reaches more than 97.6%. It has good water-wash resistance, high antibacterial and antiviral properties, and the property of eliminating fabric smoke odor.

[0043] Example 2. A preparation method and application of a synergistic antibacterial, antiviral, and deodorizing functional masterbatch, and the specific steps are as follows:

[0044] (1) By mass, 2.5 parts of o-phenylenediamine are ultrasonically dispersed in 100 parts of 95% ethanol for 60 min at a frequency of 30 kHz to prepare an o-phenylenediamine solution, and 4 parts of tartaric acid are ultrasonically dispersed in 100 parts of 95% ethanol for 60 min at a frequency of 30 kHz to prepare a tartaric acid solution. After mixing the o-phenylenediamine solution and the tartaric acid solution, they are added to a stainless steel autoclave and reacted at 200 °C for 5 h to obtain a dark brown solution. The obtained product is centrifugally washed 4 times with deionized water and absolute ethanol, and finally dried to obtain nitrogen-doped carbon quantum dots (N-CQDs).

[0045] (2) 6 parts of N-CQDs are added to 50 parts of deionized water and ultrasonically treated in an ultrasonic machine with a frequency of 30 kHz for 60 min to prepare an N-CQDs aqueous solution. 3 parts of copper nitrate are 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 subjected to condensation reflux at 80 °C. While stirring, 50 parts of 0.5 mol / L citric acid aqueous solution are gradually added dropwise to the flask and stirred at 90 °C for 5 h to obtain a dark-colored solution. The obtained product is washed and centrifuged with deionized water and absolute ethanol respectively, and finally dried to obtain an N-CQDs antibacterial agent (Cu-N-CQDs antibacterial agent) with nano-scale elemental copper loaded on the surface.

[0046] (3) 3.5 parts of suberic acid, 150 parts of Cu-N-CQDs antibacterial agent, and 10 parts of deionized water are added to 100 parts of ethylene glycol at 90 °C and stirred for 5 h to obtain a carboxylic acid-modified Cu-N-CQDs polyester slurry.

[0047] (4) Put 15 parts of carboxylic acid-modified Cu-N-CQDs polyester slurry, 80 parts of terephthalic acid, and 45 parts of ethylene glycol into a polymerization reactor for esterification and polycondensation reactions. Control the pressure and temperature of the reactor to be 0.430 MPa and 255 °C respectively, and carry out the esterification reaction for 3 h. Then turn on the vacuum pump for pre-polycondensation. At this time, the pressure and temperature of the reactor are -0.10 MPa and 270 °C respectively, and the pre-polymerization reaction is carried out for 1.5 h. Raise the vacuum degree to 100 Pa, control the temperature at 280 °C, and carry out the final polymerization reaction for 3 h. Finally, through casting and pelletizing, the Cu-N-CQDs antibacterial and antiviral masterbatch is obtained;

[0048] (5) After drying the prepared Cu-N-CQDs antibacterial and antiviral masterbatch and polyethylene terephthalate at 100 °C for 18 h, add the Cu-N-CQDs antibacterial and antiviral masterbatch to polyethylene terephthalate at a ratio of 15%. After mixing evenly, add it to a melt spinning machine for spinning to obtain antibacterial and antiviral fibers.

[0049] The breaking strength of the antibacterial and antiviral fibers spun from the Cu-N-CQDs antibacterial and antiviral masterbatch prepared by the present invention and polyethylene terephthalate is 3.4 cN / dtex, the breaking elongation rate is 20%, the antibacterial effects on Staphylococcus aureus, Escherichia coli, and Candida albicans can reach 99.9%, and the antiviral effect on influenza A virus H1N1 reaches 99.9%. By detecting the photocatalytic degradation effect of the antibacterial and antiviral fibers on nicotine by ultra-high performance liquid chromatography (UPLC) under simulated sunlight, it is found that after 75 minutes of sunlight irradiation, the degradation effect of the antibacterial and antiviral fibers on nicotine can reach more than 99.8%. After the fibers are washed 50 times, the antibacterial rates against Escherichia coli and Staphylococcus aureus still reach more than 98%, the antiviral effect on influenza A virus H1N1 reaches 99.3%, and after 75 minutes of sunlight irradiation, the degradation effect on nicotine reaches more than 98.1%. It has good water-wash resistance, high antibacterial and antiviral properties, and the property of eliminating fabric smoke odor.

[0050] Example 3, a preparation method and application of a synergistic antibacterial, antiviral, and deodorizing functional masterbatch, the specific steps are as follows:

[0051] (1) By mass, disperse 3.5 parts of o-phenylenediamine in 100 parts of 95% ethanol by ultrasonic dispersion at a frequency of 40 kHz for 40 min to prepare an o-phenylenediamine solution, disperse 4 parts of 4-aminobenzenesulfonic acid in 100 parts of 95% ethanol by ultrasonic dispersion at a frequency of 40 kHz for 40 min to prepare a 4-aminobenzenesulfonic acid solution. After mixing the o-phenylenediamine solution and the 4-aminobenzenesulfonic acid solution, add them to a stainless steel autoclave and react at 220 °C for 8 h to obtain a dark brown solution. The obtained product is centrifugally washed 3 times with deionized water and absolute ethanol, and finally dried to obtain nitrogen-doped carbon quantum dots (N-CQDs);

[0052] (2) Add 7 parts of N-CQDs to 50 parts of deionized water, and ultrasonicate in an ultrasonic machine with a frequency of 40 kHz for 40 min to prepare an N-CQDs aqueous solution. Dissolve 3 parts of copper chloride in 50 parts of deionized water to prepare a copper ion aqueous solution. Mix the N-CQDs aqueous solution and the copper ion aqueous solution in a flask, and then carry out condensation reflux at 80 °C. While stirring, gradually add 50 parts of 0.3 mol / L citric acid aqueous solution dropwise into the flask, and stir at 90 °C for 10 h to obtain a dark solution. Wash and centrifuge the obtained product with deionized water and absolute ethanol respectively, and finally dry to obtain an N-CQDs antibacterial agent (Cu-N-CQDs antibacterial agent) with nano elemental copper loaded on the surface;

[0053] (3) Add 4.5 parts of dodecanedioic acid, 120 parts of Cu-N-CQDs antibacterial agent and 10 parts of deionized water to 100 parts of ethylene glycol at 80 °C, and stir for 2 h to obtain a carboxylic acid-modified Cu-N-CQDs polyester slurry;

[0054] (4) Put 15 parts of carboxylic acid-modified Cu-N-CQDs polyester slurry, 80 parts of terephthalic acid and 35 parts of ethylene glycol into a polymerization reactor, and carry out esterification and polycondensation reactions. Control the pressure and temperature of the reactor to be 0.37 MPa and 235 °C respectively, and carry out the esterification reaction for 3 h; then turn on the vacuum pump for pre-polycondensation. At this time, the pressure and temperature of the reactor are -0.10 MPa and 265 °C respectively, and the pre-polycondensation reaction is 1 h; increase the vacuum degree to 60 Pa, control the temperature at 278 °C, and carry out the final polycondensation reaction for 2.5 h. Finally, through casting and pelletizing, a Cu-N-CQDs antibacterial and antiviral masterbatch is obtained;

[0055] (5) After drying the prepared Cu-N-CQDs antibacterial and antiviral masterbatch and polyethylene terephthalate at 100 °C for 24 h, add the Cu-N-CQDs antibacterial and antiviral masterbatch to polyethylene terephthalate at a ratio of 15%, mix evenly and then add it to a melt spinning machine for spinning to obtain antibacterial and antiviral fibers.

[0056] The breaking strength of the antibacterial and antiviral fiber spun from the Cu-N-CQDs antibacterial and antiviral masterbatch prepared by the present invention and polyethylene terephthalate is 3.5 cN / dtex, and the breaking elongation is 15%. The antibacterial effects against Staphylococcus aureus, Escherichia coli, and Candida albicans can reach 99.5%, and the antiviral effect against influenza A virus (H1N1) reaches 99.3%. By detecting the photocatalytic degradation effect of the antibacterial and antiviral fiber on nicotine by ultra-high performance liquid chromatography (UPLC) under simulated sunlight, 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 the fiber is washed 50 times, the antibacterial rates against Escherichia coli and Staphylococcus aureus still reach more than 97%, the antiviral effect against influenza A virus (H1N1) reaches 97.7%, and after 75 minutes of sunlight irradiation, the degradation effect on nicotine reaches more than 97.3%. It has good water-wash resistance, high antibacterial and antiviral properties, and the property of eliminating fabric smoke odor.

[0057] Example 4, a preparation method and application of a synergistic antibacterial, antiviral and deodorizing functional masterbatch, the specific steps are as follows:

[0058] (1) By mass, 4.5 parts of o-phenylenediamine are ultrasonically dispersed in 100 parts of 95% ethanol for 50 min at a frequency of 30 kHz to prepare an o-phenylenediamine solution, and 6 parts of folic acid are ultrasonically dispersed in 100 parts of 95% ethanol for 50 min at a frequency of 30 kHz to prepare a folic acid solution. After mixing the o-phenylenediamine solution and the folic acid solution, they are added to a stainless steel autoclave and reacted at 240 °C for 10 h to obtain a dark brown solution. The obtained product is centrifugally washed 5 times with deionized water and absolute ethanol, and finally dried to obtain nitrogen-doped carbon quantum dots (N-CQDs);

[0059] (2) 8 parts of N-CQDs are added to 50 parts of deionized water and ultrasonically treated in an ultrasonic machine with a frequency of 30 kHz for 50 min to prepare an N-CQDs aqueous solution. 4 parts of copper sulfate are 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 subjected to condensation reflux at 80 °C. While stirring, 50 parts of 0.4 mol / L citric acid aqueous solution are gradually added dropwise to the flask and stirred at 80 °C for 6 h to obtain a dark solution. The obtained product is washed and centrifuged with deionized water and absolute ethanol respectively, and finally dried to obtain an N-CQDs antibacterial agent (Cu-N-CQDs antibacterial agent) loaded with nano-elemental copper on the surface;

[0060] (3) 1.5 parts of sebacic acid, 180 parts of Cu-N-CQDs antibacterial agent and 10 parts of deionized water are added to 100 parts of ethylene glycol at 85 °C and stirred for 5 h to obtain a carboxylic acid-modified Cu-N-CQDs polyester slurry;

[0061] (4) Put 15 parts of carboxylic acid-modified Cu-N-CQDs polyester slurry, 80 parts of terephthalic acid, and 40 parts of ethylene glycol into a polymerization reactor, and carry out esterification and polycondensation reactions. Control the pressure and temperature of the reactor to be 0.42 MPa and 235 °C respectively, and carry out the esterification reaction for 2 h; then turn on the vacuum pump for pre-polycondensation. At this time, the pressure and temperature of the reactor are -0.09 MPa and 270 °C respectively, and the pre-polymerization reaction is carried out for 1.5 h; increase the vacuum degree to 75 Pa, control the temperature at 279 °C, and carry out the final polymerization reaction for 2 h. Finally, through casting and pelletizing, the Cu-N-CQDs antibacterial and antiviral masterbatch is obtained;

[0062] (5) After drying the prepared Cu-N-CQDs antibacterial and antiviral masterbatch and polyethylene terephthalate at 100 °C for 24 h, add the Cu-N-CQDs antibacterial and antiviral masterbatch to polyethylene terephthalate at a ratio of 20%, mix evenly and then add it to a melt spinning machine for spinning to obtain antibacterial and antiviral fibers.

[0063] The breaking strength of the antibacterial and antiviral fibers spun from the Cu-N-CQDs antibacterial and antiviral masterbatch prepared by the present invention and polyethylene terephthalate is 2.2 cN / dtex, the elongation at break is 24%, the antibacterial effect on Staphylococcus aureus, Escherichia coli, and Candida albicans can reach 99.9%, and the antiviral effect on influenza A virus H1N1 reaches 99.9%. By detecting the photocatalytic degradation effect of the antibacterial and antiviral fibers on nicotine under simulated sunlight by ultra-high performance liquid chromatography (UPLC), it is found that after 75 minutes of sunlight irradiation, the degradation effect of the antibacterial and antiviral fibers on nicotine can reach more than 99.3%. After the fibers are washed 50 times, the antibacterial rates against Escherichia coli and Staphylococcus aureus still reach more than 99%, the antiviral effect on influenza A virus H1N1 reaches 99.6%, and after 75 minutes of sunlight irradiation, the degradation effect on nicotine reaches more than 97.6%. It has good wash resistance, high antibacterial and antiviral properties, and the property of eliminating fabric smoke odor.

[0064] Example 5, A preparation method and application of a synergistic antibacterial, antiviral and deodorizing functional masterbatch, the specific steps are as follows:

[0065] (1) By mass, disperse 3.5 parts of o-phenylenediamine in 100 parts of 95% ethanol by ultrasonic dispersion at a frequency of 50 kHz for 30 min to prepare an o-phenylenediamine solution, disperse 10 parts of acetic acid in 100 parts of 95% ethanol by ultrasonic dispersion at a frequency of 50 kHz for 30 min to prepare an acetic acid solution, mix the o-phenylenediamine solution and the acetic acid solution and then add them to a stainless steel autoclave, react at 260 °C for 14 h to obtain a dark brown solution, and wash the obtained product 5 times by centrifugation with deionized water and absolute ethanol, and finally dry to obtain nitrogen-doped carbon quantum dots (N-CQDs);

[0066] (2) Add 9 parts of N-CQDs to 50 parts of deionized water and ultrasonicate in an ultrasonic machine with a frequency of 50 kHz for 30 min to prepare an N-CQDs aqueous solution. Dissolve 4 parts of copper sulfate in 50 parts of deionized water to prepare a copper ion aqueous solution. Mix the N-CQDs aqueous solution and the copper ion aqueous solution in a flask, and then carry out condensation reflux at 80 °C. While stirring, gradually add 50 parts of 0.3 mol / L ascorbic acid aqueous solution dropwise into the flask, and stir at 70 °C for 5 h to obtain a dark solution. Wash and centrifuge the obtained product with deionized water and absolute ethanol respectively, and finally dry to obtain an N-CQDs antibacterial agent with nano elemental copper loaded on the surface (Cu-N-CQDs antibacterial agent);

[0067] (3) Add 3.5 parts of adipic acid, 160 parts of Cu-N-CQDs antibacterial agent and 6 parts of deionized water to 100 parts of ethylene glycol at 90 °C, and stir for 3 h to obtain a carboxylic acid-modified Cu-N-CQDs polyester slurry;

[0068] (4) Put 20 parts of carboxylic acid-modified Cu-N-CQDs polyester slurry, 80 parts of terephthalic acid and 45 parts of ethylene glycol into a polymerization reactor, and carry out esterification and polycondensation reactions. Control the pressure and temperature of the reactor to be 0.36 MPa and 245 °C respectively, and carry out the esterification reaction for 3 h; then turn on the vacuum pump for pre-polycondensation. At this time, the pressure and temperature of the reactor are -0.09 MPa and 265 °C respectively, and the pre-polycondensation reaction is 0.5 h; increase the vacuum degree to 80 Pa, control the temperature at 280 °C, and carry out the final polycondensation reaction for 3 h. Finally, through casting and pelletizing, a Cu-N-CQDs antibacterial and antiviral masterbatch is obtained;

[0069] (5) After drying the prepared Cu-N-CQDs antibacterial and antiviral masterbatch and polyethylene terephthalate at 100 °C for 24 h, add the Cu-N-CQDs antibacterial and antiviral masterbatch to polyethylene terephthalate at a ratio of 13%, mix evenly and then add it to a melt spinning machine for spinning to obtain antibacterial and antiviral fibers.

[0070] The breaking strength of the antibacterial and antiviral fiber spun from the Cu-N-CQDs antibacterial and antiviral masterbatch prepared by the present invention and polyethylene terephthalate is 3.1 cN / dtex, and the elongation at break is 20%. The antibacterial effects on Staphylococcus aureus, Escherichia coli, and Candida albicans can reach 99.7%, and the antiviral effect on influenza A virus (H1N1) reaches 99.3%. By detecting the photocatalytic degradation effect of the antibacterial and antiviral fiber on nicotine under simulated sunlight by ultra-high performance liquid chromatography (UPLC), 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 99.4%. After the fiber is washed 50 times, the antibacterial rates against Escherichia coli and Staphylococcus aureus still reach more than 98%, the antiviral effect on influenza A virus (H1N1) reaches 98.2%, and after 75 minutes of sunlight irradiation, the degradation effect on nicotine reaches more than 97.8%. It has good water-wash resistance, high antibacterial and antiviral properties, and the ability to eliminate fabric smoke odor.

Claims

1. A preparation method of a synergistic antibacterial, antiviral and deodorizing functional masterbatch, characterized in that: The method comprises the following steps: (1) By mass, 2 - 5 parts of o-phenylenediamine are ultrasonically dispersed in 100 parts of 95% ethanol to prepare an o-phenylenediamine solution, and 2 - 10 parts of an acid are ultrasonically dispersed in 100 parts of 95% ethanol to prepare an acid solution. After mixing the o-phenylenediamine solution and the acid solution, they are added into a stainless steel autoclave and reacted at 160 - 260 °C for 0.5 - 18 h to obtain a dark brown solution. The obtained product is washed with deionized water and absolute ethanol, centrifuged and separated, and finally dried to obtain nitrogen-doped carbon quantum dots N-CQDs; wherein, the conditions for ultrasonic dispersion of o-phenylenediamine and the acid refer to a time of 20 - 60 min and an ultrasonic frequency of 30 - 60 kHz; the acid refers to one of benzenesulfonic acid, folic acid, boric acid, acetic acid, terephthalic acid, and tartaric acid; (2) 3 - 10 parts of N-CQDs are ultrasonically dispersed in 50 parts of deionized water to prepare an N-CQDs aqueous solution, and 3 - 4 parts of a copper salt are 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 while condensing and refluxing and stirring, 50 parts of a reducing agent aqueous solution are added dropwise into the flask, and stirred at 60 - 90 °C for 3 - 20 h to obtain a dark-colored solution; the obtained product is washed with deionized water and absolute ethanol, centrifuged and separated, and finally dried to obtain a Cu-N-CQDs antibacterial agent; (3) 3 - 5 parts of an aliphatic dibasic acid, 5 - 10 parts of deionized water, and 100 - 200 parts of the Cu-N-CQDs antibacterial agent are added to 100 parts of ethylene glycol at 80 - 90 °C, and stirred for 0.5 - 5 h to obtain a carboxylic acid-modified Cu-N-CQDs polyester slurry; (4) 10 - 20 parts of the carboxylic acid-modified Cu-N-CQDs polyester slurry, 80 parts of terephthalic acid, and 35 - 45 parts of ethylene glycol are added into a polymerization reactor, first esterified, then pre-polymerized and finally polymerized, and finally pelletized through casting and granulation to obtain an antibacterial and antiviral functional masterbatch.

2. The preparation method of a synergistic antibacterial, antiviral and deodorizing functional masterbatch according to claim 1, characterized in that, In step (2), the conditions for ultrasonic dispersion of the nitrogen-doped carbon quantum dots refer to a time of 20 - 60 min and an ultrasonic frequency of 30 - 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 - 0.5 mol / L of citric acid, hydrazine hydrate, sodium borohydride, ascorbic acid, sodium hypophosphite, and tetrabutylammonium borohydride aqueous solutions.

3. The preparation method and application of a synergistic antibacterial, antiviral and deodorizing functional masterbatch according to claim 1, characterized in that, In step (3), the aliphatic dibasic acid refers to one of adipic acid, suberic acid, sebacic acid, and dodecanedioic acid.

4. The preparation method of a synergistic antibacterial, antiviral and deodorizing functional masterbatch according to claim 1, characterized in that, In step (4), the reaction conditions for esterification are a temperature of 235 to 255 °C, a pressure of 0.3 to 0.4 MPa, and a time of 2 to 3 h; the reaction conditions for prepolymerization are a temperature of 260 to 270 °C, a pressure of -0.09 to -0.10 MPa, and a time of 0.5 to 1.5 h; the reaction conditions for final polymerization are a temperature of 270 to 280 °C, a pressure of 20 to 100 Pa (absolute pressure), and a time of 2 to 3 h.

5. Application of a synergistic antibacterial, antiviral, and deodorizing functional masterbatch, Characterized in that: The antibacterial and antiviral masterbatch prepared by the preparation method according to any one of claims 1 to 4 and the matrix resin are dried at 90 to 120 °C for a period of time, and then the two are mixed evenly in proportion and added to a melt spinning machine for spinning to obtain antibacterial and antiviral fibers.

6. The application of a synergistic antibacterial, antiviral, and deodorizing functional masterbatch according to claim 5, Characterized in that, The matrix resin is one of polyethylene terephthalate, polytrimethylene terephthalate, and polybutylene terephthalate; the ratio of the antibacterial and antiviral masterbatch to the matrix resin is that the antibacterial and antiviral masterbatch accounts for 10 to 20% of the matrix resin.

7. The application of a synergistic antibacterial, antiviral, and deodorizing functional masterbatch according to claim 6, Characterized in that, The breaking strength of the antibacterial and antiviral fiber is 2.2 to 3.5 cN / dtex, the elongation at break is 15 to 30%, the antibacterial effect against Staphylococcus aureus, Escherichia coli, and Candida albicans reaches over 99%, the antiviral effect against influenza A virus (H1N1) reaches over 99%. By detecting the photocatalytic degradation effect of the antibacterial and antiviral fiber on nicotine under simulated sunlight by ultra-high performance liquid chromatography (UPLC), it is found that after 75 minutes of sunlight irradiation, the degradation effect of the antibacterial and antiviral fiber on nicotine reaches over 99%. After the fiber is washed 50 times, the antibacterial rate against Escherichia coli and Staphylococcus aureus still reaches over 97%, the antiviral effect against influenza A virus (H1N1) reaches over 97%, and after 75 minutes of sunlight irradiation, the degradation effect on nicotine reaches over 97%.