CN115044073A - Preparation method and application of nano-copper master batch with antibacterial and antiviral functions - Google Patents
Preparation method and application of nano-copper master batch with antibacterial and antiviral functions Download PDFInfo
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- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
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- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
The invention relates to a preparation method and application of a nano-copper antibacterial and antiviral functional master batch, in particular to a preparation method and application of a functional master batch for realizing antibacterial and antiviral effects through synergism of nano-copper and titanium dioxide. Firstly, generating nano elemental copper on the surface of titanium dioxide by an in-situ reduction method, then modifying the titanium dioxide carboxylic acid loaded with the nano elemental copper, and introducing polyamide 6 through in-situ polymerization to obtain the antibacterial and antiviral master batch. The antibacterial and antiviral master batch can be melt-spun with polyamide resin according to a certain proportion to obtain the antibacterial and antiviral fiber. The antibacterial and antiviral master batch prepared by the invention does not cause harm to the environment in the using process, and the antibacterial and antiviral fiber prepared by the master batch has the characteristics of high efficiency, lasting antibacterial and antiviral property.
Description
Technical Field
The invention belongs to the field of preparation of high-molecular functional master batches, relates to a preparation method and application of a nano-copper antibacterial and antiviral functional master batch, and particularly relates to a preparation method and application of a functional master batch for realizing antibacterial and antiviral effects through nano-copper and titanium dioxide.
Background
The health risk caused by pathogenic bacteria brings a severe examination to people who are suddenly prevented, and arouses the public health safety awareness of the living environment. The harm to human health caused by breeding and cross infection of pathogenic bacteria is difficult to estimate. The textile becomes an important transmission medium of pathogenic bacteria, the antibacterial function of the textile is also paid more and more attention, and the development of the antibacterial and antiviral functional fiber has important significance.
The antibacterial fiber includes organic antibacterial fiber, inorganic antibacterial fiber, etc. The organic antibacterial agent has high bactericidal strength, high speed and good effect, but has poor heat resistance, easy migration, easy decomposition, easy generation of microbial drug resistance, high toxicity to human bodies, short service life and the like, thereby greatly limiting the application range of the organic antibacterial agent. The inorganic antibacterial agent has the advantages of broad-spectrum antibacterial, good stability, lasting effect, high safety and the like, and is the key point of the current antibacterial agent research.
In recent years, the antibacterial fiber prepared by melt spinning the silver-containing antibacterial agent in a master batch blending mode is greatly developed in China, but the silver-containing antibacterial agent is expensive and easily degraded by heating, and can damage stem cells, brain cells, liver cells and the like. The use of antibacterial nano silver in clothing and other textiles has been restricted by publicity abroad. TiO 2 2 High heat resistance, wide sources, low cost, remarkable antibacterial effect, high research value and high production practicability. TiO 2 2 Usually, the dispersibility in polyamide is poor, and the formed agglomerate influences the spinnability of later fiber, namely TiO 2 Belongs to a photocatalytic antibacterial antiviral agent, can excite the antibacterial antiviral property of the compound under the condition of illumination, and has limited use conditions. The nano Cu serving as an antibacterial antiviral agent can well solve the problems, has good antibacterial and antiviral properties, does not overflow ions during antibacterial and antiviral processes, and is healthy and environment-friendly.
Disclosure of Invention
The purpose of the invention is to provideA preparation method and application of a nano-copper antibacterial and antiviral functional master batch, in particular to a preparation method and application of a functional master batch for realizing antibacterial and antiviral effects through the synergistic effect of nano-copper and titanium dioxide. By loading nano Cu powder on TiO which is uniformly dispersed 2 Can improve the dispersibility of the nano Cu, improve the antibacterial and antiviral effects, and simultaneously, the TiO 2 Also has certain antibacterial and antiviral effects, and can be used for synergistically resisting bacteria and viruses to further improve the antibacterial and antiviral effects. The nano elemental copper plays a role in resisting bacteria and viruses by releasing Reactive Oxygen Species (ROS), and does not pollute the environment during resisting bacteria and viruses. The size of the nano elemental copper obtained by the invention is 2-10nm, the nano elemental copper has higher catalytic reaction antibacterial and antiviral activity, the nano copper can activate oxygen in water and air to generate ROS (reactive oxygen species), and the ROS (hydroxyl free radicals, superoxide free radicals and hydrogen peroxide) have strong oxidability and can directly or indirectly damage the structure and the function of cells, so that cell membranes are ruptured to cause the death of bacteria. Further, Cu @ TiO modified by carboxylic acid 2 Not only has better compatibility with polyamide 6, but also is carboxylic acid modified Cu @ TiO in-situ polymerization of polyamide 6 monomer 2 Can be uniformly and stably dispersed in polyamide 6, and avoids nanoscale Cu @ TiO 2 The problem of agglomeration. The nano-copper has more exposed surface defects, and carboxyl can be well complexed with the nano-copper to maintain Cu @ TiO 2 The nano-copper is always in a reduction state, active oxygen free radicals are continuously released to play the role of resisting bacteria and viruses, and the complexed carboxyl can promote the nano-copper to generate the active oxygen free radicals, so that the antibacterial and antiviral effects are further improved. Therefore, the master batch obtained by the invention has high-efficiency and durable antibacterial and antiviral effects, and the antibacterial and antiviral master batch can be spun into fibers by using different matrixes, so that the higher requirements of different fields on the antibacterial and antiviral performance of the fibers are met. Prepared Cu @ TiO by using aliphatic dibasic acid 2 The carboxylic acid is modified, the carboxyl can be combined with the exposed defects on the surface of the nano Cu, the stability of the nano Cu structure is facilitated, the antibacterial and antiviral aging is prolonged, the generation of peroxy radicals is facilitated, and the antibacterial and antiviral effects are enhanced.
According to a first aspect of the present invention, the present invention provides a method for preparing a nano-copper master batch with antibacterial and antiviral functions, comprising the following steps:
(1) 2-5 parts of TiO by mass 2 TiO is prepared by ultrasonic dispersion in 50 parts of deionized water 2 And (3) dissolving 0.2-1.0 part of copper salt in 50 parts of deionized water to prepare a copper ion aqueous solution. Adding TiO into the mixture 2 Mixing caprolactam slurry and a copper ion aqueous solution in a flask, carrying out condensation reflux, dropwise adding 50 parts of a reducing agent aqueous solution into the flask while stirring, and stirring at 60-90 ℃ for 3-24 h to obtain a dark solution. Washing the obtained product with deionized water and absolute ethyl alcohol, performing centrifugal separation, and finally drying to obtain titanium dioxide (Cu @ TiO) with surface loaded with nano elemental copper 2 ) An antibacterial agent. The size of the generated nano simple substance copper is 2-10 nm;
(2) 3-5 parts of aliphatic dibasic acid, 5-10 parts of deionized water and 100-200 parts of Cu @ TiO 2 And adding 100 parts of liquid caprolactam at the temperature of 80-90 ℃, and stirring for 0.5-5 h to obtain the titanium dioxide caprolactam slurry with the carboxylic acid modified surface generating nano elemental copper.
(3) Adding 30-40 parts of carboxylic acid modified titanium dioxide caprolactam slurry with nano elemental copper generated on the surface, 100 parts of caprolactam and 3-5 parts of deionized water into a polymerization reaction kettle, opening a ring, performing prepolymerization, performing polycondensation, and finally performing belt casting, grain cutting and extraction to obtain the antibacterial and antiviral polyamide 6 functional master batch.
The preparation method of the nano-copper master batch with antibacterial and antiviral functions comprises the step (1) of preparing the TiO master batch 2 The ultrasonic dispersion condition is that the time is 20-60 min, and the ultrasonic frequency is 30-60 kHz;
in the preparation method of the nano-copper master batch with antibacterial and antiviral functions, in the step (1), the copper salt is one of copper chloride, copper sulfate and copper nitrate;
according to the preparation method of the nano-copper master batch with antibacterial and antiviral functions, in the step (1), the reducing agent aqueous solution is 0.1-0.5 mol/L of one of citric acid, hydrazine hydrate, sodium borohydride, ascorbic acid, sodium hypophosphite and tetrabutylammonium borohydride aqueous solution;
in the preparation method of the nano-copper master batch with antibacterial and antiviral functions, in the step (2), the aliphatic dibasic acid is one of adipic acid, suberic acid, sebacic acid and dodecanedioic acid;
according to the preparation method of the nano-copper master batch with the antibacterial and antiviral functions, in the step (3), the reaction conditions of ring-opening prepolymerization are that the temperature is 200-260 ℃, the pressure is 0.1-1.0 MPa, and the time is 2-5 h;
according to the preparation method of the nano-copper master batch with the antibacterial and antiviral functions, in the step (3), the condensation polymerization reaction conditions are that the temperature is 240-260 ℃, the pressure is-0.02-0.10 MPa, and the time is 2-5 hours.
The second aspect of the invention provides the application of the nano-copper antibacterial and antiviral master batch, which adopts the following technical scheme:
drying the prepared antibacterial and antiviral master batch and polyamide resin at 90-120 ℃ for a period of time, blending the two according to a certain proportion, uniformly mixing, and adding the mixture into a melt spinning machine for spinning to obtain the antibacterial and antiviral fiber.
The application of the antibacterial and antiviral master batch is characterized in that the polyamide resin is one of polyamide 6 and polyamide 66;
according to the application of the antibacterial and antiviral functional master batch, the antibacterial and antiviral master batch accounts for 10-20% of the polyamide resin in the ratio of the antibacterial and antiviral master batch to the polyamide resin;
the application of the antibacterial and antiviral master batch has the advantages that the breaking strength of spun fibers is 2.8-4.0 cN/dtex, the elongation at break is 15-30%, the antibacterial effect on staphylococcus aureus, escherichia coli and candida albicans can reach more than 99%, the antiviral effect on H1N1 influenza A virus can reach more than 99%, the antibacterial rate on escherichia coli and staphylococcus aureus can still reach more than 97% after the fibers are washed for 50 times, the antiviral effect on H1N1 influenza A virus can reach more than 97%, and the antibacterial and antiviral master batch has good water washing resistance and high-efficiency antibacterial and antiviral performance.
Due to the adoption of the technical scheme, the invention can obtain the following beneficial effects:
1. the invention adopts the nano Cu as the main antibacterial antiviral agent, has no ion overflow and does not cause harm to the environment.
2. The invention adopts TiO 2 The antibacterial agent loaded with the nano Cu has good dispersibility and compatibility in polyamide and has small influence on the spinning performance and the fiber mechanical property of the polyamide.
3. The nano copper in the antibacterial and antiviral master batch is always in a reduction state, plays an antibacterial and antiviral role by continuously releasing active oxygen free radicals, and has high-efficiency and lasting antibacterial and antiviral effects.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Embodiment 1, a preparation method and application of a master batch with efficient antibacterial and antiviral functions, specifically comprising the following steps:
(1) according to the mass portion, 2 portions of TiO 2 Adding into 50 parts of deionized water, and carrying out ultrasonic treatment in an ultrasonic machine with the frequency of 60kHz for 20min to prepare TiO 2 A caprolactam slurry. 0.2 part of copper sulfate was dissolved in 50 parts of deionized water to prepare a copper ion aqueous solution. Adding TiO into the mixture 2 Mixing caprolactam slurry and a copper ion aqueous solution in a flask, then carrying out condensation reflux at the temperature of 80 ℃, dropwise adding 50 parts of 0.1mol/L citric acid aqueous solution into the flask while stirring, and stirring for 3 hours at the temperature of 60 ℃ to obtain a dark solution. Washing and centrifuging the obtained product by using deionized water and absolute ethyl alcohol respectively, and finally drying to obtain Cu @ TiO 2 An antibacterial agent.
(2) 3 parts of suberic acid, 100 parts of Cu @ TiO 2 Adding 5 parts of deionized water into 100 parts of liquid caprolactam at the temperature of 80 ℃, and stirring for 0.5h to obtain carboxylic acid modified Cu @ TiO 2 Caprolactam slurry.
(3) 30 parts of carboxylic acid modified Cu @ TiO 2 Adding caprolactam slurry, 100 parts of caprolactam and 3 parts of deionized water into a polymerization reaction kettle, performing ring-opening prepolymerization at 200 ℃ and 0.1MPa for 2 hours, performing polycondensation at 240 ℃ and-0.02 MPa for 2 hours, and finally performing belt casting, grain cutting and extraction to obtain the efficient antibacterial and antiviral master batch.
(4) The prepared Cu @ TiO 2 Drying the antibacterial and antiviral master batch and polyamide 6 at 110 ℃ for 24h, and then adding Cu @ TiO 2 The antibacterial and antiviral master batch is added with polyamide 6 according to the proportion of 10 percent, and the mixture is added into a melt spinning machine for spinning after being uniformly mixed to obtain the antibacterial and antiviral fiber.
Cu @ TiO prepared by the invention 2 The antibacterial and antiviral fiber obtained by spinning the antibacterial and antiviral master batch and polyamide 6 has the breaking strength of 4.0cN/dtex, the elongation at break of 15 percent, the antibacterial effect on staphylococcus aureus, escherichia coli and candida albicans of 99.5 percent, the antiviral effect on influenza A H1N1 of 99.3 percent, the antibacterial rate on escherichia coli and staphylococcus aureus of more than 98 percent after the fiber is washed for 50 times, the antiviral effect on influenza A H1N1 of 97.7 percent, and good water washing resistance and high-efficiency antibacterial and antiviral performance.
Embodiment 2, a preparation method and application of a master batch with high-efficiency antibacterial and antiviral functions, comprising the following specific steps:
(1) according to the mass portion, 5 portions of TiO 2 Adding into 50 parts of deionized water, and performing ultrasonic treatment in an ultrasonic machine with the frequency of 30kHz for 60min to prepare TiO 2 A caprolactam slurry. 1 part of copper nitrate was dissolved in 50 parts of deionized water to prepare a copper ion aqueous solution. Adding TiO into the mixture 2 Mixing caprolactam slurry and a copper ion aqueous solution in a flask, then carrying out condensation reflux at the temperature of 80 ℃, dropwise adding 50 parts of 0.5mol/L citric acid aqueous solution into the flask while stirring, and stirring for 5 hours at the temperature of 90 ℃ to obtain a dark solution. Washing and centrifuging the obtained product by using deionized water and absolute ethyl alcohol respectively, and finally drying to obtain Cu @ TiO 2 An antibacterial agent.
(2) 5 parts of suberic acid and 200 parts of Cu @ TiO 2 And 10 part of deionized water is added into 100 parts of liquid caprolactam at the temperature of 90 ℃, and the mixture is stirred for 5 hours to obtain carboxylic acid modified Cu @ TiO 2 Caprolactam slurry.
(3) 40 parts of carboxylic acid modified Cu @ TiO 2 Adding caprolactam slurry, 100 parts of caprolactam and 5 parts of deionized water into a polymerization reaction kettle, performing ring-opening prepolymerization at 260 ℃ and 1.0MPa for 5 hours, performing polycondensation at 260 ℃ and-0.10 MPa for 5 hours, and finally performing belt casting, grain cutting and extraction to obtain the efficient antibacterial and antiviral master batch.
(4) The prepared Cu @ TiO 2 Drying the antibacterial and antiviral master batch and polyamide 6 at 110 ℃ for 36h, and then adding Cu @ TiO 2 Adding polyamide 6 into the antibacterial and antiviral master batch according to a proportion of 15%, uniformly mixing, and then adding the mixture into a melt spinning machine for spinning to obtain the antibacterial and antiviral fiber.
Cu @ TiO prepared by the invention 2 The antibacterial and antiviral fiber obtained by spinning the antibacterial and antiviral master batch and polyamide 6 has the breaking strength of 3.2cN/dtex, the elongation at break of 20 percent, the antibacterial effect on staphylococcus aureus, escherichia coli and candida albicans of 99.9 percent, the antiviral effect on influenza A H1N1 of 99.9 percent, the antibacterial rate on escherichia coli and staphylococcus aureus of more than 98 percent after the fiber is washed for 50 times, the antiviral effect on influenza A H1N1 of 99.3 percent, and good water washing resistance and high-efficiency antibacterial and antiviral performance.
Embodiment 3, a preparation method and application of a master batch with high-efficiency antibacterial and antiviral functions, comprising the following specific steps:
(1) according to the mass portion, 3 portions of TiO 2 Adding into 50 parts of deionized water, and carrying out ultrasonic treatment in an ultrasonic machine with the frequency of 40kHz for 40min to prepare TiO 2 A caprolactam slurry. 0.5 part of copper chloride was dissolved in 50 parts of deionized water to prepare an aqueous copper ion solution. Adding TiO into the mixture 2 Mixing caprolactam slurry and a copper ion aqueous solution in a flask, then carrying out condensation reflux at the temperature of 80 ℃, dropwise adding 50 parts of 0.3mol/L citric acid aqueous solution into the flask while stirring, and stirring for 10 hours at the temperature of 90 ℃ to obtain a dark solution. Washing and centrifuging the obtained product by using deionized water and absolute ethyl alcohol respectively, and finally drying to obtain Cu@TiO 2 An antibacterial agent.
(2) 3 parts of dodecanedioic acid and 100 parts of Cu @ TiO 2 Adding 10 parts of deionized water into 100 parts of liquid caprolactam at 80 ℃, and stirring for 2 hours to obtain carboxylic acid modified Cu @ TiO 2 Caprolactam slurry.
(3) 30 parts of carboxylic acid modified Cu @ TiO 2 Adding caprolactam slurry, 100 parts of caprolactam and 4 parts of deionized water into a polymerization reaction kettle, performing ring-opening prepolymerization at 230 ℃ and 0.6MPa for 4 hours, performing polycondensation at 250 ℃ and-0.05 MPa for 4 hours, and finally performing belt casting, grain cutting and extraction to obtain the efficient antibacterial and antiviral master batch.
(4) The prepared Cu @ TiO 2 Drying the antibacterial and antiviral master batch and polyamide 6 at 110 ℃ for 30h, and then adding Cu @ TiO 2 Adding polyamide 6 into the antibacterial and antiviral master batch according to a proportion of 20%, uniformly mixing, and then adding the mixture into a melt spinning machine for spinning to obtain the antibacterial and antiviral fiber.
Cu @ TiO prepared by the invention 2 The antibacterial and antiviral fiber obtained by spinning the antibacterial and antiviral master batch and polyamide 6 has the breaking strength of 4.0cN/dtex, the elongation at break of 15 percent, the antibacterial effect on staphylococcus aureus, escherichia coli and candida albicans of 99.5 percent, the antiviral effect on H1N1 influenza A virus of 99.3 percent, the antibacterial rate on escherichia coli and staphylococcus aureus of more than 97 percent after the fiber is washed for 50 times, the antiviral effect on H1N1 influenza A virus of 97.7 percent, and better water washing resistance and high-efficiency antibacterial and antiviral performance.
Embodiment 4, a preparation method and application of a master batch with high-efficiency antibacterial and antiviral functions, comprising the following specific steps:
(1) according to the mass portion, 4 portions of TiO 2 Adding into 50 parts of deionized water, and carrying out ultrasonic treatment in an ultrasonic machine with the frequency of 30kHz for 50min to prepare TiO 2 A caprolactam slurry. An aqueous solution of copper ions was prepared by dissolving 0.7 parts of copper sulfate in 50 parts of deionized water. Adding TiO into the mixture 2 Mixing caprolactam slurry and copper ion aqueous solution in a flask, condensing and refluxing at 80 ℃, dropwise adding 50 parts of 0.4mol/L citric acid aqueous solution into the flask while stirring, and stirring at 80 DEGStirring at deg.C for 6h to obtain a dark solution. Washing and centrifuging the obtained product by using deionized water and absolute ethyl alcohol respectively, and finally drying to obtain Cu @ TiO 2 An antibacterial agent.
(2) 3 parts of sebacic acid and 200 parts of Cu @ TiO 2 Adding 10 parts of deionized water into 100 parts of liquid caprolactam at 85 ℃, and stirring for 5 hours to obtain carboxylic acid modified Cu @ TiO 2 And (3) caprolactam sizing agent.
(3) 40 parts of carboxylic acid modified Cu @ TiO 2 Adding caprolactam slurry, 100 parts of caprolactam and 5 parts of deionized water into a polymerization reaction kettle, firstly carrying out ring-opening prepolymerization at 250 ℃ and 0.5Mpa for 4 hours, then carrying out polycondensation at 240 ℃ and-0.06 Mpa for 3 hours, and finally carrying out belt casting, grain cutting and extraction to obtain the high-efficiency antibacterial antiviral master batch.
(4) The prepared Cu @ TiO 2 Drying the antibacterial and antiviral master batch and polyamide 6 at 120 ℃ for 24h, and then adding Cu @ TiO 2 The antibacterial and antiviral master batch is added with polyamide 6 according to the proportion of 20 percent, and the mixture is added into a melt spinning machine for spinning after being uniformly mixed to obtain the antibacterial and antiviral fiber.
Cu @ TiO prepared by the invention 2 The antibacterial and antiviral fiber obtained by spinning the antibacterial and antiviral master batch and polyamide 6 has the breaking strength of 2.8cN/dtex, the elongation at break of 24 percent, the antibacterial effect on staphylococcus aureus, escherichia coli and candida albicans of 99.9 percent, the antiviral effect on influenza A H1N1 of 99.9 percent, the antibacterial rate on escherichia coli and staphylococcus aureus of more than 99 percent after the fiber is washed for 50 times, the antiviral effect on influenza A H1N1 of 99.6 percent, and good water washing resistance and high-efficiency antibacterial and antiviral performance.
Embodiment 5, a preparation method and application of a master batch with high-efficiency antibacterial and antiviral functions, comprising the following specific steps:
(1) according to the mass portion, 4 portions of TiO 2 Adding into 50 parts of deionized water, and carrying out ultrasonic treatment in an ultrasonic machine with the frequency of 50kHz for 30min to prepare TiO 2 A caprolactam slurry. 0.6 part of copper sulfate was dissolved in 50 parts of deionized water to prepare a copper ion aqueous solution. Adding TiO into the mixture 2 Mixing caprolactam slurry and copper ion water solution in a flaskThe mixture was refluxed by condensation at 80 ℃ and 50 parts of 0.3mol/L ascorbic acid aqueous solution was added dropwise to the flask while stirring, and stirred at 70 ℃ for 5 hours to obtain a dark solution. Washing and centrifuging the obtained product by using deionized water and absolute ethyl alcohol respectively, and finally drying to obtain Cu @ TiO 2 An antibacterial agent.
(2) 3 parts of adipic acid and 150 parts of Cu @ TiO 2 Adding 6 parts of deionized water into 100 parts of 90 ℃ liquid caprolactam, and stirring for 3 hours to obtain carboxylic acid modified Cu @ TiO 2 Caprolactam slurry.
(3) 40 parts of carboxylic acid modified Cu @ TiO 2 Adding caprolactam slurry, 100 parts of caprolactam and 4 parts of deionized water into a polymerization reaction kettle, performing ring-opening prepolymerization at 240 ℃ and 0.8MPa for 5 hours, performing polycondensation at 250 ℃ and-0.09 MPa for 2 hours, and finally performing belt casting, grain cutting and extraction to obtain the efficient antibacterial and antiviral master batch.
(4) The prepared Cu @ TiO 2 Drying the antibacterial and antiviral master batch and polyamide 6 at 100 ℃ for 36h, and then adding Cu @ TiO 2 The antibacterial and antiviral master batch is added with polyamide 6 according to the proportion of 15 percent, and the mixture is added into a melt spinning machine for spinning after being uniformly mixed to obtain the antibacterial and antiviral fiber.
Cu @ TiO prepared by the invention 2 The antibacterial and antiviral fiber obtained by spinning the antibacterial and antiviral master batch and polyamide 6 has the breaking strength of 3.5cN/dtex, the elongation at break of 20 percent, the antibacterial effect on staphylococcus aureus, escherichia coli and candida albicans of 99.7 percent, the antiviral effect on influenza A H1N1 of 99.3 percent, the antibacterial rate on escherichia coli and staphylococcus aureus of more than 98 percent after the fiber is washed for 50 times, the antiviral effect on influenza A H1N1 of 98.2 percent, and the fiber has better water washing resistance and high-efficiency antibacterial and antiviral performance.
Claims (7)
1. A preparation method of nano-copper master batch with antibacterial and antiviral functions is characterized by comprising the following steps: the method comprises the following steps:
(1) 2-5 parts of TiO by mass 2 TiO is prepared by ultrasonic dispersion in 50 parts of deionized water 2 An aqueous solution of 0.2 to 1.0 part of copper saltPreparing copper ion aqueous solution in 50 parts of deionized water; adding TiO into the mixture 2 Mixing caprolactam slurry and a copper ion aqueous solution in a flask, carrying out condensation reflux, dropwise adding 50 parts of a reducing agent aqueous solution into the flask while stirring, and stirring at 60-90 ℃ for 3-24 hours to obtain a dark solution; washing and centrifugally separating the obtained product by using deionized water and absolute ethyl alcohol, and finally drying to obtain a titanium dioxide antibacterial agent with the surface generating nano elemental copper;
(2) adding 3-5 parts of aliphatic dibasic acid, 5-10 parts of deionized water and 100-200 parts of titanium dioxide with nano-elementary copper generated on the surface into 100 parts of 80-90 ℃ liquid caprolactam, and stirring for 0.5-5 hours to obtain carboxylic acid modified titanium dioxide caprolactam slurry with nano-elementary copper generated on the surface;
(3) adding 30-40 parts of carboxylic acid modified titanium dioxide caprolactam slurry with nano elemental copper generated on the surface, 100 parts of caprolactam and 3-5 parts of deionized water into a polymerization reaction kettle, opening a ring, performing prepolymerization, performing polycondensation, and finally performing belt casting, grain cutting and extraction to obtain the antibacterial and antiviral polyamide 6 functional master batch.
2. The method for preparing the nano-copper master batch with antibacterial and antiviral functions according to claim 1, wherein in the step (1), TiO is added 2 The ultrasonic dispersion condition is that the time is 20-60 min, and the ultrasonic frequency is 30-60 kHz; the copper salt is one of copper chloride, copper sulfate and copper nitrate; the reducing agent aqueous solution is one of 0.1-0.5 mol/L citric acid, hydrazine hydrate, sodium borohydride, ascorbic acid, sodium hypophosphite and tetrabutylammonium borohydride aqueous solution.
3. The preparation method and application of the nano-copper antibacterial and antiviral master batch according to claim 1, wherein in the step (2), the aliphatic dibasic acid is one of adipic acid, suberic acid, sebacic acid and dodecanedioic acid.
4. The preparation method and the application of the nano-copper antibacterial and antiviral master batch according to claim 1 are characterized in that in the step (3), the ring-opening prepolymerization reaction conditions are that the temperature is 200-260 ℃, the pressure is 0.1-1.0 MPa, and the time is 2-5 h; the reaction conditions of polycondensation are that the temperature is 240-260 ℃, the pressure is-0.02 to-0.10 MPa, and the time is 2-5 h.
5. The application of the nano-copper master batch with the antibacterial and antiviral functions is characterized in that: drying the antibacterial and antiviral master batch prepared by the preparation method of any one of claims 1 to 4 and polyamide resin at 90-120 ℃ for a period of time, uniformly mixing the antibacterial and antiviral master batch and the polyamide resin according to a proportion, and adding the mixture into a melt spinning machine for spinning to obtain the antibacterial and antiviral fiber.
6. The application of the nano-copper antibacterial and antiviral master batch as claimed in claim 5, wherein the polyamide resin is one of polyamide 6 and polyamide 66; the proportion of the antibacterial and antiviral master batch to the polyamide resin is that the antibacterial and antiviral master batch accounts for 10-20% of the polyamide resin.
7. The application of the nano-copper antibacterial and antiviral functional master batch according to claim 5 is characterized in that the breaking strength of the antibacterial and antiviral fiber is 2.8-4.0 cN/dtex, the elongation at break is 15-30%, the antibacterial effect on staphylococcus aureus, escherichia coli and candida albicans can reach more than 99%, the antiviral effect on H1N1 influenza A virus can reach more than 99%, the antibacterial rate on escherichia coli and staphylococcus aureus can still reach more than 97% after the fiber is washed for 50 times, and the antiviral effect on H1N1 influenza A virus can reach more than 97%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115323522A (en) * | 2022-09-20 | 2022-11-11 | 江苏集萃先进纤维材料研究所有限公司 | Antibacterial polyamide fiber and preparation method thereof |
| CN115418774A (en) * | 2022-09-20 | 2022-12-02 | 江苏集萃先进纤维材料研究所有限公司 | Bio-based antibacterial one-way moisture-conducting woven belt and preparation method thereof |
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- 2022-06-02 CN CN202210624962.9A patent/CN115044073A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115323522A (en) * | 2022-09-20 | 2022-11-11 | 江苏集萃先进纤维材料研究所有限公司 | Antibacterial polyamide fiber and preparation method thereof |
| CN115418774A (en) * | 2022-09-20 | 2022-12-02 | 江苏集萃先进纤维材料研究所有限公司 | Bio-based antibacterial one-way moisture-conducting woven belt and preparation method thereof |
| CN115323522B (en) * | 2022-09-20 | 2023-08-18 | 江苏集萃先进纤维材料研究所有限公司 | Antibacterial polyamide fiber and preparation method thereof |
| CN115418774B (en) * | 2022-09-20 | 2024-01-30 | 江苏集萃先进纤维材料研究所有限公司 | Bio-based antibacterial unidirectional moisture-guiding woven belt and preparation method thereof |
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