CN116019126A - Composite antibacterial agent and preparation method thereof - Google Patents
Composite antibacterial agent and preparation method thereof Download PDFInfo
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- CN116019126A CN116019126A CN202211580235.3A CN202211580235A CN116019126A CN 116019126 A CN116019126 A CN 116019126A CN 202211580235 A CN202211580235 A CN 202211580235A CN 116019126 A CN116019126 A CN 116019126A
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- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 11
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- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 claims abstract description 31
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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Abstract
The invention discloses a composite antibacterial agent, which comprises the following components in percentage by weight: 2.5 to 4 percent of organic antibacterial agent, 0.8 to 1.2 percent of chitosan, 0.1 to 0.2 percent of methylbenzotriazole, 0.2 to 0.5 percent of inorganic antibacterial agent and the balance of deionized water; wherein the organic antibacterial agent at least comprises polyhexamethylene guanidine hydrochloride, and the content of the polyhexamethylene guanidine hydrochloride in the composite antibacterial agent is 0.5-1%. The invention also discloses a preparation method of the composite antibacterial agent. According to the invention, through the synergistic effect of the components, more stable organic antibacterial groups and inorganic metal cations with good dispersibility exist in the solution, so that the antibacterial property is improved.
Description
Technical Field
The invention belongs to the technical field of antibacterial agents, and particularly relates to a composite antibacterial agent and a preparation method thereof.
Background
Most of the composite antibacterial agents in the market are added with metal or organic antibacterial agents based on the original aqueous solution to enhance the antibacterial effect. However, most metals are poorly soluble in water and often do not have good dispersion, which often compromises antimicrobial ability. For example, the antibacterial effect can be greatly enhanced by incorporating an appropriate amount of nano silver into the antibacterial agent, since nano silver hydrolyzes silver ions in water, and free silver ions adhere to bacterial cell wall pores to increase cell permeability, thereby causing bacterial death. However, nano silver is easy to accumulate and difficult to disperse, and is oxidized black in solution, so that the nano silver does not meet the commercial requirements. Therefore, the selection of the proper amount of organic antibacterial agent is another idea for preparing the composite antibacterial agent, but a plurality of organic antibacterial agents are usually easy to volatilize and can not be well and continuously attached to the surface of an object, so that the aim of long-time antibacterial is fulfilled.
With the increase of market demands, products combining inorganic antibacterial agents and organic antibacterial agents are appeared, but the products are usually easy to have problems of coagulation, discoloration, adhesion and the like, and are the problems to be solved at present.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a composite antibacterial agent with good dispersibility and good antibacterial property and a preparation method thereof.
In order to achieve the above object, the technical scheme of the present invention is as follows:
the formula of the composite antibacterial agent comprises the following components in percentage by weight: 2.5 to 4 percent of organic antibacterial agent, 0.8 to 1.2 percent of chitosan, 0.1 to 0.2 percent of methylbenzotriazole, 0.2 to 0.5 percent of inorganic antibacterial agent and the balance of deionized water; wherein the organic antibacterial agent at least comprises polyhexamethylene guanidine hydrochloride, and the content of the polyhexamethylene guanidine hydrochloride in the composite antibacterial agent is 0.5-1%.
The invention further adopts the technical scheme that: the inorganic antibacterial agent comprises one of nano silver nitrate, nano silver chloride and nano zinc oxide.
The invention further adopts the technical scheme that: the size of the inorganic antibacterial agent is in the range of 0.5-80nm.
The invention further adopts the technical scheme that: the organic antibacterial agent also comprises one of sodium polyaspartic acid, epsilon-polylysine and epsilon-polylysine hydrochloride.
The invention further adopts the technical scheme that: the pH value of the composite antibacterial agent is 6-6.5.
Another object of the present invention is to provide a method for preparing a composite antibacterial agent, the method comprising the steps of:
step A1: weighing an organic antibacterial agent, methyl benzotriazole, an inorganic antibacterial agent and chitosan according to the proportion; wherein the organic antibacterial agent comprises polyhexamethylene guanidine hydrochloride;
step A2: mixing the organic antibacterial agent with deionized water, mechanically stirring at a medium speed at 25-35 ℃, and uniformly mixing;
step A3: adding the methylbenzotriazole, continuously stirring, and then adding the inorganic antibacterial agent and the chitosan, continuously stirring and uniformly mixing;
step A4: and (3) adjusting the pH value, and adjusting the solution formed in the step A3 into a uniform mixed state.
The invention further adopts the technical scheme that: in the step A3, the methylbenzotriazole is added after being ground into powder with the particle size smaller than 10 microns.
The invention further adopts the technical scheme that: in the steps A2 and A3, the stirring speed is 400-800rpm.
The invention further adopts the technical scheme that: the step A4 specifically comprises the following steps: preparing 0.1mol/L hydrochloric acid diluted solution with concentrated hydrochloric acid, and regulating pH of the solution to 6-6.5 to uniformly disperse chitosan in the solution to form white emulsion.
The nano silver chloride, silver nitrate, nano oxidation and the like are adopted as inorganic antibacterial materials, so that metal ions can be hydrolyzed in water, meanwhile, the nano silver-based antibacterial material has better dispersing effect compared with nano silver, and the color problem of metal is avoided while the antibacterial effect of the metal ions is maintained.
The pH value of the solution is adjusted to 6-6.5 by a method of adjusting the pH value with dilute acid, and chitosan is in a very good dispersion state in the solution, so that the solution is not easy to precipitate.
Wherein, the chitosan is a natural polymer with wide sources, and has the characteristics of good film forming property, degradability, good biocompatibility and the like; meanwhile, the chitosan also has a certain antibacterial effect, and can be used as a natural antibacterial polymer raw material. The pH value is regulated by weak acid, so that the modified amino acid can be uniformly dispersed in aqueous solution, and simultaneously hydroxyl and amino in the structure have good reactivity and are easy to carry out chemical modification, so that the multifunction is realized;
the polyhexamethylene guanidine hydrochloride is an organic antibacterial agent with high-efficiency sterilization effect, has good sterilization effect on various bacteria, is low in cost, can realize broad-spectrum antibacterial effect, and has the characteristics of no toxicity, no color and no smell;
the addition of the methylbenzotriazole reduces the corrosion rate of metals, and the methylbenzotriazole is used as a common antirust agent and corrosion inhibitor, and can enhance the corrosion inhibition effect on metals such as silver, zinc and the like when being matched with antibacterial materials, so that the antibacterial agent is more stable and efficient.
The beneficial effects of the invention are as follows:
(1) The method of adding chitosan solves the problems that inorganic antibacterial agent is easy to precipitate and inorganic and organic antibacterial agents are not easy to combine, and due to the low adhesiveness of chitosan, the chitosan can be adhered with other insoluble substances such as inorganic antibacterial agent and the like and uniformly dispersed in the solution, so that the whole solution achieves a good dispersing effect. When the chitosan solution is coated on the surface of an object, the chitosan solution is stable and not easy to volatilize, so that the continuous antibacterial effect can be achieved by cooperating with other antibacterial materials, and the whole chitosan solution after pH adjustment is in a white emulsion shape, so that the chitosan solution meets the commercial requirement;
(2) The inorganic and organic antibacterial agents are mixed for use, so that the defects of the inorganic and organic antibacterial agents are reduced, wherein the organic antibacterial agents of hydrochloride can generate a plurality of anions in water, are easy to combine with metal cations, and promote the forward hydrolysis reaction of the metal ions in the solution, so that the problem of dispersing the inorganic antibacterial agents can be well solved; the organic antibacterial agent is volatile, and in the coexistence state with the inorganic nano metal material, the organic antibacterial agent is influenced by metal ions to reduce the volatility, so that the solution is more stable. Under the interaction of the two, more stable organic antibacterial groups and inorganic metal cations exist in the solution, so that the damage effect on bacterial cell membranes and cell walls is enhanced, and the antibacterial property is improved.
(3) The composite antibacterial agent is nontoxic and harmless, is safe and reliable, has low cost, and is suitable for commercial application.
Drawings
FIG. 1 is a chart of the zone of inhibition of Staphylococcus aureus of examples and comparative examples;
FIG. 2 is a chart of the zone of inhibition of E.coli for examples and comparative examples.
Detailed Description
The following detailed description of the present invention is provided in connection with, but not limited to, exemplary embodiments of the invention, as well as all other embodiments of the invention, which can be obtained by one of ordinary skill in the art without undue effort from the embodiments of the invention, are within the scope of the present invention.
Example 1
A100 g compound antibacterial agent comprises the following components in a formula: 3g of organic antibacterial agent A; 1g of polyhexamethylene guanidine hydrochloride; 1.2g of chitosan; 0.2g of methylbenzotriazole; 0.5g of inorganic antibacterial agent; the rest is deionized water.
In this example, all materials were purchased commercially, wherein the polyhexamethylene guanidine hydrochloride content was 20%, the methylbenzotriazole content was 99.5%, the organic antimicrobial was high purity grade, and the inorganic antimicrobial was nano grade.
In this example, the organic antimicrobial agent A is sodium polyaspartate and the inorganic antimicrobial agent is silver chloride, the particle size of which is about 30-70nm.
The preparation method of the composite antibacterial agent comprises the following steps:
step A1: accurately weighing an organic antibacterial agent A, polyhexamethylene guanidine hydrochloride, methylbenzotriazole, an inorganic antibacterial agent and chitosan;
step A2: adding the organic antibacterial agent A and polyhexamethylene guanidine hydrochloride into a 250mL three-neck flask, adding a proper amount of deionized water, mechanically stirring at 30 ℃ at 600rpm, and uniformly mixing;
step A3: grinding the methylbenzotriazole into powder with the particle size smaller than 10 microns, adding the powder into a flask, directly adding the nano-scale inorganic antibacterial agent and chitosan in a state of purchasing, and simultaneously continuously mechanically stirring and uniformly mixing;
step A4: preparing 0.1mol/L hydrochloric acid dilute solution with concentrated hydrochloric acid, regulating the pH of the solution to 6-6.5, and uniformly dispersing chitosan in the solution to form an emulsion with low viscosity.
Comparative example 1
Comparative example 1 differs from example 1 in that polyhexamethylene guanidine hydrochloride is not added, and the remainder is referred to example 1.
Example 2
A100 g compound antibacterial agent comprises the following components in a formula: 1g of polyhexamethylene guanidine hydrochloride; 1.2g of chitosan; 0.2g of methylbenzotriazole; 0.5g of inorganic antibacterial agent; the rest is deionized water.
In this example, all materials were commercially available, wherein the polyhexamethylene guanidine hydrochloride content was 20%, the methylbenzotriazole content was 99.5%, and the inorganic antimicrobial agent was nano-sized.
In this embodiment, the inorganic antimicrobial agent is silver chloride, which has a particle size of about 30-70nm.
The preparation of the composite antibacterial agent comprises the following steps:
step A1: accurately weighing polyhexamethylene guanidine hydrochloride, methylbenzotriazole, an inorganic antibacterial agent and chitosan;
step A2: adding polyhexamethylene guanidine hydrochloride into a 250mL three-neck flask, adding a proper amount of deionized water, mechanically stirring at 30 ℃ at 600rpm, and uniformly mixing;
step A3: grinding the methylbenzotriazole into powder with the particle size smaller than 10 microns, adding the powder into a flask, directly adding the nano-scale inorganic antibacterial agent and chitosan in a state of purchasing, and simultaneously continuously mechanically stirring and uniformly mixing;
step A4: preparing 0.1mol/L hydrochloric acid dilute solution with concentrated hydrochloric acid, regulating the pH of the solution to 6-6.5, and uniformly dispersing chitosan in the solution to form an emulsion with low viscosity.
Example 3
A100 g compound antibacterial agent comprises the following components in a formula: 3g of organic antibacterial agent A; 1g of polyhexamethylene guanidine hydrochloride; 1.2g of chitosan; 0.2g of methylbenzotriazole; 0.5g of inorganic antibacterial agent; the rest is deionized water.
In this example, all materials were purchased commercially, wherein the polyhexamethylene guanidine hydrochloride content was 20%, the methylbenzotriazole content was 99.5%, the organic antimicrobial was high purity grade, and the inorganic antimicrobial was nano grade.
In this example, the organic antimicrobial agent A is epsilon-polylysine, and the inorganic antimicrobial agent is silver chloride, with a particle size of about 30-70nm.
The preparation of the composite antibacterial agent comprises the following steps:
step A1: accurately weighing an organic antibacterial agent A, polyhexamethylene guanidine hydrochloride, methylbenzotriazole, an inorganic antibacterial agent and chitosan;
step A2: adding the organic antibacterial agent A and polyhexamethylene guanidine hydrochloride into a 250mL three-neck flask, adding a proper amount of deionized water, mechanically stirring at 30 ℃ at 600rpm, and uniformly mixing;
step A3: grinding the methylbenzotriazole into powder with the particle size smaller than 10 microns, adding the powder into a flask, directly adding the nano-scale inorganic antibacterial agent and chitosan in a state of purchasing, and simultaneously continuously mechanically stirring and uniformly mixing;
step A4: preparing 0.1mol/L hydrochloric acid dilute solution with concentrated hydrochloric acid, regulating the pH of the solution to 6-6.5, and uniformly dispersing chitosan in the solution to form an emulsion with low viscosity.
Example 4
A100 g compound antibacterial agent comprises the following components in a formula: 3g of organic antibacterial agent A; 1g of polyhexamethylene guanidine hydrochloride; 1.2g of chitosan; 0.2g of methylbenzotriazole; 0.5g of inorganic antibacterial agent; the rest is deionized water.
In this example, all materials were purchased commercially, wherein the polyhexamethylene guanidine hydrochloride content was 20%, the methylbenzotriazole content was 99.5%, the organic antimicrobial was high purity grade, and the inorganic antimicrobial was nano grade.
In this example, the organic antimicrobial agent A is polyaspartic acid, the inorganic antimicrobial agent is silver chloride, and the particle size is about 30-70nm.
The preparation of the composite antibacterial agent comprises the following steps:
step A1: accurately weighing an organic antibacterial agent A, polyhexamethylene guanidine hydrochloride, methylbenzotriazole, an inorganic antibacterial agent and chitosan;
step A2: adding the organic antibacterial agent A and polyhexamethylene guanidine hydrochloride into a 250mL three-neck flask, adding a proper amount of deionized water, mechanically stirring at 30 ℃ at 600rpm, and uniformly mixing;
step A3: grinding the methylbenzotriazole into powder with the particle size smaller than 10 microns, adding the powder into a flask, directly adding the nano-scale inorganic antibacterial agent and chitosan in a state of purchasing, and simultaneously continuously mechanically stirring and uniformly mixing;
step A4: preparing 0.1mol/L hydrochloric acid dilute solution with concentrated hydrochloric acid, regulating the pH of the solution to 6-6.5, and uniformly dispersing chitosan in the solution to form an emulsion with low viscosity.
Examples:
a100 g compound antibacterial agent comprises the following components in a formula: 3g of organic antibacterial agent A; 1g of polyhexamethylene guanidine hydrochloride; 1.2g of chitosan; 0.2g of methylbenzotriazole; 0.5g of inorganic antibacterial agent; the rest is deionized water.
In this example, all materials were purchased commercially, wherein the polyhexamethylene guanidine hydrochloride content was 20%, the methylbenzotriazole content was 99.5%, the organic antimicrobial was high purity grade, and the inorganic antimicrobial was nano grade.
In this example, the organic antimicrobial agent A is epsilon-polylysine hydrochloride and the inorganic antimicrobial agent is silver chloride, with a particle size of about 30-70nm.
The preparation of the composite antibacterial agent comprises the following steps:
step A1: accurately weighing an organic antibacterial agent A, polyhexamethylene guanidine hydrochloride, methylbenzotriazole, an inorganic antibacterial agent and chitosan;
step A2: adding the organic antibacterial agent A and polyhexamethylene guanidine hydrochloride into a 250mL three-neck flask, adding a proper amount of deionized water, mechanically stirring at 30 ℃ at 600rpm, and uniformly mixing;
step A3: grinding the methylbenzotriazole into powder with the particle size smaller than 10 microns, adding the powder into a flask, directly adding the nano-scale inorganic antibacterial agent and chitosan in a state of purchasing, and simultaneously continuously mechanically stirring and uniformly mixing;
step A4: preparing 0.1mol/L hydrochloric acid dilute solution with concentrated hydrochloric acid, regulating the pH of the solution to 6-6.5, and uniformly dispersing chitosan in the solution to form an emulsion with low viscosity.
Commercial comparative 1
Adopts the sterilizing liquid sold in the market.
The components of examples 1 to 5 and comparative examples are summarized in Table one:
list one
Antibacterial performance test:
the antibacterial effect of each embodiment is tested by performing a bacteriostasis circle experiment. The test selects staphylococcus aureus, escherichia coli and bacillus subtilis as representatives as test strains to test the broad-spectrum antibacterial property of the antibacterial agent and compare the antibacterial agent with commercial antibacterial liquid.
The test method is as follows: bacterial suspensions of staphylococcus aureus and escherichia coli are cultured in advance, the bacterial suspension is diluted to be at the concentration of 107CFU/mL, 0.2mL of the bacterial suspension is coated on a solid culture medium, a filter paper sheet is attached to the culture medium, and 20ul of antibacterial liquid of each embodiment is dripped on the filter paper sheet. After incubation at 37℃for 24 hours, the size of the zone of inhibition around the filter paper was measured and 7 diameters were taken and the average value calculated.
The test results are shown in Table II:
watch II
Fig. 1 shows a physical diagram of a bacteriostasis zone of different embodiments, wherein average diameter of the bacteriostasis zone is obtained through multipoint measurement, and the data are summarized in a second table. As can be seen from the results of Table II, the examples 1 to 5 of the present invention all obtained a good antibacterial effect, which is comparable to that of commercial antibacterial agents. The average inhibition zone diameter obtained in comparative example 1 is far smaller than that of the examples, so that the polyhexamethylene guanidine hydrochloride is an indispensable component for greatly improving the antibacterial effect of the antibacterial liquid. This is because polyhexamethylene guanidine hydrochloride is used as an organic hydrochloride, a large amount of chloride ions can be ionized in water, and negatively charged chloride ions attract positively charged metal cations, so that the hydrolysis reaction of the metal in the aqueous solution is promoted to move forward, and the concentration of the metal cations in the solution is increased. The cell membrane and the cell wall of the bacteria contain negatively charged proteins, and metal cations can be adsorbed on the negatively charged proteins to destroy the normal respiration and metabolism of the cells, so that the aim of killing the bacteria is fulfilled, the polyhexamethylene guanidine hydrochloride promotes the generation of metal ions in the solution, and the antibacterial effect of the solution is greatly enhanced.
In the embodiment 4, polyaspartic acid is adopted as an organic antibacterial material, the prepared antibacterial liquid is white and milky, has better antibacterial effect on various bacteria, and is a product meeting the market requirement.
In addition, the antibacterial solution prepared by using the other organic hydrochloride- "epsilon-polylysine hydrochloride" in example 5 shows the optimal antibacterial effect on both gram-positive bacteria (staphylococcus aureus) and gram-negative bacteria (escherichia coli), is an excellent antibacterial component, and further shows that the organic component of the hydrochloride has the promoting effect on the amount of metal ions in the aqueous solution, thereby improving the antibacterial effect.
The test results of the inhibition zone of the nano inorganic antibacterial material are shown in Table III:
average inhibition zone diameter of various bacteria
| Name of the name | Proportion of | Bacillus subtilis | Coli bacterium |
| ZnO | 0.20％ | 1.53 | 1.92 |
| ZnO | 0.35％ | 1.52 | 1.80 |
| ZnO | 0.50％ | 1.62 | 1.88 |
| Ag | 0.20％ | 1.45 | 2.01 |
| Ag | 0.35％ | 1.63 | 2.15 |
| Ag | 0.50％ | 1.85 | 2.57 |
| AgNO 3 | 0.20％ | 1.53 | 1.47 |
| AgNO 3 | 0.35％ | 1.58 | 1.87 |
| AgNO 3 | 0.50％ | 1.80 | 2.05 |
| AgCl | 0.20％ | 1.83 | 2.47 |
| AgCl | 0.50％ | 2.48 | 2.45 |
Table III shows the average inhibition zone diameters of inorganic metal antibacterial agents with different proportions on enterobacteria and bacillus subtilis, and as can be seen from the Table III, the inhibition zone diameters are increased and the antibacterial effect is increased along with the increase of the concentration of nano metal. Different nano zinc oxide, nano silver chloride, silver nitrate and the like have similar or even better antibacterial effects than nano silver, and are inorganic materials which are enough to replace nano silver.
The above embodiment is only used for further illustrating a composite antibacterial agent and a preparation method thereof, but the invention is not limited to the embodiment, and any simple modification, equivalent variation and modification of the above embodiment according to the technical substance of the invention falls within the protection scope of the technical proposal of the invention.
Claims (9)
1. A composite antimicrobial agent, characterized by: the formula comprises the following components in percentage by weight: 2.5 to 4 percent of organic antibacterial agent, 0.8 to 1.2 percent of chitosan, 0.1 to 0.2 percent of methylbenzotriazole, 0.2 to 0.5 percent of inorganic antibacterial agent and the balance of deionized water; wherein the organic antibacterial agent at least comprises polyhexamethylene guanidine hydrochloride, and the content of the polyhexamethylene guanidine hydrochloride in the composite antibacterial agent is 0.5-1%.
2. The composite antibacterial agent according to claim 1, characterized in that: the inorganic antibacterial agent comprises one of nano silver nitrate, nano silver chloride and nano zinc oxide.
3. The composite antibacterial agent according to claim 2, characterized in that: the size of the inorganic antibacterial agent is in the range of 0.5-80nm.
4. The composite antibacterial agent according to claim 1, characterized in that: the organic antibacterial agent also comprises one of sodium polyaspartic acid, epsilon-polylysine and epsilon-polylysine hydrochloride.
5. The composite antibacterial agent according to claim 1, characterized in that: the pH value of the composite antibacterial agent is 6-6.5.
6. A method of preparing the composite antibacterial agent of any one of claims 1 to 5, comprising the steps of:
step A1: weighing an organic antibacterial agent, methyl benzotriazole, an inorganic antibacterial agent and chitosan according to the proportion; wherein the organic antibacterial agent comprises polyhexamethylene guanidine hydrochloride;
step A2: mixing the organic antibacterial agent with deionized water, mechanically stirring at a medium speed at 25-35 ℃, and uniformly mixing;
step A3: adding the methylbenzotriazole, continuously stirring, and then adding the inorganic antibacterial agent and the chitosan, continuously stirring and uniformly mixing;
step A4: and (3) adjusting the pH value, and adjusting the solution formed in the step A3 into a uniform mixed state.
7. The method of manufacturing according to claim 6, wherein: in the step A3, the methylbenzotriazole is added after being ground into powder with the particle size smaller than 10 microns.
8. The method of manufacturing according to claim 6, wherein: in steps A2 and A3, the stirring speed is 400-800rpm.
9. The method of manufacturing according to claim 6, wherein: the step A4 specifically comprises the following steps: preparing 0.1mol/L hydrochloric acid diluted solution with concentrated hydrochloric acid, and regulating pH of the solution to 6-6.5 to uniformly disperse chitosan in the solution to form white emulsion.
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