A self-assembled supramolecular modified chitosan composite material, its preparation method and application

Abstract

This application relates to the technical field of daily chemical products, and specifically discloses a self-assembled supramolecular modified chitosan composite material, its preparation method and application. In terms of mass percentage, the self-assembled supramolecular modified chitosan composite material of this application includes: 10-20% carboxymethyl deacetylated chitosan, 0.2-1.0% sodium bentonite modified by cationic polymer, and the balance water. In this application, carboxymethyl deacetylated chitosan and sodium bentonite modified by cationic polymer are compounded. During the mixing process, carboxymethyl deacetylated chitosan and sodium bentonite modified by cationic polymer undergo supramolecular self-assembly, and carboxymethyl deacetylated chitosan is orderly intercalated into sodium bentonite modified by cationic polymer to prepare a self-assembled supramolecular modified chitosan composite material, which ultimately shows a very good effect of improving the scalp microecology, repairing the skin and reducing skin inflammation.

Description

Technical Field

[0001] The present application relates to the technical field of daily chemical products, and in particular to a self-assembled supramolecular modified chitosan composite material, a preparation method thereof, and an application thereof. Background Art

[0002] With the improvement of living standards, people's life rhythm is getting faster and their work pressure is increasing accordingly. In addition, with the increase of age, a large part of the population has the problem of excessive sebum secretion on the skin (including the scalp). Excessive sebum secretion easily causes dirt, especially fat-soluble organic substances and many kinds of microorganisms to accumulate, which easily allows bacteria, fungi, viruses, etc. to penetrate directly and cause infections, leading to inflammatory reactions, and making the skin prone to problems such as skin microecological imbalance, inflammation, and damaged skin barrier.

[0003] Therefore, there is an urgent need to provide raw materials with barrier repair functions to improve the skin microecology, repair the skin, and reduce skin inflammation. Summary of the Invention

[0004] The purpose of the present application is to overcome the deficiencies of the above-mentioned prior art and provide a self-assembled supramolecular modified chitosan composite material, a preparation method thereof, and an application thereof. The self-assembled supramolecular modified chitosan composite material designed by the present application can improve the scalp microecology, repair the skin, and reduce skin inflammation.

[0005] To achieve the above purpose, the technical solution adopted by the present application is as follows:

[0006] The present application provides a self-assembled supramolecular modified chitosan composite material. Calculated by mass percentage, the self-assembled supramolecular modified chitosan composite material includes:

[0007] 10-20% carboxymethyl deacetylated chitosan, 0.2-1.0% sodium bentonite modified by a cationic polymer, and the balance water.

[0008] Supramolecules generally refer to aggregates composed of two or more molecules held together by intermolecular interactions, with a complex and organized structure, maintaining a certain integrity, and having a clear microscopic structure and macroscopic properties.

[0009] In the present application, carboxymethyl deacetylated chitosan and sodium bentonite modified by a cationic polymer are compounded. During the mixing process, carboxymethyl deacetylated chitosan and sodium bentonite modified by a cationic polymer perform supramolecular self-assembly, and carboxymethyl deacetylated chitosan is orderly intercalated into sodium bentonite modified by a cationic polymer to obtain a self-assembled supramolecular modified chitosan composite material.

[0010] Among them, the spacing between bentonites in the sodium bentonite modified by cationic polymer increases, and carboxymethyl deacetylated chitosan molecules can more easily enter the intercalation structure of bentonite. Carboxymethyl deacetylated chitosan and sodium bentonite modified by cationic polymer maintain structural stability through hydrogen bonds and van der Waals forces, and the final product has good stability.

[0011] In the self-assembled supramolecular modified chitosan composite material of the present application, after the bentonite is modified, not only the interlayer spacing of the bentonite becomes larger, but also the surface of the bentonite has a certain positive charge, so that after the subsequent assembly with carboxymethyl deacetylated chitosan, there is a synergistic effect between the sodium bentonite modified by the cationic polymer and the carboxymethyl deacetylated chitosan, and the final product shows a good effect of improving the scalp microecology (specifically, the antibacterial concentration for Staphylococcus epidermidis is >100000 mg / kg, the minimum inhibitory concentration for Propionibacterium acnes is <9200 mg / kg, and the minimum inhibitory concentration for Malassezia furfur is <3800 mg / kg), repairing the skin and reducing skin inflammation.

[0012] As a preferred embodiment of the self-assembled supramolecular modified chitosan composite material described in the present application, the weight average molecular weight of the carboxymethyl deacetylated chitosan is 100 kDa to 180 kDa, and the degree of deacetylation is 70 to 95%.

[0013] The present application adopts carboxymethyl deacetylated chitosan with a weight average molecular weight and a degree of deacetylation within the above-mentioned range. The sodium bentonite modified by the cationic polymer has good dispersibility in the carboxymethyl deacetylated chitosan solution. The self-assembled supramolecular modified chitosan composite material finally prepared is not prone to precipitation and stratification. The product quality is better and is more conducive to the product improving the scalp microecology, repairing the skin and reducing skin inflammation.

[0014] When the weight average molecular weight of carboxymethyl deacetylated chitosan is lower than 100 kDa, the viscosity of the obtained carboxymethyl deacetylated chitosan solution is low, and the final product is prone to the phenomenon of modified bentonite precipitation and stratification after being placed for a period of time. When the weight average molecular weight of carboxymethyl deacetylated chitosan is higher than 180 kDa, the viscosity of the obtained carboxymethyl deacetylated chitosan solution is too high, and the sodium bentonite modified by the cationic polymer is not easy to disperse in the chitosan solution, resulting in poor quality of the final product (improving scalp microecology, repairing skin and reducing skin inflammation, etc.).

[0015] Moreover, chitosan is the product of chitin after deacetylation. The degree of deacetylation determines the content of amino groups on the polysaccharide molecular chain. The lower the degree of deacetylation, the more difficult it is for chitosan to dissolve in water. However, the higher the degree of deacetylation, the more charged groups are generated due to the protonation of amino groups in dilute acid solutions, resulting in changes in its structure and differences in properties. Therefore, the degree of deacetylation of the carboxymethyl deacetylated chitosan used in this application should be controlled between 70% and 95%.

[0016] As a preferred embodiment of the self-assembled supramolecular modified chitosan composite material described in this application, the particle size of the cationic polymer modified sodium bentonite is 30 - 80 μm.

[0017] When the cationic polymer modified sodium bentonite in this application adopts the above particle size, when the particle size of the cationic polymer modified sodium bentonite is less than 30 μm, not only does the grinding cost increase sharply, but during the subsequent self-assembly reaction, the particles of the cationic polymer modified sodium bentonite with too small a particle size are prone to agglomeration due to electrostatic interaction, and it is not easy for carboxymethyl deacetylated chitosan to intercalate into the interlayer structure of the bentonite; when the particle size of the cationic polymer modified sodium bentonite is greater than 80 μm, the particle size of the cationic polymer modified sodium bentonite is too large, and after being prepared into the final product, the cationic polymer modified sodium bentonite is prone to precipitation and the product is unstable.

[0018] As a preferred embodiment of the self-assembled supramolecular modified chitosan composite material described in this application, the cationic polymer includes at least one of polyquaternium-11, polyquaternium-16, polyquaternium-24, polyquaternium-28, polyquaternium-37, and polyquaternium-73.

[0019] Using the above types of cationic polymers can improve the performance of the self-assembled supramolecular modified chitosan composite material in improving the scalp microecology, repairing the skin and alleviating inflammation, as well as improving stability.

[0020] As a preferred embodiment of the preparation method of the cationic polymer modified sodium bentonite described in this application, it includes the following steps:

[0021] 1) Mix bentonite with water, stir and then let it stand, and obtain washed bentonite after removing the upper layer solution;

[0022] 2) Add the sodium salt solution to the washed bentonite prepared in step 1), stir and then let it stand, and obtain sodium bentonite after removing the upper layer solution;

[0023] 3) Immerse the sodium bentonite prepared in step 2) in the cationic polymer solution, stir and then let it stand, remove the upper layer solution, and then calcine at high temperature and perform ball milling treatment to obtain the cationic polymer modified sodium bentonite.

[0024] The purpose of modifying bentonite in the present application is to improve the performance and stability of the self-assembled supramolecular modified chitosan composite material.

[0025] In the technical solution of the present application, commercially available bentonite (usually calcium-based bentonite) usually contains more impurities. However, the final product of the present application is a suspension. The presence of these impurities can easily affect the stability and performance of the final product. Therefore, the use of water washing in step 1) is beneficial to reduce the impurities in the sodium bentonite modified by the cationic polymer and improve the performance and stability of the final product.

[0026] In the present application, through step 2), commercially available bentonite is soaked in a sodium salt solution, and sodium ions enter the interlayer structure of the bentonite, replacing the calcium ions therein, thereby reducing the van der Waals force between the layers, increasing the interlayer spacing, and improving the adsorption, cation exchange and water absorption and swelling properties of the bentonite, thereby obtaining sodium bentonite; compared with calcium-based bentonite, the interlayer spacing of the sodium bentonite is larger, and its adsorption, cation exchange and water absorption and swelling properties are better than those of calcium-based bentonite.

[0027] Furthermore, the sodium bentonite is further modified with a cationic polymer through step 3), and the cationic polymer exhibits weak acidity, which can further weaken the van der Waals force between layers and increase the interlayer spacing. In addition, after the cationic polymer modification, the bentonite exhibits a certain positive charge. When it is subsequently compounded with a carboxymethyl deacetylated chitosan solution, the bactericidal performance of the final product can be further improved, and the performance of the final product in improving the scalp microecology, repairing the scalp and reducing inflammation can be enhanced.

[0028] Furthermore, through the high temperature activation treatment and ball milling treatment steps of step 3), the high temperature activation treatment can bring out the water on the surface of bentonite and the bound water in the framework, thereby improving the porosity and adsorption performance of bentonite. Bentonite after high temperature activation is often prone to caking. Compared with ordinary grinding treatment, ball milling treatment adds grinding balls during the grinding process, which can fully grind the caking bentonite into fine bentonite particles, and the subsequent bentonite is also more likely to self-assemble with carboxymethyl deacetylated chitosan to form a supramolecular structure.

[0029] The cationic polymer-modified sodium bentonite obtained by the above-mentioned steps can inhibit the growth of harmful bacteria, has a good effect of regulating microecology, and can also improve the anti-inflammatory and repair effects.

[0030] Preferably, the sodium salt solution is a sodium salt solution that is neutral (pH is about 7) after being dissolved in water; the sodium salt solution is at least one of sodium sulfate, sodium bisulfate, sodium chloride, and sodium nitrate solution.

[0031] The present application uses the above-mentioned types of sodium salt solutions, cationic polymers and their concentrations, which can better improve the stability of the self-assembled supramolecular modified chitosan composite material, and is beneficial to the effects of the self-assembled supramolecular modified chitosan composite material in improving the scalp microecology, repairing the skin and reducing skin inflammation, etc.

[0032] As a preferred embodiment of the self-assembled supramolecular modified chitosan composite material described in the present application, in step 1), the mass ratio of the bentonite to water is 1:(4-8); in step 2), the mass ratio of the washed bentonite to the sodium salt solution is 1:(4-8); in step 3), the mass ratio of the sodium-modified bentonite to the cationic polymer solution is 1:(4-8).

[0033] As a preferred embodiment of the self-assembled supramolecular modified chitosan composite material described in the present application, the concentration of sodium ions in the sodium salt solution is 1-3 mol / L, and the concentration of the cationic polymer in the cationic polymer solution is 0.5-2 wt%.

[0034] When the concentration of the cationic polymer in the cationic polymer solution is too high, the amount of the cationic polymer attached to the surface of the bentonite will increase. Chitosan itself is also a polymer. The increase in the cationic polymer will make it difficult for chitosan to intercalate into the bentonite.

[0035] As a preferred embodiment of the self-assembled supramolecular modified chitosan composite material described in the present application, in step 1), the stirring time is 30-90 min, the stirring speed is 80-150 rpm, and the standing time is 60-120 min;

[0036] In steps 2) and 3), the stirring time is 3-5 h, the stirring speed is 80-150 rpm, and the standing time is 60-120 min;

[0037] In step 3), the calcination temperature is 130-200 °C, and the calcination time is 90-150 min.

[0038] In the technical solution of the present application, the calcination temperature cannot be too high or too low, and should be controlled between 130-200 °C. When the calcination temperature is lower than 130 °C, the surface water and the bound water in the framework of the bentonite are not easily removed, which is not conducive to subsequent self-assembly. When the calcination temperature is higher than 200 °C, the cationic polymer attached to the surface of the bentonite is prone to structural changes or even carbonization, which is not conducive to the preparation of the self-assembled supramolecular modified chitosan composite material.

[0039] The present application also provides a preparation method of the above-mentioned self-assembled supramolecular modified chitosan composite material, comprising the following steps:

[0040] (1) Mix water and carboxymethyl chitosan uniformly to obtain a carboxymethyl chitosan solution;

[0041] (2) Mix the carboxymethyl chitosan solution with sodium bentonite modified by a cationic polymer, and after high-speed shear dispersion treatment and ultrasonic treatment, a self-assembled supramolecular modified chitosan composite material is obtained;

[0042] The rotation speed of the high-speed shear dispersion treatment is 6000-12000 rpm, and the time of the high-speed shear dispersion treatment is 20-40 min;

[0043] The power of the ultrasonic treatment is 400-800 W, and the time of the ultrasonic treatment is 40-80 min.

[0044] In the technical solution of the present application, the viscosity of the carboxymethyl chitosan solution is relatively large. After adding sodium bentonite modified by a cationic polymer, it is very difficult to disperse the sodium bentonite modified by a cationic polymer in the carboxymethyl chitosan solution by conventional stirring treatment, and it is very difficult to self-assemble into a supramolecule. The sodium bentonite modified by a cationic polymer is likely to precipitate, resulting in poor product quality. For example, the antibacterial effects of the product against Propionibacterium acnes and Malassezia furfur become poor, and the anti-inflammatory and skin repair effects also become poor.

[0045] The high-speed shear dispersion treatment can uniformly disperse the sodium bentonite modified by a cationic polymer in the carboxymethyl chitosan solution, which is beneficial to the self-assembly of the sodium bentonite modified by a cationic polymer and the carboxymethyl chitosan solution into a supramolecular structure.

[0046] In the technical solution of the present application, the ultrasonic treatment can discharge the bubbles in the preparation process of the self-assembled supramolecular modified chitosan composite material and improve the stability of the final product.

[0047] The present application also provides an application of the above self-assembled supramolecular modified chitosan composite material in the preparation of daily chemicals.

[0048] In some embodiments of the present application, the addition amount of the self-assembled supramolecular modified chitosan composite material in the daily chemicals is 0.1-15 wt%.

[0049] Compared with the prior art, the present application has the following beneficial effects:

[0050] The present application provides a self-assembled supramolecular modified chitosan composite material, a preparation method thereof, and an application thereof. In the present application, carboxymethyl deacetylated chitosan and sodium bentonite modified with a cationic polymer are compounded. During the mixing process, the carboxymethyl deacetylated chitosan and the sodium bentonite modified with the cationic polymer perform supramolecular self-assembly, and the carboxymethyl deacetylated chitosan is orderly intercalated into the sodium bentonite modified with the cationic polymer to obtain a self-assembled supramolecular modified chitosan composite material. In the self-assembled supramolecular modified chitosan composite material of the present application, after the bentonite is modified, not only does the layer spacing of the bentonite become larger, but also the surface of the bentonite carries a certain amount of positive charge, so that after subsequent assembly with carboxymethyl deacetylated chitosan, there is a synergistic effect between the sodium bentonite modified with the cationic polymer and the carboxymethyl deacetylated chitosan, and the final product exhibits good effects of improving the scalp microecology, repairing the skin, and reducing skin inflammation. Description of the Drawings

[0051] Figure 1 SEM image of the self-assembled supramolecular modified chitosan composite material prepared in Example 1. Detailed Embodiments

[0052] To better illustrate the purpose, technical solution, and advantages of the present application, the present application will be further described below in conjunction with the drawings and specific embodiments.

[0053] In the following examples and comparative examples, unless otherwise specified, the experimental methods used are all conventional methods, and the materials, reagents, etc. used, unless otherwise specified, can all be obtained from commercial channels, and the component raw materials used in each parallel experiment are all of the same kind.

[0054] Unless otherwise specified, the percentages mentioned in the present application are all mass percentages.

[0055] The bentonite used in the present application is commercially available ordinary bentonite.

[0056] The carboxymethyl deacetylated chitosan used in the examples and comparative examples of the present application and the chitosan in the comparative examples are all sourced from Guangdong Zhongyan Zhijue Technology Co., Ltd. Carboxymethyl deacetylated chitosan obtained from other sources and meeting the molecular weight and deacetylation degree requirements of the present application can also be used in the present application.

[0057] The polyquaternium-11, polyquaternium-16, polyquaternium-24, polyquaternium-28, polyquaternium-37, and polyquaternium-73 used in the present application are sourced from Dongguan Jumicrobiology Technology Co., Ltd.

[0058] Example 1. A self-assembled supramolecular modified chitosan composite material and a preparation method thereof

[0059] This example provides a self-assembled supramolecular modified chitosan composite material, which comprises components in the following mass percentages: 0.4% of sodium bentonite modified by cationic polymer, 17% of carboxymethyl deacetylated chitosan, and 82.6% of deionized water.

[0060] The particle size of the sodium bentonite modified by cationic polymer is 50 μm, the weight-average molecular weight of the carboxymethyl deacetylated chitosan is 130 ± 2 kDa (about 130 kDa), and the degree of deacetylation is 80 ± 3% (about 80%).

[0061] The preparation method of the self-assembled supramolecular modified chitosan composite material is as follows:

[0062] (1) Mix water and carboxymethyl deacetylated chitosan evenly to obtain a carboxymethyl deacetylated chitosan solution;

[0063] (2) Add sodium bentonite modified by cationic polymer to the carboxymethyl deacetylated chitosan solution, mix evenly, subject the mixture to high-speed shear dispersion treatment at 9000 rpm for 30 min, and then subject it to ultrasonic treatment at 500 W for 60 min to obtain the self-assembled supramolecular modified chitosan composite material.

[0064] Among them, the preparation method of the sodium bentonite modified by cationic polymer is as follows:

[0065] 1) Mix commercially available bentonite with 6 times its mass of water, stir at 120 rpm for 60 min, then let it stand for 90 min, and remove the upper-layer solution to obtain washed bentonite;

[0066] 2) Add 6 times the mass of 2 mol / L sodium chloride solution to the washed bentonite, stir at 120 rpm for 4 h, then let it stand for 90 min, and remove the upper-layer sodium chloride solution to obtain sodium bentonite;

[0067] 3) Add 6 times the mass of 1 wt% polyquaternium-16 solution to the sodium bentonite, stir at 120 rpm for 4 h, then let it stand for 90 min, remove the upper-layer polyquaternium-16 solution, and then calcine at 160 °C for 120 min, and obtain the sodium bentonite modified by cationic polymer after ball milling treatment.

[0068] The scanning electron micrograph of the self-assembled supramolecular modified chitosan composite material is as Figure 1 shown, and the self-assembled supramolecular modified chitosan composite materials of the remaining examples are similar to Figure 1 this.

[0069] Example 2. A self-assembled supramolecular modified chitosan composite material and its preparation method

[0070] This example provides a self-assembled supramolecular modified chitosan composite material, which includes the following components by mass percentage: 0.2% sodium bentonite modified by cationic polymer, 10% carboxymethyl deacetylated chitosan, and 89.8% deionized water.

[0071] The particle size of the sodium bentonite modified by cationic polymer is 80 μm, the weight-average molecular weight of the carboxymethyl deacetylated chitosan is 105 ± 2 kDa (about 105 kDa), and the degree of deacetylation is 75 ± 3% (about 75%).

[0072] The preparation method of the self-assembled supramolecular modified chitosan composite material is as follows:

[0073] (1) Mix water and carboxymethyl deacetylated chitosan evenly to obtain a carboxymethyl deacetylated chitosan solution;

[0074] (2) Add sodium bentonite modified by cationic polymer to the carboxymethyl deacetylated chitosan solution, mix evenly, subject the mixture to high-speed shear dispersion treatment at 12000 rpm for 20 min, and then subject it to ultrasonic treatment at 800 W for 40 min to obtain the self-assembled supramolecular modified chitosan composite material.

[0075] Among them, the preparation method of the sodium bentonite modified by cationic polymer is as follows:

[0076] 1) Mix bentonite with 4 times its mass of water, stir at 150 rpm for 30 min, then let it stand for 120 min, and remove the upper-layer solution to obtain washed bentonite;

[0077] 2) Add 4 times the mass of 0.5 mol / L sodium sulfate solution to the washed bentonite, stir at 150 rpm for 3 h, then let it stand for 120 min, and remove the upper-layer sodium sulfate solution to obtain sodium bentonite;

[0078] 3) Add 4 times the mass of 1.8 wt% polyquaternium-11 solution to the sodium bentonite, stir at 150 rpm for 3 h, then let it stand for 120 min, remove the upper-layer polyquaternium-11 solution, and then calcine at 200 °C for 90 min, and obtain sodium bentonite modified by cationic polymer after ball milling.

[0079] Example 3. A self-assembled supramolecular modified chitosan composite material and its preparation method

[0080] This example provides a self-assembled supramolecular modified chitosan composite material, which includes the following components by mass percentage: 1.0% sodium bentonite modified by cationic polymer, 20% carboxymethyl deacetylated chitosan, and 79.0% deionized water.

[0081] The particle size of the sodium bentonite modified by cationic polymer is 30 μm, the weight-average molecular weight of carboxymethyl chitosan is 175 ± 2 kDa (about 175 kDa), and the degree of deacetylation is 80 ± 3% (about 80%).

[0082] The preparation method of the self-assembled supramolecular modified chitosan composite material is as follows:

[0083] (1) Mix water and carboxymethyl chitosan evenly to obtain a carboxymethyl chitosan solution;

[0084] (2) Add sodium bentonite modified by cationic polymer to the carboxymethyl chitosan solution, mix evenly, subject the mixture to high-speed shear dispersion treatment at 6000 rpm for 40 min, and then subject it to ultrasonic treatment at 400 W for 80 min to obtain a self-assembled supramolecular modified chitosan composite material.

[0085] Among them, the preparation method of the sodium bentonite modified by cationic polymer is as follows:

[0086] 1) Mix bentonite with 8 times its mass of water, stir at 80 rpm for 90 min, then let it stand for 60 min, and remove the upper-layer solution to obtain washed bentonite;

[0087] 2) Add 8 times the mass of 1 mol / L sodium nitrate solution to the washed bentonite, stir at 80 rpm for 5 h, then let it stand for 60 min, and remove the upper-layer sodium sulfate solution to obtain sodium bentonite;

[0088] 3) Add 8 times the mass of 0.8 wt% polyquaternium-73 solution to the sodium bentonite, stir at 80 rpm for 5 h, then let it stand for 60 min, remove the upper-layer polyquaternium-73 solution, and then calcine at 130 °C for 150 min, and obtain sodium bentonite modified by cationic polymer after ball milling treatment.

[0089] Examples 4 - 5, A Self-Assembled Supramolecular Modified Chitosan Composite Material and Its Preparation Method

[0090] Examples 4 - 5 provide a self-assembled supramolecular modified chitosan composite material. Among them, the preparation methods of the self-assembled supramolecular modified chitosan composite material and the sodium bentonite modified by cationic polymer are the same as those in Example 1. The only difference is that some parameters of carboxymethyl chitosan are different from those in Example 1, and the differences are shown in Table 1 below.

[0091] Table 1

[0092]

[0093] Examples 6 - 11, A Self-Assembled Supramolecular Modified Chitosan Composite Material and Its Preparation Method

[0094] Examples 6 - 11 provide a self - assembled supramolecular modified chitosan composite material and its preparation method. Among them, the dosage and particle size of sodium bentonite modified by cationic polymer, the dosage, molecular weight and deacetylation degree of carboxymethyl chitosan deacetylated chitosan in the self - assembled supramolecular modified chitosan composite material are the same as those in Example 1. The difference lies in that the preparation method of sodium bentonite modified by cationic polymer is different from that in Example 1. The differences between the preparation method of sodium bentonite modified by cationic polymer and that in Example 1 are shown in Table 2 below.

[0095] Table 2

[0096]

[0097]

[0098] Comparative Example 1

[0099] The difference between this comparative example and Example 1 is only that the preparation method of the self - assembled supramolecular modified chitosan composite material is different. The preparation method of the self - assembled supramolecular modified chitosan composite material is as follows:

[0100] (1) Mix water and carboxymethyl chitosan deacetylated chitosan evenly to obtain a carboxymethyl chitosan deacetylated chitosan solution;

[0101] (2) Add sodium bentonite modified by cationic polymer (the preparation method is the same as that in Example 1) to the carboxymethyl chitosan deacetylated chitosan solution, mix, mix evenly at 150 rpm, and then ultrasonically treat at 500 W for 60 min to obtain a self - assembled supramolecular modified chitosan composite material.

[0102] Comparative Example 2

[0103] The difference between the self - assembled supramolecular modified chitosan composite material of this comparative example and that of Example 1 is that in Comparative Example 2, the carboxymethyl chitosan deacetylated chitosan in Example 1 is changed to ordinary chitosan (the weight - average molecular weight of chitosan is 130 ± 2 kDa, and the deacetylation degree is 80 ± 3%), and the remaining steps and parameters are the same as those in Example 1.

[0104] Comparative Example 3

[0105] The difference between the self - assembled supramolecular modified chitosan composite material of this comparative example and that of Example 1 is that in Comparative Example 3, the carboxymethyl chitosan deacetylated chitosan with a deacetylation degree of 80 ± 3% in Example 1 is changed to carboxymethyl chitosan deacetylated chitosan with a deacetylation degree of 99 ± 1% (the deacetylation degree is about 100%), the molecular weight of carboxymethyl chitosan deacetylated chitosan remains unchanged, and the remaining steps and parameters are the same as those in Example 1.

[0106] Comparative Example 4

[0107] The difference between the self-assembled supramolecular modified chitosan composite material of this comparative example and that of Example 1 is that in Comparative Example 4, the carboxymethyl chitosan with a weight-average molecular weight of 130±2 kDa in Example 1 was changed to carboxymethyl chitosan with a weight-average molecular weight of 220±2 kDa, and the degree of deacetylation of the carboxymethyl chitosan remained unchanged. The remaining steps and parameters were the same as those in Example 1.

[0108] Comparative Example 5

[0109] The difference between the self-assembled supramolecular modified chitosan composite material of this comparative example and that of Example 1 is that in Comparative Example 5, the sodium bentonite modified by the cationic polymer in Example 1 was changed to commercially available ordinary bentonite (ball-milled into bentonite with a particle size of 50 μm). The remaining steps and parameters were the same as those in Example 1.

[0110] Comparative Example 6

[0111] The difference between the self-assembled supramolecular modified chitosan composite material of this comparative example and that of Example 1 is that the preparation method of the sodium bentonite modified by the cationic polymer is different. The sodium bentonite modified by the cationic polymer in Comparative Example 6 does not undergo the sodiumation treatment in step 2).

[0112] Comparative Example 7

[0113] The difference between the self-assembled supramolecular modified chitosan composite material of this comparative example and that of Example 1 is that the preparation method of the sodium bentonite modified by the cationic polymer is different. The sodium bentonite modified by the cationic polymer in Comparative Example 7 does not undergo the cationic polymer modification treatment in step 3).

[0114] Comparative Example 8

[0115] The difference between the self-assembled supramolecular modified chitosan composite material of this comparative example and that of Example 1 is that the preparation method of the sodium bentonite modified by the cationic polymer is different. The sodium bentonite modified by the cationic polymer in Comparative Example 8 does not undergo the high-temperature calcination treatment in step 3).

[0116] Comparative Example 9

[0117] The difference between the self-assembled supramolecular modified chitosan composite material of this comparative example and that of Example 1 is that the preparation method of the sodium bentonite modified by the cationic polymer is different. In Comparative Example 9, sodium chloride in step 2) was changed to sodium carbonate with a concentration of 0.5 mol / L, and the remaining steps and parameters were the same as those in Example 1.

[0118] Comparative Example 10

[0119] The difference between the self-assembled supramolecular modified chitosan composite material of this comparative example and that of Example 1 lies in the different preparation methods of the cationic polymer modified sodium bentonite. In Comparative Example 10, the 1 wt% polyquaternium-16 solution in step 3) was changed to a 3 wt% polyquaternium-16 solution, and the remaining steps and parameters were the same as those in Example 1.

[0120] Comparative Example 11

[0121] The difference between the self-assembled supramolecular modified chitosan composite material of this comparative example and that of Example 1 lies in the different preparation methods of the cationic polymer modified sodium bentonite. In Comparative Example 11, the 1 wt% polyquaternium-16 solution in step B3 was changed to a 1 wt% cetyltrimethylammonium chloride solution, and the remaining steps and parameters were the same as those in Example 1.

[0122] Comparative Example 12

[0123] The difference between the self-assembled supramolecular modified chitosan composite material of this comparative example and that of Example 1 lies in the different preparation methods of the cationic polymer modified sodium bentonite. In Comparative Example 12, the calcination temperature in step 3) was changed from 160 °C to 250 °C, and the remaining steps and parameters were the same as those in Example 1.

[0124] Test Example 1. Stability Test

[0125] Test samples: The self-assembled supramolecular modified chitosan composite materials prepared in Examples 1 to 11 and the materials prepared in Comparative Examples 1 to 12.

[0126] Test steps: The test samples were left standing at 25 °C for 28 days for room temperature stability test (numbered 1); the test samples were left standing at -17 °C for 7 days, restored to room temperature, then left standing at 45 °C for 7 days, and the above operations were repeated, and finally restored to room temperature for high and low temperature cycle stability test (numbered 2). After 28 days, if the appearance of the test samples in the two stability tests did not change, it was considered to pass.

[0127] The test results are shown in Table 3 below.

[0128] Table 3

[0129]

[0130]

[0131] The test results show that the self-assembled supramolecular modified chitosan composite materials of the examples of the present invention all have good stability and passed the 28-day room temperature stability test and high and low temperature cycle stability test.

[0132] During the preparation of the self-assembled supramolecular modified chitosan composite of Comparative Example 1, high-speed shearing treatment was not carried out, and the mixing of cationic polymer-modified sodium bentonite and modified chitosan was uneven. The cationic polymer-modified sodium bentonite and modified chitosan could not self-assemble to form supramolecules, resulting in the precipitation of cationic polymer-modified sodium bentonite and the appearance of precipitates at the bottom. Comparative Example 3 changed the degree of deacetylation of carboxymethyl chitosan. After carboxymethyl chitosan was mixed with cationic polymer-modified sodium bentonite, it was unstable under high-temperature conditions. Comparative Example 4 used carboxymethyl chitosan with a larger molecular weight to prepare the self-assembled supramolecular modified chitosan composite. High-molecular-weight carboxymethyl chitosan was prone to solidification at low temperatures. Therefore, under the condition of -17°C, the self-assembled supramolecular modified chitosan composite showed a solidification phenomenon. Comparative Example 5 used commercially available bentonite to form the self-assembled supramolecular modified chitosan composite. The commercially available bentonite was not modified, and the interlayer spacing in the bentonite was small, which was not conducive to the intercalation of carboxymethyl chitosan, and the final product was prone to instability. Comparative Example 6 was not subjected to sodium treatment, and Comparative Example 8 was not subjected to high-temperature calcination treatment. The interlayer spacing in the bentonite was still small, which was not conducive to the intercalation of carboxymethyl chitosan, and the final product was unstable. Comparative Example 10 changed the concentration of the cationic polymer, and Comparative Example 11 changed the type of the cationic polymer. The changes in the above two conditions were prone to cause the instability of the product.

[0133] Test Example 2, Scalp Microecology Test

[0134] Test Samples: Self-assembled supramolecular modified chitosan composites prepared in Examples 1 to 11 and materials prepared in Comparative Examples 1 to 12.

[0135] Test Method: "Disinfection Technical Specification" (2002 Edition) of the Ministry of Health - 2.1.8.3 Minimum Inhibitory Concentration Test (Agar Dilution Method).

[0136] Test Strains: Test Strains: Staphylococcus epidermidis ATCC 12228; Propionibacterium acnes ATCC 11827; Malassezia furfur ATCC 44344, all from the Guangdong Institute of Microbiology.

[0137] Table 4

[0138]

[0139]

[0140] Staphylococcus epidermidis is a major component of the normal skin commensal flora in healthy individuals, not only defending against potential pathogenic microorganisms but also inhibiting the overgrowth of existing opportunistic pathogens. Propionibacterium acnes is a dominant flora on the skin, inhabiting hair follicles and sebaceous glands, and Propionibacterium acnes is one of the etiological factors inducing acne. Malassezia furfur is an important factor inducing or exacerbating diseases such as seborrheic dermatitis, alopecia, pityriasis capitis, folliculitis, pruritus, and tinea capitis.

[0141] As shown in Table 4 above, the antibacterial concentration of the self-assembled supramolecular modified chitosan composite material in the embodiment of the present invention against Staphylococcus epidermidis is >100000 mg / L, the minimum antibacterial concentration against Propionibacterium acnes is <9200 mg / L, and the minimum antibacterial concentration against Malassezia furfur is <3800 mg / L, indicating that the self-assembled supramolecular modified chitosan composite material in the embodiment of the present invention does not inhibit the colonization of normal skin flora, inhibits the reproduction of harmful flora, and has a good effect on regulating the microecology.

[0142] In Comparative Example 1, the self-assembled supramolecular modified chitosan composite material was not subjected to high-speed shear dispersion during the preparation process. During the formation of the modified chitosan composite material, the self-assembly effect of cationic polymer-modified sodium bentonite and modified chitosan was poor, resulting in a poor antibacterial effect of the final product against Propionibacterium acnes and Malassezia furfur. In Comparative Example 2, unmodified chitosan was combined with modified bentonite. The antibacterial effect of unmodified chitosan itself was poor, and its compatibility with modified bentonite was poor, resulting in a poor antibacterial effect of the final product.

[0143] In Comparative Example 3, the degree of deacetylation of carboxymethyl chitosan was changed. The amino groups on the polysaccharide molecular weight in carboxymethyl chitosan changed, and the properties of carboxymethyl chitosan changed, resulting in a poor antibacterial effect of the final product against Propionibacterium acnes and Malassezia furfur.

[0144] In Comparative Example 4, the molecular weight of carboxymethyl chitosan was changed, and the antibacterial effect of the final product against Propionibacterium acnes and Malassezia furfur became poor, indicating that carboxymethyl chitosan with a weight-average molecular weight of 100 kDa to 180 kDa is preferably used in the present invention.

[0145] Comparative Examples 5 to 8 showed poor antibacterial effects against Propionibacterium acnes and Malassezia furfur, indicating that only after the bentonite was modified and then self-assembled with carboxymethyl chitosan, the resulting modified chitosan composite material had a good effect on regulating the microecology. In the present invention, the bentonite needs to be subjected to sodium modification, cationic polymer modification, and high-temperature calcination treatment, and the resulting modified chitosan composite material prepared from the bentonite has a good effect on regulating the microecology. In Comparative Example 9, the sodium modification was carried out using a slightly alkaline sodium salt solution, and when subsequent treatment was carried out, the effect of the cationic polymer modification was weakened, resulting in a poor antibacterial effect of the final product against Propionibacterium acnes and Malassezia furfur.

[0146] In Comparative Example 10, the concentration of the cationic polymer was changed, and in Comparative Example 11, the type of the cationic polymer was changed. Finally, the modified chitosan composite material showed an inhibitory effect on Staphylococcus epidermidis, and the inhibitory effects on Propionibacterium acnes and Malassezia furfur became weaker, indicating that during the cationic modification process, the concentration and type of the cationic polymer had a great influence on the effect of the final product in regulating the microecology. If the concentration of the cationic polymer was too low, the modification effect was poor, but if the concentration of the cationic polymer was too high, the amount of the cationic polymer attached to the surface of the modified bentonite increased, affecting the subsequent intercalation of carboxymethyl chitosan.

[0147] In the present invention, the concentration of the cationic polymer is preferably 0.5 to 2 wt%, and the type of the cationic polymer is preferably polyquaternary ammonium salt. In Comparative Example 12, the calcination temperature during the preparation of the cationic polymer-modified sodium bentonite was changed. Under the condition of increasing the temperature, the cationic polymer attached to the surface of the bentonite was easily evaporated or even carbonized at high temperature, resulting in a weaker inhibitory effect of the final product against Propionibacterium acnes and Malassezia furfur, and a poorer effect of the final product in regulating the microecology.

[0148] Test Example 3. Anti-inflammatory effect test

[0149] Inflammation is one of the most common diseases in clinical practice and is a defense response of the human body to ensure the removal of harmful stimuli and the repair of damaged tissues. When human immune cells are affected by inflammatory factors, some small-molecular-weight, soluble proteins or polypeptides that can transmit information between cells and have specific immune regulatory functions are secreted by the body itself and can participate in or cause inflammatory reactions. These substances are called inflammatory factors, including NO, TNF-α, IL-6, IL-8, etc. These inflammatory factors have direct or indirect effects on cell inflammation.

[0150] In this test, the LPS-induced mouse fibroblast L929 was used as an in vitro inflammatory cell model, and the relative mRNA expression level of the inflammatory factor (IL-8) was measured to evaluate whether the test substance had in vitro anti-inflammatory efficacy.

[0151] Test samples: The self-assembled supramolecular modified chitosan composites prepared in Examples 1 to 11 and the materials prepared in Comparative Examples 1 to 12 were formulated into a solution with a mass concentration of 1 wt% using H-DMEM medium containing 10% FBS.

[0152] Test procedure: Take L929 cells in the logarithmic phase and add 2×10 5 cells to each well of a 6-well culture plate, add H-DMEM medium containing 10% FBS (referred to as the culture medium), and culture at 37°C, 5% CO 2 , saturated humidity environment for 24 h; aspirate the culture medium, add 1 mL of culture medium to the negative control group, add 1 mL of 5 μg / mL LPS solution to the model control group and the test sample groups respectively to induce modeling for 18 hours, aspirate the culture medium, add 1 mL of culture medium to the negative control group and the model control group respectively, and add 1 mL of the corresponding sample solution to each sample group, and continue to culture for 24 h. After the culture is completed, extract the total RNA of L929 cells in each well, reverse transcribe and perform fluorescence quantitative PCR, and the real-time fluorescence quantitative results are calculated by method.

[0153] The test results are shown in Table 5 below:

[0154] Table 5

[0155]

[0156] After treatment with LPS solution induction, compared with the negative control group, the relative expression level of IL-8 mRNA in the model control group increased rapidly, indicating that the production of IL-8 inflammatory factors in L929 cells increased. After adding the self-assembled supramolecular modified chitosan composites of Examples or Comparative Examples to the test sample groups, the relative expression level of IL-8 mRNA decreased, and the production of inflammatory factors became less, and the test samples showed a certain anti-inflammatory effect. Among them, the relative expression levels of IL-8 mRNA in Examples 1 to 11 were lower than those in Comparative Examples 1 to 12, indicating that the anti-inflammatory effects of Examples 1 to 11 were better than those of Comparative Examples 1 to 12. The anti-inflammatory effect of Example 1 was better than that of Comparative Example 1, indicating that the preparation steps of the self-assembled supramolecular modified chitosan composites had a great influence on the anti-inflammatory effect of the final product. In the preparation process of the self-assembled supramolecular modified chitosan composite of Comparative Example 1, high-speed shear dispersion was not carried out, and the self-assembly effect of cationic polymer-modified sodium bentonite and modified chitosan was not good during the formation of the modified chitosan composite, resulting in a poor anti-inflammatory effect of the final product.

[0157] The anti-inflammatory effect of Example 1 is better than that of Comparative Examples 2-4, indicating that the type of chitosan, the molecular weight of the modified chitosan, and the degree of deacetylation have a great impact on the effect of the final product. The modified chitosan of the present invention is preferably carboxymethyl chitosan, the weight-average molecular weight of the modified chitosan is preferably between 100 kDa and 180 kDa, and the degree of deacetylation is preferably between 70% and 95%.

[0158] The anti-inflammatory effect of Example 1 is better than that of Comparative Examples 5-8, indicating that the modification treatment of bentonite has a great impact on the anti-inflammatory effect of the final product. In the present invention, commercially available bentonite needs to be subjected to sodium modification treatment, cationic polymer modification treatment and high-temperature calcination treatment before it can be used to prepare the self-assembled supramolecular modified chitosan composite material. Without one of these steps, the anti-inflammatory effect of the final product is poor.

[0159] The anti-inflammatory effect of Example 1 is better than that of Comparative Example 9, indicating that in the sodium modification treatment, a neutral sodium salt solution is required for sodium modification treatment. Using a slightly alkaline sodium salt solution for sodium modification treatment will weaken the effect of subsequent cationic polymer modification, resulting in a poor anti-inflammatory effect of the final product. The anti-inflammatory effect of Example 1 is better than that of Comparative Examples 10-11, indicating that during the cationic polymer modification treatment, the type of cationic polymer and the concentration of the cationic polymer solution during the modification process have an impact on the anti-inflammatory effect of the final product. In the present invention, the concentration of the cationic polymer is preferably 0.5-2 wt%, and the type of cationic polymer is preferably polyquaternary ammonium salt.

[0160] The anti-inflammatory effect of Example 1 is better than that of Comparative Example 12, indicating that the calcination temperature in the preparation of sodium-modified bentonite by cationic polymer modification affects the anti-inflammatory effect of the final product. Under the condition of too high temperature, the cationic polymer attached to the surface of bentonite is prone to evaporation and even denaturation at high temperature, and the composite effect of sodium-modified bentonite by cationic polymer modification and modified chitosan becomes poor, resulting in a poor anti-inflammatory effect of the final product. In the present invention, the calcination temperature is preferably 130-200 °C.

[0161] Test Example 4. Repair effect test

[0162] SIRT1 is a nuclear protein that can deacetylate class III histones, and can also interact with a variety of non-histones and cytokines. It can also directly participate in transcriptional silencing, chromatin modification, regulation of cell meiosis cycle checkpoints, enhance DNA double-strand damage repair ability and inhibit rDNA recombination, and increase genomic stability, thereby delaying aging and inhibiting apoptosis.

[0163] In this experiment, by using 0.1 μg / mL H 2 O 2Keratinocytes HaCaT induced for 1 hour were used as an in vitro repair model, and the repair effect of the test sample was evaluated by measuring the relative expression level of Sirt1 mRNA.

[0164] Test sample: The same as in Test Example 3.

[0165] Test procedure: Take HaCaT cells in the logarithmic phase and add 2×10 5 cells to each well of a 6-well culture plate, add H-DMEM medium containing 10% FBS (referred to as the culture medium), and culture at 37°C, 5% CO 2 , saturated humidity environment for 24 h; aspirate the culture medium, add 1 mL of culture medium to the negative control group, and add 1 mL of 0.1 μg / mL H 2 O 2 to the model control group and the test sample groups respectively for induction for 1 hour, aspirate the culture medium, add 1 mL of culture medium to the negative control group and the model control group respectively, and add 1 mL of the corresponding sample solution to each sample group, and continue to culture for 24 h. After the culture is completed, extract the total RNA of HaCaT cells in each well, reverse transcribe for fluorescence quantitative PCR, and the real-time fluorescence quantitative results are calculated by method.

[0166] Table 6

[0167]

[0168] The results are shown in Table 6. After treatment with H 2 O 2 solution, compared with the negative control group, the relative expression level of SIRT1mRNA in the model control group decreased, indicating that less SIRT1 was produced by HaCaT cells and the anti-damage repair ability of the cells became weaker. After treatment with H 2 O 2 solution and then adding the test sample, the relative expression level of SIRT1 mRNA increased to varying degrees, indicating that more SIRT1 protein was produced by the cells and the anti-damage repair ability was stronger, and the test sample showed a repair effect.

[0169] The repair effect of Example 1 is better than that of Comparative Example 1, indicating that the preparation steps of the self-assembled supramolecular modified chitosan composite material have a great influence on the final product's repair effect. In Comparative Example 1, the self-assembled supramolecular modified chitosan composite material was not subjected to high-speed shear dispersion during the preparation process. During the formation of the modified chitosan composite material, the self-assembly effect of cationic polymer-modified sodium bentonite and modified chitosan was not good, resulting in a poor repair effect of the final product.

[0170] The repair effect of Example 1 is better than that of Comparative Examples 2-4, indicating that the type of chitosan, the molecular weight of modified chitosan, and the degree of deacetylation have a great impact on the repair effect of the final product. In the present invention, the modified chitosan is preferably carboxymethyl chitosan, the weight-average molecular weight of the modified chitosan is preferably between 100 kDa and 180 kDa, and the degree of deacetylation is preferably between 70% and 95%.

[0171] The repair effect of Example 1 is better than that of Comparative Examples 5-8, indicating that the modification treatment of bentonite has a great impact on the repair effect of the final product. In the present invention, commercially available bentonite needs to be subjected to sodium modification treatment, cationic polymer modification treatment, and high-temperature calcination treatment before it can be used to prepare the self-assembled supramolecular modified chitosan composite material. Without one of these steps, the repair effect of the final product is relatively poor.

[0172] The repair effect of Example 1 is better than that of Comparative Example 9, indicating that in the sodium modification treatment, a neutral sodium salt solution needs to be used for sodium modification treatment. Using an alkaline sodium salt solution for sodium modification treatment will weaken the effect of subsequent cationic polymer modification, resulting in a poor repair effect of the final product.

[0173] The repair effect of Example 1 is better than that of Comparative Examples 10-11, indicating that in the process of cationic polymer modification treatment, the type of cationic polymer and the concentration of the cationic polymer solution during the modification process have an impact on the repair effect of the final product. In the present invention, the concentration of the cationic polymer is preferably 0.5-2 wt%, and the type of cationic polymer is preferably polyquaternary ammonium salt.

[0174] The repair effect of Example 1 is better than that of Comparative Example 12, indicating that the calcination temperature in the preparation of sodium-modified bentonite by cationic polymer modification affects the repair effect of the final product. Under the condition of too high temperature, the cationic polymer attached to the surface of bentonite is prone to evaporation or even denaturation at high temperature, the composite effect of cationic polymer-modified sodium bentonite and modified chitosan becomes poor, and the repair effect of the final product becomes poor. In the present invention, the calcination temperature is preferably 130-200 °C.

[0175] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application rather than to limit the protection scope of the present application. Although the present application has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that the technical solutions of the present application can be modified or equivalently replaced without departing from the essence and scope of the technical solutions of the present application.

Claims

1. A self-assembled supramolecular modified chitosan composite material, characterized in that: In terms of mass percentage, the self-assembled supramolecular modified chitosan composite material comprises: 10-20% carboxymethyl deacetylated chitosan, 0.2-1.0% cationic polymer modified sodium bentonite and the balance water; The carboxymethyl deacetylated chitosan has a weight average molecular weight of 100 kDa to 180 kDa and a deacetylation degree of 70 to 95%; The preparation method of the cationic polymer-modified sodium bentonite comprises the following steps: 1) Mixing bentonite with water, stirring and then standing, and removing the upper layer solution to obtain washed bentonite; 2) adding the sodium salt solution to the washed bentonite prepared in step 1), stirring and then standing, and removing the upper layer of solution to obtain sodium bentonite; 3) Soaking the sodium bentonite prepared in step 2) in a cationic polymer solution, stirring and then standing, removing the upper solution, and then calcining at high temperature and ball milling to obtain the cationic polymer-modified sodium bentonite.

2. The self-assembled supramolecular modified chitosan composite material according to claim 1, characterized in that: The particle size of the sodium bentonite modified by the cationic polymer is 30 to 80 μm.

3. The self-assembled supramolecular modified chitosan composite material according to claim 1, characterized in that: The cationic polymer includes at least one of polyquaternium-11, polyquaternium-16, polyquaternium-24, polyquaternium-28, polyquaternium-37 and polyquaternium-73.

4. The self-assembled supramolecular modified chitosan composite material according to claim 1, characterized in that: In step 1), the mass ratio of the bentonite to water is 1:(4-8); in step 2), the mass ratio of the washed bentonite to the sodium salt solution is 1:(4-8); in step 3), the mass ratio of the sodium bentonite to the cationic polymer solution is 1:(4-8).

5. The self-assembled supramolecular modified chitosan composite material according to claim 1, characterized in that: The concentration of sodium ions in the sodium salt solution is 1-3 mol / L, and the concentration of cationic polymer in the cationic polymer solution is 0.5-2 wt %.

6. The self-assembled supramolecular modified chitosan composite material according to claim 1, characterized in that: In the step 1), the stirring time is 30 to 90 minutes, the stirring speed is 80 to 150 rpm, and the standing time is 60 to 120 minutes; In the step 2) and step 3), the stirring time is 3 to 5 hours, the stirring speed is 80 to 150 rpm, and the standing time is 60 to 120 minutes; In the step 3), the calcination temperature is 130-200° C., and the calcination time is 90-150 min.

7. The method for preparing the self-assembled supramolecular modified chitosan composite material according to any one of claims 1 to 6, characterized in that: The following steps are involved: (1) mixing water and carboxymethyl deacetylated chitosan uniformly to obtain a carboxymethyl deacetylated chitosan solution; (2) mixing the carboxymethyl deacetylated chitosan solution and the sodium bentonite modified by the cationic polymer, and subjecting the mixture to high-speed shear dispersion treatment and ultrasonic treatment to obtain a self-assembled supramolecular modified chitosan composite material; The rotation speed of the high-speed shearing and dispersing treatment is 6000-12000 rpm, and the time of the high-speed shearing and dispersing treatment is 20-40 min; The power of the ultrasonic treatment is 400-800W, and the time of the ultrasonic treatment is 40-80min.

8. Use of the self-assembled supramolecular modified chitosan composite material according to any one of claims 1 to 6 in the preparation of daily chemicals.

Images