CN109403021B - Nano carbon crystal pure cotton surface antibacterial fiber and preparation method thereof - Google Patents
Nano carbon crystal pure cotton surface antibacterial fiber and preparation method thereof Download PDFInfo
- Publication number
- CN109403021B CN109403021B CN201811286176.2A CN201811286176A CN109403021B CN 109403021 B CN109403021 B CN 109403021B CN 201811286176 A CN201811286176 A CN 201811286176A CN 109403021 B CN109403021 B CN 109403021B
- Authority
- CN
- China
- Prior art keywords
- nano carbon
- carbon crystal
- pure cotton
- fiber
- crystal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
Abstract
A nanometer carbon crystal pure cotton surface antibacterial fiber and a preparation method thereof, the surface antibacterial fiber is obtained by fixing modified nanometer carbon crystal to pure cotton fiber fabric; the modified nano carbon crystal is obtained by hydroxylating and silanizing the nano carbon crystal, and then modifying and chlorinating the nano carbon crystal by quaternary ammonium salt. The invention takes pure cotton fiber as a matrix material to prepare the nano carbon crystal antibacterial fabric with excellent washability, and the antibacterial fiber has high sterilization rate and good stability.
Description
Technical Field
The invention belongs to the technical field of textile materials, and particularly relates to a nano carbon crystal pure cotton surface antibacterial fiber and a preparation method thereof.
Background
The pure cotton fiber fabric is popular among people due to the advantages of good biodegradability, low price, high mechanical performance, wearing comfort and the like, and is the most fiber material contacting with human bodies. However, in the process of contacting human skin, some bacteria harmful to human body can rapidly propagate by using human dander, sweat and other secretions as nutrient sources, produce metabolites with pungent smell, even spread diseases, and threaten human health and development. Therefore, the development of textile fabrics with health care functions of antibiosis, deodorization, etc. is highly regarded by the textile industry.
At present, the common natural antibacterial agent has poor antibacterial performance, the organic antibacterial agent has poor heat resistance and low stability, and the inorganic antibacterial agent has good stability, but the common antibacterial agents except silver have low antibacterial performance. The report reports that the composite antibacterial material obtained by coating the nano silver on the quaternary ammonium salt shows strong bactericidal performance, however, the silver itself has harm to human body, so the research and development of novel composite antibacterial materials are inevitable trends in the development of antibacterial deodorization. The nano carbon crystal is expected to solve the problems due to excellent antibacterial performance, safety and no toxicity. But the poor dispersibility caused by the serious agglomeration phenomenon of the nano carbon crystal limits the further development and utilization of the nano carbon crystal. Although the prior art has a plurality of methods for modifying the nano carbon crystal, the nano carbon crystal and pure cotton fiber system which are suitable for the system of the invention are not suitable.
Disclosure of Invention
The invention aims to provide a nano carbon crystal pure cotton surface antibacterial fiber, and simultaneously provides a preparation method thereof, which is another aim of the invention.
In order to achieve the purpose, the invention adopts the technical scheme that:
a nano carbon crystal pure cotton surface antibacterial fiber is obtained by fixedly carrying modified nano carbon crystals to a pure cotton fiber matrix; the modified nano carbon crystal is obtained by hydroxylating and silanizing the nano carbon crystal, and then modifying and chlorinating the nano carbon crystal by quaternary ammonium salt.
The solid loading amount of the modified nano carbon crystal is 0.9-1.5% of the weight of the pure cotton fiber matrix.
The preparation method of the nano carbon crystal pure cotton surface antibacterial fiber comprises the following steps:
1) pretreating pure cotton fibers: boiling the pure cotton fiber with distilled water for half an hour to remove impurities which are attached to the fiber and are easy to dissolve in water, and placing the fiber in an oven for drying;
2) preparing 200-250mL of ethanol and water at a volume ratio of 1: 1, adding 5-10g of modified nano carbon crystal, stirring at a high speed of 1500rpm by a magnetic stirrer for 20-30min to form a suspension, and adding glacial acetic acid to adjust the pH value of the solution to 5.0-5.5;
3) adding the pretreated pure cotton fiber, reacting for 20-30min at 70-80 ℃, controlling the liquid carrying rate to be 140-85 ℃ after the reaction is finished, drying for 10-15min at 80-85 ℃, and then drying for 10-15min at 120-125 ℃ to obtain the nano carbon crystal pure cotton surface antibacterial fiber.
The modified nano carbon crystal is prepared by the following steps:
a) hydroxylation and silanization treatment of the nano carbon crystal: adding 2-10g of nano carbon crystal into 250mL of deionized water, placing the mixture into a 500mL beaker, and directly adding 20-25g of FeSO4·7H2O, ultrasonic treatment for 30-40min until FeSO is obtained4·7H2Dissolving O completely, placing the beaker in an ice bath-ultrasonic environment, and adding 30-40mL of concentrateAdding 30-40mL hydrogen peroxide (30 v/v%) dropwise, standing for 1-2H, and sequentially adding 2-3mL concentrated sulfuric acid and 1-3mL H2O2Circularly replenishing for 5-6 times until the color of the system changes from green yellow to light yellow, then changing the color to dark, and finally performing vacuum drying at 50-60 ℃ to obtain hydroxylated nano carbon crystals;
b) dispersing hydroxylated nano carbon crystals in 250mL of ethanol, performing ultrasonic treatment for 30-40min, adding 10-15mL of 3-bromoethyltrimethoxysilane, adding 3-5mL of deionized water and 1-3mL of acetic acid, stirring at 50-60 ℃ for reaction for 24h, performing centrifugal separation on the obtained silylated nano carbon crystals after the reaction is finished, dispersing in the ethanol, centrifuging, repeating the dispersion in the ethanol and the centrifugal operation for 3-4 times, and performing vacuum drying at 50-60 ℃ to obtain gray-black silylated nano carbon crystals;
c) modification and chlorination of nano carbon crystal quaternary ammonium salt: dissolving 2-3g of poly 4-vinylpyridine (PVP) in 250mL of nitromethane, adding the silylated nanocarbon crystals obtained in the step 2), ultrasonically dispersing for 40-50min, stirring and reacting at 60-70 ℃ for 12h, adding 3-5g of hydantoin compounds, reacting for 24h, centrifugally separating the obtained high molecular quaternary ammonium salt type product after the reaction is finished, dispersing and centrifuging in ethanol, repeating the steps of dispersing in ethanol and centrifuging for 3-4 times, and drying in vacuum at 50-60 ℃ to obtain light gray high molecular quaternary ammonium salt modified nanocarbon crystals;
d) ultrasonically dispersing the obtained high-molecular quaternary ammonium salt modified nano carbon crystal into 200mL of deionized water, adding 20-25g of 10wt% sodium hypochlorite solution into the dispersion liquid, stirring for 4-6h under the ice water bath condition, after the reaction is finished, carrying out centrifugal separation to obtain a solid product, washing with the deionized water, centrifuging again, repeatedly washing and centrifuging for 4-5 times, and carrying out vacuum drying for 3-5h to obtain the nano carbon crystal.
Compared with the prior art, the invention has the following positive effects:
the nano carbon crystal antibacterial fabric with excellent washability is prepared by taking the pure cotton fiber as a base material, the antibacterial fiber has high sterilization rate and good stability, the sterilization effect on escherichia coli and staphylococcus aureus can still reach 86.78% and 87.23% after the nano carbon crystal antibacterial fabric is washed in water at the temperature of 20 ℃ for 60 times, the nano carbon crystal antibacterial fabric shows good washability, and the antibacterial effect is superior to that of similar antibacterial products sold in the market. The nano carbon crystal has stable chemical property, good biocompatibility, rich surface groups and huge specific surface area, but poor dispersibility caused by serious agglomeration of the nano carbon crystal limits further development and utilization of the nano carbon crystal. The invention modifies the surface of the nano carbon crystal by the macromolecular quaternary ammonium salt, so that the surface of the nano carbon crystal is provided with a large amount of charges, and the repulsion between particles is enhanced, thereby achieving the purpose of deagglomeration. Meanwhile, the nano carbon crystal and the pure cotton fiber are firmly combined, and the washing resistance is good.
Drawings
FIG. 1 shows the variation of the nano carbon crystal content and the sterilization rate with the number of cleaning times.
Detailed Description
The present invention will be described in further detail with reference to the following examples and accompanying drawings.
Example 1
A nano carbon crystal pure cotton surface antibacterial fiber is obtained by fixedly carrying modified nano carbon crystals to a pure cotton fiber matrix; the modified nano carbon crystal is obtained by hydroxylating and silanizing the nano carbon crystal, and then modifying and chlorinating the nano carbon crystal by quaternary ammonium salt. The solid loading of the modified nano carbon crystal is 1.5 percent of the weight of the pure cotton fiber matrix.
The preparation method of the nano carbon crystal pure cotton surface antibacterial fiber comprises the following steps:
1) pretreating pure cotton fibers: boiling the pure cotton fiber with distilled water for half an hour to remove impurities which are attached to the fiber and are easy to dissolve in water, and placing the fiber in an oven for drying;
2) preparing 200-250mL of solution with the volume ratio of ethanol to water being 1: 1, adding 5g of modified nano carbon crystal, stirring at 1000rpm of a magnetic stirrer for 20min to form suspension, and adding glacial acetic acid to adjust the pH value of the solution to 5.0;
3) adding the pretreated pure cotton fiber, reacting for 20min at 70 ℃, controlling the liquid carrying rate to be 150% after the reaction is finished, drying for 10min at 80 ℃, and then drying for 10min at 120 ℃ to obtain the nano carbon crystal pure cotton surface antibacterial fiber.
The modified nano carbon crystal is prepared by the following steps:
a) hydroxylation and silanization treatment of the nano carbon crystal: 2g of nano carbon crystal is added into 250mL of deionized water and placed into a 500mL beaker, and 20g of FeSO is directly added4·7H2O, ultrasonic treatment for 30-40min until FeSO is obtained4·7H2Fully dissolving O, placing a beaker in an ice bath-ultrasonic environment, adding 30mL of concentrated sulfuric acid, dropwise adding 30mL of hydrogen peroxide (30 v/v%), standing for 1-2H, and sequentially adding 2-3mL of concentrated sulfuric acid and 1-3mL of H2O2Circularly replenishing for 5 times until the color of the system is changed from green yellow to light yellow, then changing the color to dark, and finally carrying out vacuum drying at 50 ℃ to obtain hydroxylated nano carbon crystals;
b) dispersing hydroxylated nano carbon crystals in 250mL of ethanol, carrying out ultrasonic treatment for 30min, adding 10mL of 3-bromoethyl trimethoxy silane, adding 3-5mL of deionized water and 1-3mL of acetic acid, stirring and reacting at 50 ℃ for 24h, carrying out centrifugal separation on the obtained silylated nano carbon crystals after the reaction is finished, dispersing and centrifuging in ethanol, repeating the dispersion and centrifugation operations in the ethanol for 3 times, and carrying out vacuum drying at 50 ℃ to obtain gray-black silylated nano carbon crystals;
c) modification and chlorination of nano carbon crystal quaternary ammonium salt: dissolving 2g of poly-4-vinylpyridine (PVP) in 250mL of nitromethane, adding the silylated nanocarbon crystal obtained in the step 2), performing ultrasonic dispersion for 40min, stirring and reacting at 60 ℃ for 12h, adding 3g of hydantoin compounds, reacting for 24h, after the reaction is finished, centrifugally separating the obtained high-molecular quaternary ammonium salt type product, dispersing and centrifuging in ethanol, repeating the dispersion and centrifugation operations in the ethanol for 3 times, and performing vacuum drying at 50-60 ℃ to obtain light gray high-molecular quaternary ammonium salt modified nanocarbon crystal;
d) ultrasonically dispersing the obtained high-molecular quaternary ammonium salt modified nano carbon crystal into 200mL of deionized water, adding 20g of 10wt% sodium hypochlorite solution into the dispersion liquid, stirring for 4h under the ice-water bath condition, after the reaction is finished, carrying out centrifugal separation to obtain a solid product, washing with the deionized water, centrifuging again, repeatedly washing and centrifuging for 4 times, and carrying out vacuum drying for 3h to obtain the nano carbon crystal.
Example 2
A nano carbon crystal pure cotton surface antibacterial fiber is obtained by fixedly carrying modified nano carbon crystals to a pure cotton fiber matrix; the modified nano carbon crystal is obtained by hydroxylating and silanizing the nano carbon crystal, and then modifying and chlorinating the nano carbon crystal by quaternary ammonium salt. The solid loading amount of the modified nano carbon crystal is 1.0 percent of the weight of the pure cotton fiber matrix.
The preparation method of the nano carbon crystal pure cotton surface antibacterial fiber comprises the following steps:
1) pretreating pure cotton fibers: boiling the pure cotton fiber with distilled water for half an hour to remove impurities which are attached to the fiber and are easy to dissolve in water, and placing the fiber in an oven for drying;
2) preparing 250mL of solution with the volume ratio of ethanol to water being 1: 1, adding 10g of modified nano carbon crystal, stirring at 1500rpm for 30min by a magnetic stirrer to form suspension, and adding glacial acetic acid to adjust the pH value of the solution to 5.5;
3) adding the pretreated pure cotton fiber, reacting at 80 ℃ for 30min, controlling the liquid carrying rate to be 140% after the reaction is finished, drying at 85 ℃ for 15min, and then drying at 125 ℃ for 15min to obtain the nano carbon crystal pure cotton surface antibacterial fiber.
The modified nano carbon crystal is prepared by the following steps:
a) hydroxylation and silanization treatment of the nano carbon crystal: adding 10g of nano carbon crystal into 250mL of deionized water, placing the mixture into a 500mL beaker, and directly adding 25g of FeSO4·7H2O, ultrasonic treatment for 30-40min until FeSO is obtained4·7H2Fully dissolving O, placing a beaker in an ice bath-ultrasonic environment, adding 40mL of concentrated sulfuric acid, dropwise adding 40mL of hydrogen peroxide (30 v/v%), standing for 2H, and sequentially adding 2-3mL of concentrated sulfuric acid and 1-3mL of H2O2Circularly replenishing for 6 times until the color of the system is changed from green yellow to light yellow, then changing the color to dark, and finally carrying out vacuum drying at 60 ℃ to obtain hydroxylated nano carbon crystals;
b) dispersing hydroxylated nano carbon crystals in 250mL of ethanol, performing ultrasonic treatment for 40min, adding 15mL of 3-bromoethyl trimethoxy silane, adding 3-5mL of deionized water and 1-3mL of acetic acid, stirring and reacting at 60 ℃ for 24h, performing centrifugal separation on the obtained silylated nano carbon crystals after the reaction is finished, dispersing and centrifuging in ethanol, repeating the dispersion and centrifugation operations in the ethanol for 4 times, and performing vacuum drying at 60 ℃ to obtain grayish black silylated nano carbon crystals;
c) modification and chlorination of nano carbon crystal quaternary ammonium salt: dissolving 3g of poly-4-vinylpyridine (PVP) in 250mL of nitromethane, adding the silylated nanocarbon crystal obtained in the step b), performing ultrasonic dispersion for 50min, stirring and reacting at 70 ℃ for 12h, adding 5g of hydantoin compounds, reacting for 24h, after the reaction is finished, centrifugally separating the obtained high molecular quaternary ammonium salt type product, dispersing and centrifuging in ethanol, repeating the dispersion and centrifugation operations in the ethanol for 4 times, and performing vacuum drying at 60 ℃ to obtain light gray high molecular quaternary ammonium salt modified nanocarbon crystal;
d) ultrasonically dispersing the obtained high-molecular quaternary ammonium salt modified nano carbon crystal into 200mL of deionized water, adding 25g of 10wt% sodium hypochlorite solution into the dispersion liquid, stirring for 6h under the condition of ice water bath, after the reaction is finished, carrying out centrifugal separation to obtain a solid product, washing with the deionized water, centrifuging again, repeatedly washing and centrifuging for 5 times, and carrying out vacuum drying for 5h to obtain the nano carbon crystal.
Example 3
A nanometer carbon crystal pure cotton surface antibacterial fiber and a preparation method thereof are different from the embodiment 1 in that:
the solid loading of the modified nano carbon crystal is 1.25 percent of the weight of the pure cotton fiber matrix.
The modified nano carbon crystal is prepared by the following steps:
a) hydroxylation and silanization treatment of the nano carbon crystal: adding 8g of nano carbon crystal into 250mL of deionized water, placing the mixture into a 500mL beaker, and directly adding 22g of FeSO4·7H2O, ultrasonic treatment for 35min until FeSO4·7H2Fully dissolving O, placing a beaker in an ice bath-ultrasonic environment, adding 35mL of concentrated sulfuric acid, dropwise adding 35mL of hydrogen peroxide (30 v/v%), standing for 1.5H, and sequentially adding 2-3mL of concentrated sulfuric acid and 1-3mL of H2O2Circularly replenishing until the color of the system is changed from green yellow to light yellow, then changing the color to dark, and finally drying in vacuum at 55 ℃ to obtain hydroxylated nano carbon crystals;
b) dispersing hydroxylated nano carbon crystals in 250mL of ethanol, carrying out ultrasonic treatment for 35min, adding 12mL of 3-bromoethyltrimethoxysilane, adding 3-5mL of deionized water and 1-3mL of acetic acid, stirring and reacting at 55 ℃ for 24h, carrying out centrifugal separation on the obtained silylated nano carbon crystals after the reaction is finished, dispersing and centrifuging in the ethanol, repeating the dispersion and centrifugation operations in the ethanol for 3 times, and carrying out vacuum drying at 55 ℃ to obtain grayish black silylated nano carbon crystals;
c) modification and chlorination of nano carbon crystal quaternary ammonium salt: dissolving 2g of poly-4-vinylpyridine (PVP) in 250mL of nitromethane, adding the silylated nanocarbon crystals obtained in the step 2), performing ultrasonic dispersion for 45min, stirring and reacting at 66 ℃ for 12h, adding 4g of hydantoin compounds, reacting for 24h, after the reaction is finished, centrifugally separating the obtained high-molecular quaternary ammonium salt type product, dispersing and centrifuging in ethanol, repeating the dispersion and centrifugation operations in the ethanol for 4 times, and performing vacuum drying at 55 ℃ to obtain light gray high-molecular quaternary ammonium salt modified nanocarbon crystals;
d) ultrasonically dispersing the obtained high molecular quaternary ammonium salt modified nano carbon crystal into 200mL of deionized water, adding 20-25g of 10wt% sodium hypochlorite solution into the dispersion liquid, stirring for 5h under the ice-water bath condition, after the reaction is finished, carrying out centrifugal separation to obtain a solid product, washing with the deionized water, centrifuging again, repeatedly washing and centrifuging for 4 times, and carrying out vacuum drying for 4h to obtain the nano carbon crystal.
Measurement of Performance
1. Stability of
And (3) placing the prepared nano carbon crystal pure cotton fiber sample in a 55 ℃ oven, and measuring the loss rate of the nano carbon crystal of the sample after two weeks. The results are shown in Table 1. As can be seen from the data of table 1, the nano carbon crystal antibacterial pure cotton fiber has good thermal stability.
Table 1 stability of antimicrobial pure cotton fiber samples
| Initial content/%) | Content/% after two weeks | Rate of loss/%) | |
| Content of modified nano carbon crystal | 1.25 | 1.13 | 9.60 |
2. Experiment for measuring washing fastness
According to GB/T20944.3-2008 and antibacterial textile standard FZ/T73023-2006, 20g of prepared pure cotton antibacterial fiber is weighed and placed in a household drum-type washing machine, 6L of water at 20 ℃ is added, 180g of other fabrics without antibacterial agents are added to serve as washing-accompanying fabrics, 12g of non-phosphorus detergent is added, the pure cotton antibacterial fiber is washed for 25min, the pure cotton antibacterial fiber is dewatered for 3min after drainage and marked as washing for 5 times, and by means of the circulation, samples are taken to determine the sterilization effect and the antibacterial agent content of the samples under different washing times, and the attenuation curve of the antibacterial performance of the samples along with the washing times is made. Wherein the change of the content of the modified nano carbon crystal is calculated by adopting a drying and weighing method.
TABLE 2 variation of antibacterial property of nano carbon crystal pure cotton fiber with washing frequency
As can be seen from Table 2, the pure cotton fiber treated by the modified nanocarbon crystal has a very strong sterilization effect, and has good washing stability when washed in water at 20 ℃, the sterilization effect on Escherichia coli after 30 times of washing is 89.26%, and the sterilization effect on Escherichia coli after 60 times of washing can still reach 88.54%. As can be seen from fig. 1, the antibacterial rate of the antibacterial pure cotton fiber has a great relationship with the content of the nanocarbon crystals, and as the content of the nanocarbon crystals decreases, the antibacterial rate also decreases, and decreases significantly in the previous 10 times of cleaning processes, and then changes slowly, which is caused by the modified nanocarbon crystals adsorbed on the surface of the pure cotton fiber being not firmly combined with the pure cotton fiber in the cleaning process and easily falling off, and as the content of the adsorbed nanocarbon crystals decreases, the nanocarbon crystals immobilized on the surface of the pure cotton fiber show good water washing stability, and can be used as raw material fibers of textiles such as medical and household articles.
3. Determination of fungicidal Properties
Referring to a shaking beaker method in FZ/T73023-2006 antibacterial knitwear and 2002 edition of disinfection technical Specification, wherein test strains are escherichia coli (ATCC) and staphylococcus aureus (ATCC 6538), and a test group comprises nano carbon crystal pure cotton antibacterial fibers and commercially available Sanqian brand and Langsha brand cotton antibacterial underwear.
TABLE 3 comparison of antibacterial Properties of different kinds of pure cotton antibacterial fiber (Water temperature 20 ℃ C.)
The data in table 3 show that the prepared antibacterial pure cotton fiber has better antibacterial effect, which is superior to the similar products in the market, in addition, the prepared sample still has good antibacterial effect after being washed for 60 times, according to antibacterial knitwear standard FZ/T73023-2006, after being washed for 60 times, the antibacterial rate of the antibacterial fabric on staphylococcus aureus and escherichia coli is respectively more than 80% and 70%, and the antibacterial level can reach 3A, so the nano carbon crystal pure cotton antibacterial fabric has excellent antibacterial property.
Claims (1)
1. A method for preparing nano carbon crystal pure cotton surface antibacterial fiber is characterized in that the surface antibacterial fiber is obtained by fixedly loading modified nano carbon crystal on a pure cotton fiber substrate; the modified nano carbon crystal is obtained by hydroxylating and silanizing the nano carbon crystal, and then modifying and chlorinating the nano carbon crystal by quaternary ammonium salt, wherein the solid loading of the modified nano carbon crystal is 0.9-1.5% of the weight of a pure cotton fiber matrix, and the preparation method comprises the following steps:
1) pretreatment of pure cotton fibers: boiling the pure cotton fiber with distilled water for half an hour to remove impurities which are attached to the fiber and are easy to dissolve in water, and placing the fiber in an oven for drying;
2) preparing 200-250mL of ethanol and water at a volume ratio of 1: 1, adding 5-10g of modified nano carbon crystal, stirring at a high speed of 1500rpm by a magnetic stirrer for 20-30min to form a suspension, and adding glacial acetic acid to adjust the pH value of the solution to 5.0-5.5;
3) adding the pretreated pure cotton fiber, reacting for 20-30min at 70-80 ℃, controlling the liquid carrying rate to be 140-;
the modified nano carbon crystal is prepared by the following steps:
a) hydroxylation treatment of the nano-carbon crystal: adding 2-10g of nano carbon crystal into 250mL of deionized water, placing the mixture into a 500mL beaker, and directly adding 20-25g of FeSO4·7H2O, ultrasonic treatment for 30-40min until FeSO is obtained4·7H2Fully dissolving O, placing a beaker in an ice bath-ultrasonic environment, adding 30-40mL of concentrated sulfuric acid, dropwise adding 30-40mL of 30v/v% hydrogen peroxide, standing for 1-2H, and sequentially supplementing 2-3mL of concentrated sulfuric acid and 1-3mL of H2O2Circularly replenishing for 5-6 times until the color of the system changes from green yellow to light yellow, then changing the color to dark, and finally performing vacuum drying at 50-60 ℃ to obtain hydroxylated nano carbon crystals;
b) silylation treatment of nanocarbon crystals: dispersing hydroxylated nano carbon crystals in 250mL of ethanol, performing ultrasonic treatment for 30-40min, adding 10-15mL of 3-bromoethyltrimethoxysilane, adding 3-5mL of deionized water and 1-3mL of acetic acid, stirring at 50-60 ℃ for reaction for 24h, performing centrifugal separation on the obtained silylated nano carbon crystals after the reaction is finished, dispersing in ethanol, centrifuging, repeating the steps of dispersing in ethanol and centrifuging for 3-4 times, and performing vacuum drying at 50-60 ℃ to obtain gray-black silylated nano carbon crystals;
c) modification of nano carbon crystal quaternary ammonium salt: dissolving 2-3g of poly 4-vinylpyridine in 250mL of nitromethane, adding the silylated nanocarbon crystal obtained in the step b), performing ultrasonic dispersion for 40-50min, stirring and reacting at 60-70 ℃ for 12h, adding 3-5g of hydantoin compounds, reacting for 24h, after the reaction is finished, centrifugally separating the obtained high molecular quaternary ammonium salt type product, dispersing and centrifuging in ethanol, repeating the dispersion and centrifugation operations in the ethanol for 3-4 times, and performing vacuum drying at 50-60 ℃ to obtain light gray high molecular quaternary ammonium salt modified nanocarbon crystal;
d) chlorination of nano carbon crystals: ultrasonically dispersing the obtained high-molecular quaternary ammonium salt modified nano carbon crystal into 200mL of deionized water, adding 20-25g of 10wt% sodium hypochlorite solution into the dispersion liquid, stirring for 4-6h under the ice water bath condition, after the reaction is finished, carrying out centrifugal separation to obtain a solid product, washing with the deionized water, centrifuging again, repeatedly washing and centrifuging for 4-5 times, and carrying out vacuum drying for 3-5h to obtain the nano carbon crystal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811286176.2A CN109403021B (en) | 2018-10-31 | 2018-10-31 | Nano carbon crystal pure cotton surface antibacterial fiber and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811286176.2A CN109403021B (en) | 2018-10-31 | 2018-10-31 | Nano carbon crystal pure cotton surface antibacterial fiber and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109403021A CN109403021A (en) | 2019-03-01 |
| CN109403021B true CN109403021B (en) | 2021-04-16 |
Family
ID=65470702
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811286176.2A Active CN109403021B (en) | 2018-10-31 | 2018-10-31 | Nano carbon crystal pure cotton surface antibacterial fiber and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109403021B (en) |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6969769B2 (en) * | 2002-06-14 | 2005-11-29 | Vanson Halosource, Inc. | N-halamine siloxanes for use in biocidal coatings and materials |
| WO2009039348A1 (en) * | 2007-09-19 | 2009-03-26 | Rotter Martin J | Cleaning pads with abrasive loaded filaments and anti-microbial agent |
| CN101250815A (en) * | 2008-03-24 | 2008-08-27 | 王加旺 | Method for manufacturing halogen amine antimicrobial material |
| CN105253882B (en) * | 2015-10-09 | 2018-01-05 | 南京理工大学 | Ultra-dispersed antimicrobial nano diamond and preparation method thereof |
| CN105237681B (en) * | 2015-10-28 | 2017-11-10 | 江南大学 | A kind of halogen amine antiseptic coating modification nanometer titanium dioxide composite material and preparation method thereof |
| CN108338162A (en) * | 2018-02-09 | 2018-07-31 | 郑州人造金刚石及制品工程技术研究中心有限公司 | A kind of novel water sterilization filler and preparation method thereof containing nanometer carbon crystal |
| CN108524101A (en) * | 2018-04-18 | 2018-09-14 | 郑州人造金刚石及制品工程技术研究中心有限公司 | A kind of nanometer carbon crystal antibacterial nursing type 3D urine pads |
-
2018
- 2018-10-31 CN CN201811286176.2A patent/CN109403021B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN109403021A (en) | 2019-03-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112941899B (en) | MXenes-AgNPs synergistic antibacterial cotton fabric and preparation method thereof | |
| CN102936835B (en) | Preparation method of nano-silver antibacterial real silk | |
| CN105177995A (en) | Preparation method for anti-bacteria pure cotton fabric | |
| CN109942751A (en) | A kind of preparation method of plastics anti-biotic material | |
| CN106192074B (en) | A kind of preparation method of the graphene oxide being loaded with nano silver particles/seaweed composite fibre | |
| CN111411510B (en) | Antibacterial, anti-mite and antiviral finishing agent, plush fabric and preparation method and application thereof | |
| CN107439593A (en) | A kind of silver-colored chitosan anti-bacteria material and preparation method thereof | |
| Andra et al. | Surface cationization of cellulose to enhance durable antibacterial finish in phytosynthesized silver nanoparticle treated cotton fabric | |
| CN106922732B (en) | Preparation method and application of sterilization material taking loofah sponge as matrix | |
| CN109403021B (en) | Nano carbon crystal pure cotton surface antibacterial fiber and preparation method thereof | |
| KR100592365B1 (en) | Method for manufacturing antibacterial fiber treated with nano silver colloidal solution | |
| CN105753115B (en) | A kind of triple sterilization composite materials and preparation method thereof | |
| CN107675290A (en) | A kind of preparation method of antiseptic nano-fiber mixed cloth | |
| CN109468844B (en) | Antibacterial fabric and production process thereof | |
| CN112609294B (en) | Environment-friendly antibacterial anti-mite fiber fabric for home textiles | |
| CN112941907B (en) | MXene two-dimensional nanosheet-based multifunctional real silk fabric and preparation method thereof | |
| CN109653005B (en) | Preparation method of antibacterial fabric based on graphene | |
| CN112695521A (en) | Halamine modified antibacterial mesoporous material and synthesis method thereof | |
| CN107326660A (en) | A kind of preparation method of anti-bacterial textile finishing agent | |
| Teli et al. | Study of grafted silver nanoparticle containing durable antibacterial bamboo rayon | |
| CN115387117A (en) | Photoresponse antibacterial fabric softener | |
| CN109487558A (en) | A kind of moisture absorption antibacterial cotton fibriia and preparation method thereof | |
| CN111155198B (en) | Preparation method of antibacterial polyester fiber | |
| CN104358123B (en) | A kind of preparation method of propionyloxyethyl trimethyl ammonium chloride chitin fiber | |
| CN102995403B (en) | The method solidifying high-performance chitosan on fabric |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |