CN113481727A - Organic-inorganic composite antibacterial powder and preparation method thereof - Google Patents
Organic-inorganic composite antibacterial powder and preparation method thereof Download PDFInfo
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- CN113481727A CN113481727A CN202110896332.2A CN202110896332A CN113481727A CN 113481727 A CN113481727 A CN 113481727A CN 202110896332 A CN202110896332 A CN 202110896332A CN 113481727 A CN113481727 A CN 113481727A
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
- D06M15/03—Polysaccharides or derivatives thereof
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- 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
- D06M11/83—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 metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
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- 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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/402—Amides imides, sulfamic acids
- D06M13/432—Urea, thiourea or derivatives thereof, e.g. biurets; Urea-inclusion compounds; Dicyanamides; Carbodiimides; Guanidines, e.g. dicyandiamides
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
Abstract
The invention discloses organic-inorganic composite antibacterial powder and a preparation method thereof. The antibacterial powder prepared by the invention integrates the characteristics of natural, organic and inorganic antibacterial agents, has broader-spectrum and high-efficiency antibacterial performance, can ensure that the finished textiles have better antibacterial effect, and is suitable for the antibacterial function treatment of various textiles, leather, other daily necessities and the like.
Description
Technical Field
The invention belongs to the technical field of antibacterial finishing agents, and particularly relates to organic-inorganic composite antibacterial powder and a preparation method thereof.
Background
At present, the production methods of the antibacterial products are divided into two main types: one is that antibacterial agent is added into raw material of product, and then is directly made into antibacterial product after molding processing; another approach is to use an antimicrobial post-application treatment, including the antimicrobial post-finishing method currently most commonly used in textiles, by adding an antimicrobial agent to the finish during the post-finishing of the textile. The antibacterial finishing agent in the market has a plurality of varieties, and the traditional antibacterial finishing agent mainly comprises four types of natural antibacterial agents, inorganic antibacterial agents, organic antibacterial agents and macromolecular antibacterial agents. Comparing and analyzing all types of antibacterial agents, it is known that although each type of antibacterial agent has its advantages, it also has some disadvantages and certain antibacterial limitations. These problems have led to the development of highly effective complex antimicrobial agents having both broad-spectrum antimicrobial activity and excellent durability and safety.
The nano silver antibacterial agent is the most common highly efficient antibacterial agent, and has the functions of mainly combining with sulfydryl in metabolic enzyme of pathogenic bacteria to inactivate the enzyme, reacting with exposed bacterial cell wall through peptidoglycan to form a reversible compound, so that the bacteria cannot transfer oxygen and energy into cells, and combining with DNA in pathogenic microorganisms to cause DNA structural denaturation and inhibit DNA replication. The main reason for the antibacterial effect of the nano silver is that the size of the structural unit is between that of macroscopic substances and microscopic atoms and molecules, the special surface effect, small-size effect, quantum size effect and macroscopic quantum tunneling effect are shown, and pathogens can easily enter the antibacterial effect of the nano silver; the nano silver particles have small size and large volume percentage occupied by the surface, the bonding state and the electronic state of the surface are different from those of the interior of the particles, the coordination of surface atoms is not complete, and the like, so that the active sites on the surface are increased, and the nano silver particles have basic conditions as an antibacterial agent; has strong penetrating power, can fully contact and attack pathogens comprehensively, thereby exerting stronger biological effect, and has the advantages of high safety, wide antibacterial range, long lasting sterilization time and the like. Especially, the killing effect of the nano silver on pathogenic bacilli, cocci and filamentous bacteria is far greater than that of the traditional silver ion bactericide, and the nano silver particles can kill pathogenic microorganisms such as bacteria, fungi, mycoplasma, chlamydia and the like. Therefore, there are a large number of patents based on nano-silver, such as chinese patent ZL201410009948.3 "a simple preparation method of a novel large-scale nano-silver hydrosol", chinese patent ZL201710694377.5 "multifunctional super-hydrophobic textile finishing agent, its preparation method and application", chinese patent ZL201010131192.1 "a nano-silver antibacterial agent and its preparation method", chinese patent ZL201010131203.6 "a transparent nano-silver antibacterial finishing agent and its preparation method", chinese patent ZL201110297232.4 "a finishing liquid for fabric antibacterial and its preparation method", chinese patent ZL201310048610.4 "a nano-silver antibacterial finishing agent and its preparation method", and so on.
However, the nano silver particles have large specific surface area and are easy to agglomerate, and chitosan is the most commonly used natural antibacterial agent at present, but compared with the traditional antibacterial agent, the antibacterial activity of the chitosan is lower, and the pH value sensitivity of the chitosan limits the application of the chitosan under the alkaline condition.
Disclosure of Invention
Based on the problems, the invention takes the natural antibacterial agent chitosan as a framework, carries out chemical modification on the natural antibacterial agent chitosan, and is grafted with the monoguanidine groups, so that the natural antibacterial agent chitosan has better antibacterial activity in a larger pH value range, and forms microsphere type composite antibacterial powder with coated nano silver particles, the introduction of the nano silver particles greatly improves the antibacterial activity, the microsphere combines the advantages of natural, organic and inorganic antibacterial agents, has more efficient and broad-spectrum antibacterial performance, and can also meet the requirement that the finished textiles can keep better antibacterial effect under different conditions.
Therefore, the invention aims to provide organic-inorganic composite antibacterial powder and a preparation method thereof, and chitosan monoguanidine hydrochloride-supported nano silver microsphere antibacterial powder is prepared by a suspension-crosslinking technology. The chitosan monoguanidine hydrochloride and the nano silver solution are used as water phases and dispersed in the mixed oil phase mixture, and the suspension-crosslinking technology is adopted to prepare the organic-inorganic natural composite antibacterial powder.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of organic-inorganic composite antibacterial powder comprises the following steps:
a1: preparation of crystal of thiourea trioxide hydrate: preparing a hydrogen peroxide acid solution with the sulfuric acid concentration of 0.5mol/L by adopting sulfuric acid and a hydrogen peroxide solution, preferably adding concentrated sulfuric acid into the hydrogen peroxide solution to prepare the hydrogen peroxide acid solution, wherein the hydrogen peroxide concentration in the solution is 30 percent, and the ratio of hydrogen peroxide: the molar ratio of thiourea dioxide is 1: (1.2-1.8) alternately mixing and feeding materials within 30 minutes, and then reacting for 2.5 hours at 45-50 ℃;
a2: preparing a chitosan concentrated solution: dissolving chitosan in a hydrochloric acid solution to prepare a chitosan acid solution with the mass percent of 1-3%, adjusting the pH value to 8-9 with a soda solution under the stirring condition, stopping stirring, separating out a white flocculent precipitate, and washing with distilled water to be neutral;
a3: heating the chitosan concentrated solution obtained in the step A2 to 50-60 ℃, and adding the sulfur trioxide urea hydrate crystals obtained in the step A1, wherein the molar ratio of the sulfur trioxide urea hydrate crystals to amino groups in chitosan is (1-1.5): 1, stirring for 10-20 min, washing with absolute ethyl alcohol, centrifugally separating, and drying to obtain chitosan monoguanidine bisulfite; dissolving the chitosan monoguanidine bisulfite in water, heating to 45-55 ℃, stirring, adding concentrated hydrochloric acid with equal molar weight, reacting for 2 hours, filtering, washing, and drying to obtain chitosan monoguanidine hydrochloride;
a4: dissolving the chitosan monoguanidine hydrochloride obtained in the step A3 in water, stirring uniformly, adding nano-silver, performing ultrasonic dispersion for 3 hours, and adding Tween80 to obtain a pre-emulsified water phase mixture; wherein the molar ratio of the chitosan monoguanidine hydrochloride to the nano-silver is (2-4): 1; the volume percentage concentration of the Tween80 in the water phase is 0.5-2%;
a5: adding an emulsifier into petroleum ether and liquid paraffin according to the volume ratio of (1-5): 1, preparing the mixture into an oil phase solvent to obtain an oil phase mixture with the volume percentage concentration of the emulsifier of 2-8%;
a6: adding the water phase mixture obtained in the step A4 into the oil phase mixture obtained in the step A5 in a spraying mode, wherein the volume ratio of the water phase mixture to the oil phase mixture is 1: (5-15), stirring for 30min, adding a cross-linking agent, wherein the addition amount of the cross-linking agent is that the molar ratio of aldehyde groups in the cross-linking agent to amino groups in the chitosan monoguanidine hydrochloride is 1-4: and (1) reacting for 4-8 h to obtain the organic-inorganic composite antibacterial powder.
Preferably, the particle size of the nano silver in the step A4 is 15-60 nm.
Preferably, the emulsifier in step a5 is selected from Span80, Tween80 or their mixed emulsifiers.
Preferably, the cross-linking agent in step a6 is one of succinaldehyde or glutaraldehyde.
An organic-inorganic composite antibacterial powder is prepared by the preparation method of the organic-inorganic composite antibacterial powder.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following advantages and positive effects:
according to the invention, the amino group of chitosan is utilized, and the guanidination of thiourea trioxide is carried out to obtain chitosan guanidinium, so that the product has higher bacteriostatic activity and wider bacteriostatic range; as a class of inorganic antibacterial agents, nano-silver is nontoxic, odorless and chemically stable, has been widely used in textiles, leather and daily necessities, and the use thereof has been proved to be safe to human beings, has a higher continuous antibacterial effect and good durability. The nano silver is coated in the microsphere, and the problems of agglomeration and loss can not occur, so that the novel antibacterial agent which is more efficient, more broad-spectrum and more durable can be prepared by compounding the chitosan guanidyl hydrochloride and the nano silver together by adopting the microsphere technology.
Drawings
Fig. 1 is a TEM topography of the organic-inorganic natural composite antibacterial powder prepared in example 1 of the present invention.
Detailed Description
The following will explain in detail an organic-inorganic composite antibacterial powder and its preparation method proposed by the present invention with reference to the accompanying drawings and specific examples. Advantages and features of the present invention will become apparent from the following description and from the claims.
Example 1
Adding 16mL of hydrogen peroxide into a beaker, adding 0.8mL of concentrated sulfuric acid, stirring to prepare a hydrogen peroxide acidic solution, weighing 10g of thiourea dioxide, alternately adding the hydrogen peroxide acidic solution and the thiourea dioxide into a conical flask, controlling the reaction temperature to be 50 ℃, stirring for 2.5 hours, and filtering to obtain a thiourea trioxide hydrate crystal; meanwhile, 10g of chitosan is weighed, 400mL of hydrochloric acid solution with the concentration of 0.2mol/L is added, and the mixture is fully stirred for 4 hours; adjusting the pH value of the chitosan solution to 8-9 by using 50g/L of soda solution, then washing the chitosan solution to the pH value of 7.0-7.5 by using distilled water, centrifuging the solution, discharging part of upper clear water, putting the upper clear water into a three-hole flask, and starting heating the flask to 50 ℃; 7.6g of sulfur trioxide urea is added within 30 minutes, and the temperature is kept for 15min after the addition is finished. After the reaction is finished, precipitating with 2 times volume of absolute ethyl alcohol, centrifuging, washing with absolute ethyl alcohol, drying at 60 ℃ in vacuum, and grinding to obtain the chitosan monoguanidine sulfite.
And dissolving the chitosan monoguanidine sulfite in water, heating to 50 ℃, adding concentrated hydrochloric acid with equal amount of substances while stirring, reacting for 3 hours, filtering, washing, and vacuum drying for one day at 60 ℃ to obtain the chitosan monoguanidine hydrochloride.
Dissolving chitosan monoguanidine hydrochloride in water, stirring and dissolving to prepare 5% chitosan monoguanidine hydrochloride solution by mass percent, putting 30mL of the chitosan monoguanidine hydrochloride solution and 0.58g of nano-silver into a beaker, ultrasonically dispersing for 1h, and then adding 0.30mL of Tween80 to obtain a pre-emulsified water-phase mixture; 200mL of petroleum ether, 100mL of liquid paraffin and 15mL of Span8080 are added into a three-neck flask and stirred uniformly to obtain an oil phase mixture. And uniformly adding the pre-emulsified water phase mixture into the oil phase mixture within 30min, controlling the reaction temperature to be 30 ℃, stirring for 0.5h, adding 3mL of glutaraldehyde, continuously stirring for 4h, standing, performing suction filtration, washing, and performing vacuum drying on the sample for one night to obtain the organic-inorganic natural composite antibacterial powder. The morphology of the obtained composite antibacterial powder is observed by a transmission electron microscope, and the result is shown in figure 1, and the obtained antibacterial powder is uniformly dispersed and has no agglomeration phenomenon.
Example 2:
chitosan monoguanidine hydrochloride was prepared as in example 1.
Weighing a certain amount of chitosan monoguanidine hydrochloride, dissolving the chitosan monoguanidine hydrochloride in water, stirring and dissolving to prepare a 5% chitosan monoguanidine hydrochloride solution in mass percentage, putting 30mL of the chitosan monoguanidine hydrochloride solution and 0.30g of nano-silver into a beaker, ultrasonically dispersing for 1h, and then adding 0.3mL of Tween80 to obtain a pre-emulsified water phase mixture; 200mL of petroleum ether, 100mL of liquid paraffin and 15mL of Span8080 are added into a three-neck flask and stirred uniformly to obtain an oil phase mixture. And uniformly adding the pre-emulsified water phase mixture into the oil phase mixture within 30min, controlling the reaction temperature to be 30 ℃, stirring for 0.5h, adding 3mL of glutaraldehyde, continuously stirring for 4h, standing, performing suction filtration, washing, and performing vacuum drying on the sample for one night to obtain the organic-inorganic natural composite antibacterial powder.
Example 3:
chitosan monoguanidine hydrochloride was prepared as in example 1.
Weighing a certain amount of chitosan monoguanidine hydrochloride, dissolving the chitosan monoguanidine hydrochloride in water, stirring and dissolving to prepare a 5% chitosan monoguanidine hydrochloride solution in percentage by mass, putting 100mL of the chitosan monoguanidine hydrochloride solution and 0.98g of nano-silver into a beaker, ultrasonically dispersing for 1h, and then adding 1mL of Tween80 to obtain a pre-emulsified water-phase mixture; 200mL of petroleum ether, 100mL of liquid paraffin and 15mL of Span80 are added into a three-neck flask and are mechanically stirred uniformly to obtain an oil phase mixture. And uniformly adding the pre-emulsified water phase mixture into the oil phase mixture within 30min, controlling the reaction temperature to be 30 ℃, stirring for 0.5h, adding 11mL of glutaraldehyde, continuously stirring for 4h, standing, performing suction filtration, washing, and performing vacuum drying on the sample for one night to obtain the organic-inorganic natural composite antibacterial powder.
Example 4:
chitosan monoguanidine hydrochloride was prepared as in example 1.
Weighing a certain amount of chitosan monoguanidine hydrochloride, dissolving the chitosan monoguanidine hydrochloride in water, stirring and dissolving to prepare a 5% chitosan monoguanidine hydrochloride solution in mass percentage, putting 40mL of the chitosan monoguanidine hydrochloride solution and 0.41g of nano-silver into a beaker, ultrasonically dispersing for 1h, and then adding 0.4mL of Tween80 to obtain a pre-emulsified water phase mixture; 210mL of petroleum ether, 108mL of liquid paraffin and 16mL of Span80 are added into a three-neck flask and are mechanically stirred uniformly to obtain an oil-phase mixture. And uniformly adding the pre-emulsified water phase mixture into the oil phase mixture within 30min, controlling the reaction temperature to be 25 ℃, stirring for 0.5h, adding 4mL of glutaraldehyde, continuously stirring for 4h, standing, performing suction filtration, washing, and performing vacuum drying on the sample for one night to obtain the organic-inorganic natural composite antibacterial powder.
Example 5:
chitosan monoguanidine hydrochloride was prepared as in example 1.
Weighing a certain amount of chitosan monoguanidine hydrochloride, dissolving the chitosan monoguanidine hydrochloride in water, stirring and dissolving to prepare a 5% chitosan monoguanidine hydrochloride solution in mass percentage, putting 30mL of the chitosan monoguanidine hydrochloride solution and 0.15g of nano-silver into a beaker, ultrasonically dispersing for 1h, and then adding 0.3mL of Tween80 to obtain a pre-emulsified water phase mixture; 200mL of petroleum ether, 100mL of liquid paraffin and 15mL of Span80 are added into a three-neck flask and are mechanically stirred uniformly to obtain an oil phase mixture. And uniformly adding the pre-emulsified water phase mixture into the oil phase mixture within 30min, controlling the reaction temperature to be 30 ℃, stirring for 0.5h, adding 3mL of glutaraldehyde, continuously stirring for 4h, standing, performing suction filtration, washing, and performing vacuum drying on the sample for one night to obtain the organic-inorganic natural composite antibacterial powder.
Example 6:
chitosan monoguanidine hydrochloride was prepared as in example 1.
Weighing a certain amount of chitosan monoguanidine hydrochloride, dissolving the chitosan monoguanidine hydrochloride in water, stirring and dissolving to prepare a 5% chitosan monoguanidine hydrochloride solution in mass percentage, putting 305mL of the chitosan monoguanidine hydrochloride solution and 0.31g of nano-silver into a beaker, ultrasonically dispersing for 1h, and then adding 0.3mL of Tween80 to obtain a pre-emulsified water phase mixture; 200mL of petroleum ether, 100mL of liquid paraffin and 6mL of Span80 are added into a three-neck flask and are mechanically stirred uniformly to obtain an oil phase mixture. And uniformly adding the pre-emulsified water phase mixture into the oil phase mixture within 30min, controlling the reaction temperature to be 30 ℃, stirring for 0.5h, adding 3mL of glutaraldehyde, continuously stirring for 4h, standing, performing suction filtration, washing, and performing vacuum drying on the sample for one night to obtain the organic-inorganic natural composite antibacterial powder.
Example 7:
chitosan monoguanidine hydrochloride was prepared as in example 1.
Weighing a certain amount of chitosan monoguanidine hydrochloride, dissolving the chitosan monoguanidine hydrochloride in water, stirring and dissolving to prepare a 5% chitosan monoguanidine hydrochloride solution in mass percentage, putting 40mL of the chitosan monoguanidine hydrochloride solution and 0.41g of nano-silver into a beaker, ultrasonically dispersing for 1h, and then adding 0.4mL of Tween80 to obtain a pre-emulsified water phase mixture; 400mL of petroleum ether, 200mL of liquid paraffin and 30mL of Span80 are added into a three-neck flask and are mechanically stirred uniformly to obtain an oil phase mixture. And uniformly adding the pre-emulsified water phase mixture into the oil phase mixture within 30min, controlling the reaction temperature to be 25 ℃, stirring for 0.5h, adding 4mL of glutaraldehyde, continuously stirring for 4h, standing, performing suction filtration, washing, and performing vacuum drying on the sample for one night to obtain the organic-inorganic natural composite antibacterial powder.
Example 8:
chitosan monoguanidine hydrochloride was prepared as in example 1.
Weighing a certain amount of chitosan monoguanidine hydrochloride, dissolving the chitosan monoguanidine hydrochloride in water, stirring and dissolving to prepare a 5% chitosan monoguanidine hydrochloride solution in mass percentage, putting 30mL of the chitosan monoguanidine hydrochloride solution and 0.31g of nano-silver into a beaker, ultrasonically dispersing for 1h, and then adding 0.3mL of Tween80 to obtain a pre-emulsified water phase mixture; 200mL of petroleum ether, 100mL of liquid paraffin and 24mL of Span80 are added into a three-neck flask and are mechanically stirred uniformly to obtain an oil phase mixture. And uniformly adding the pre-emulsified water phase mixture into the oil phase mixture within 30min, controlling the reaction temperature to be 30 ℃, stirring for 0.5h, adding 3mL of glutaraldehyde, continuously stirring for 4h, standing, performing suction filtration, washing, and performing vacuum drying on the sample for one night to obtain the organic-inorganic natural composite antibacterial powder.
The antibacterial effect was verified by the textile post-finishing method. Taking 100g of the mixture with the gram weight of 110g/m2After the pure cotton knitted fabric is subjected to oxygen bleaching treatment, resin finishing liquid containing 25g/L of the prepared organic-inorganic natural composite antibacterial powder is used for padding, the padding rate is 85%, and after drying and sizing, the antibacterial fabric is obtained from No. 1 to No. 8.
According to the regulation of national standard GB8629-2001, household washing and drying procedures adopted in textile tests, a B-type stirring washing machine and a washing procedure 8B are selected to respectively wash the cloth samples of the 1# -8# antibacterial cloth. Each sample was washed 10 times, 20 times, and 50 times, and the antibacterial performance of the washed cloth sample was measured.
According to the test method of the antibacterial performance of the product of the national standard GB1759-2002 sanitary Standard for Disposable sanitary articles of the people's republic of China, the test strains are bacteria: staphylococcus aureus (ATCC 6538), escherichia coli (ATCC 25922), fungi: candida albicans (ATCC 10231).
Note: bacteriostatic rate ". + -.": ≧ 99%, "+": not less than 90%, "x". not less than 50%, "-" < 50%.
According to the determination result, the cotton fabric finished by the composite antibacterial powder has good antibacterial property, and can prevent the occurrence and the spread of diseases and protect the health of human beings when being used in the aspects of life, medical treatment and the like.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments. Even if various changes are made to the present invention, it is still within the scope of the present invention if they fall within the scope of the claims of the present invention and their equivalents.
Claims (5)
1. The preparation method of the organic-inorganic composite antibacterial powder is characterized by comprising the following steps:
a1: preparation of crystal of thiourea trioxide hydrate: preparing a hydrogen peroxide acidic solution with the sulfuric acid concentration of 0.5mol/L by adopting sulfuric acid and a hydrogen peroxide solution, and mixing the following components in parts by weight: the molar ratio of thiourea dioxide is 1: (1.2-1.8) alternately mixing and feeding materials within 30 minutes, and then reacting for 2.5 hours at 45-50 ℃;
a2: preparing a chitosan concentrated solution: dissolving chitosan in a hydrochloric acid solution to prepare a chitosan acid solution with the mass percent of 1-3%, adjusting the pH value to 8-9 with a soda solution under the stirring condition, stopping stirring, separating out a white flocculent precipitate, and washing with distilled water to be neutral;
a3: heating the chitosan concentrated solution obtained in the step A2 to 50-60 ℃, and adding the sulfur trioxide urea hydrate crystals obtained in the step A1, wherein the molar ratio of the sulfur trioxide urea hydrate crystals to amino groups in chitosan is (1-1.5): 1, stirring for 10-20 min, washing with absolute ethyl alcohol, centrifugally separating, and drying to obtain chitosan monoguanidine bisulfite; dissolving the chitosan monoguanidine bisulfite in water, heating to 45-55 ℃, stirring, adding concentrated hydrochloric acid with equal molar weight, reacting for 2 hours, filtering, washing, and drying to obtain chitosan monoguanidine hydrochloride;
a4: dissolving the chitosan monoguanidine hydrochloride obtained in the step A3 in water, stirring uniformly, adding nano-silver, performing ultrasonic dispersion for 3 hours, and adding Tween80 to obtain a pre-emulsified water phase mixture; wherein the molar ratio of the chitosan monoguanidine hydrochloride to the nano-silver is (2-4): 1; the volume percentage concentration of the Tween80 in the water phase is 0.5-2%;
a5: adding an emulsifier into petroleum ether and liquid paraffin according to the volume ratio of (1-5): 1, preparing the mixture into an oil phase solvent to obtain an oil phase mixture with the volume percentage concentration of the emulsifier of 2-8%;
a6: adding the water phase mixture obtained in the step A4 into the oil phase mixture obtained in the step A5 in a spraying mode, wherein the volume ratio of the water phase mixture to the oil phase mixture is 1: (5-15), stirring for 30min, adding a cross-linking agent, wherein the addition amount of the cross-linking agent is that the molar ratio of aldehyde groups in the cross-linking agent to amino groups in the chitosan monoguanidine hydrochloride is 1-4: and (1) reacting for 4-8 h to obtain the organic-inorganic composite antibacterial powder.
2. The method for preparing organic-inorganic composite antibacterial powder according to claim 1, wherein the particle size of the nano silver in the step A4 is 15 to 60 nm.
3. The method of preparing organic-inorganic composite antibacterial powder according to claim 1, wherein the emulsifier in step a5 is selected from Span80, Tween80 or their mixed emulsifiers.
4. The method of claim 1, wherein the cross-linking agent in step A6 is one of succinaldehyde and glutaraldehyde.
5. An organic-inorganic composite antibacterial powder, characterized by being produced by the method for producing an organic-inorganic composite antibacterial powder according to any one of claims 1 to 4.
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| US20090293889A1 (en) * | 2007-11-28 | 2009-12-03 | Philip Morris Usa Inc. | Smokeless compressed tobacco product for oral consumption |
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| CN105494430A (en) * | 2015-12-16 | 2016-04-20 | 河北科技大学 | Silver-loaded low-molecular-weight chitosan composite microsphere antibacterial agent and preparation method thereof |
| CN110804247A (en) * | 2019-11-26 | 2020-02-18 | 泉州师范学院 | Chitosan microsphere-loaded nano-silver antibacterial polypropylene material, composite antibacterial agent and preparation method thereof |
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