Chitosan type supramolecular emulsifier as well as preparation method and application thereof

Abstract

The invention discloses a chitosan type supramolecular emulsifier as well as a preparation method and application thereof, and belongs to the technical field of supramolecular emulsifier preparation. The preparation method comprises the following steps: by taking chitosan, fatty acid, sodium aliphatate, alcohol and a solvent as raw materials, dispersing at 25-50 DEG C for 2-6 hours, then heating to 60-80 DEG C, and stirring to react for 8-15 hours to obtain a turbid liquid; and finally, carrying out spray drying on the turbid liquid to obtain the chitosan type supramolecular emulsifier. The chitosan supramolecular emulsifier prepared by the preparation method disclosed by the invention is good in emulsification stability, good in environmental adaptability and good in biocompatibility; the preparation is simple, low in cost and suitable for industrial production; the method can be used in the fields of medicines and cosmetics.

Description

Technical Field

[0001] This invention relates to a chitosan-based supramolecular emulsifier, its preparation method, and its application, belonging to the field of supramolecular emulsifier preparation technology. Background Technology

[0002] Emulsifiers, as core basic materials in pharmaceuticals, cosmetics, and other fields, play a crucial role in stabilizing immiscible systems and regulating interfacial properties. Their performance directly determines the stability, safety, and functional characteristics of emulsions. Traditional emulsifiers are mostly chemically synthesized small-molecule surfactants. Although they have high emulsification efficiency, they suffer from drawbacks such as insufficient biocompatibility, poor degradability, and irritation, facing strict limitations in high-end applications. Developing green, safe, and high-performance natural-based emulsifiers has become an industry consensus. Chitosan-based materials, due to their wide availability, excellent biocompatibility, degradability, and modifiable molecular structure, have become a research hotspot in the field of natural emulsifiers.

[0003] Chitosan, a deacetylated product of chitin, is a natural cationic polysaccharide. Its molecular chain contains numerous amino and hydroxyl groups, giving it unique interfacial and reactive activities. Chitosan oligosaccharides, low-molecular-weight degradation products of chitosan, exhibit superior water solubility and bioactivity. Carboxymethyl, hydroxyethyl, and acetylated modified chitosans, through chemical modification, optimize key properties such as hydrophilicity / hydrophobicity and water solubility, collectively forming chitosan-based material systems. However, when used as emulsifiers, single chitosan materials suffer from insufficient emulsion stability, weak interfacial adsorption capacity, and sensitivity to environmental conditions. Furthermore, the emulsifying properties of most modified chitosans depend on a specific degree of modification, resulting in complex preparation processes and poor batch-to-batch stability.

[0004] Supramolecular emulsifiers, based on the self-assembly of non-covalent bonds such as intermolecular hydrogen bonds, electrostatic interactions, and hydrophobic interactions, form stable supramolecular structures. They possess interfacial stability and functional tunability unmatched by traditional emulsifiers, making them a cutting-edge area in the field of emulsifying materials in recent years. However, the development of chitosan-based supramolecular emulsifiers still faces several bottlenecks: First, the controllability of the supramolecular structure is poor, and the self-assembly process is easily affected by pH, ionic strength, etc., making it difficult to form a uniform and stable emulsion interface structure; second, the preparation methods are complex, often requiring harsh reaction conditions or large amounts of organic solvents; and third, their functions are limited, with existing products unable to simultaneously meet multiple functional requirements, restricting their application in complex systems.

[0005] Currently, some literature discloses composite emulsifiers. For example, CN113426366A discloses a soluble chitosan-PVP composite emulsifier, its preparation method, and its application. This method involves mixing soluble chitosan and polyvinylpyrrolidone, dissolving the mixture in distilled water, and heating and stirring at 30-50°C for 1-2 hours to obtain the soluble chitosan. PVP complex emulsifiers; however, insufficient supramolecular structure regulation results in limited emulsion stability. The literature (Qian Xiaoqing, Wang Limin, Zhang Wen, Lei Dandan, Zhang Xinping, Zhang Guijun, He Kuo, Wu Zijian. Chitosan-based Pickering emulsions and their application in food [J]. Food Science, 2023, 44(21): 386-395.) mentions chitosan-protein, chitosan-polysaccharide, chitosan-polyphenol, chitosan-fatty acid, and chitosan-whey protein-resveratrol chitosan nanocomposite particles used in Pickering emulsions; these improved the ability of chitosan to stabilize emulsions, but structural regulation was difficult and environmental adaptability was weak.

[0006] Therefore, developing a chitosan-based supramolecular emulsifier to solve the problems of poor emulsion stability, complex preparation, and limited functionality of existing products, and to realize its efficient application in multiple fields, has important theoretical and practical significance. Summary of the Invention

[0007] To address the aforementioned problems, this invention provides a chitosan-based supramolecular emulsifier, its preparation method, and its applications. Specifically, this invention uses chitosan, fatty acids, sodium fatty acids, alcohol, and solvent as raw materials, disperses them at 25-50℃ for 2-6 hours, then heats to 60-80℃ and stirs for 8-15 hours to obtain a suspension; finally, the suspension is spray-dried to obtain the chitosan-based supramolecular emulsifier. The chitosan-based supramolecular emulsifier prepared by this invention exhibits good emulsification stability, good environmental adaptability, and good biocompatibility; it is simple to prepare, low in cost, and suitable for industrial production; it can be used in pharmaceuticals, cosmetics, and other fields.

[0008] The first objective of this invention is to provide a method for preparing chitosan-based supramolecular emulsifiers, comprising the following steps: Chitosan, fatty acids, sodium fatty acids, alcohol, and solvent are dispersed at 25-50℃ for 2-6 hours in a mass ratio of 1.5-25:5-20:0-10:45-93.5:150. Then, the mixture is heated to 60-80℃ and stirred for 8-15 hours to obtain a suspension. Finally, the suspension is dried to obtain chitosan supramolecular emulsifier powder.

[0009] In one embodiment of the present invention, the chitosan is one or more of chitosan, chitosan oligosaccharide, carboxymethyl chitosan, hydroxyethyl chitosan, acetylated chitosan, hydroxypropyl chitosan, succinylated chitosan, and sulfonated chitosan.

[0010] In one embodiment of the present invention, the fatty acid is one or more of the following: undecenoic acid, linolenic acid, stearic acid, linoleic acid, palmitoleic acid, myristic acid, tall oil acid, oleic acid, hydrogenated coconut oil acid, coconut oil acid, decanoic acid, lauric acid, palmitic acid, stearic acid, isostearic acid, butyloctanoic acid, docosahexaenoic acid, eicosapentaenoic acid, and hexanoic acid.

[0011] In one embodiment of the present invention, the sodium fatty acid is one or more of sodium stearate, sodium linoleate, sodium palmitate, sodium myristate, sodium oleate, sodium cocoate, sodium laurylate, sodium palmitate, and sodium isostearate.

[0012] In one embodiment of the present invention, the alcohol is one or more of butyloctanol, decanol, decyltetradecylol, arachidonicol, hexyldecylol, cetyl alcohol, cetearyl alcohol, polydimethylsiloxane alcohol, myristol, behenol, octyldodecyl alcohol, lanolin alcohol, coconut oil alcohol, isocetyl alcohol, isostearyl alcohol, stearyl alcohol, oleyl alcohol, lauryl alcohol, and palm oil alcohol.

[0013] In one embodiment of the present invention, the solvent is water.

[0014] In one embodiment of the present invention, the dispersion is ultrasonic dispersion, and the power of the ultrasound is 50-500W.

[0015] In one embodiment of the present invention, the stirring speed is 300-800 rpm.

[0016] In one embodiment of the present invention, the drying is spray drying, specifically spray drying at a temperature of 180-220°C and a pressure of 0.3-0.5 MPa for 6-12 hours.

[0017] The second objective of this invention is to prepare chitosan-based supramolecular emulsifier powder using the method described herein.

[0018] In one embodiment of the present invention, the particle size range of the chitosan supramolecular emulsifier powder is 400-600 nm.

[0019] The third objective of this invention is to apply the chitosan-based supramolecular emulsifier powder described herein in the preparation of pharmaceuticals or cosmetics.

[0020] In one embodiment of the present invention, cosmetics include ointments, creams, lotions, etc.; chitosan supramolecular emulsifier powder can enhance the moisturizing, sun protection, stability, antibacterial and other functions of cosmetics.

[0021] In one embodiment of the present invention, the medicine includes dressings, creams, etc.

[0022] The fourth objective of this invention is to provide a cosmetic product that uses the chitosan-based supramolecular emulsifier powder described in this invention.

[0023] In one embodiment of the present invention, the cosmetic preparation method is as follows: Chitosan supramolecular emulsifier powder is added to the oil phase and mixed evenly, then added to the aqueous phase and homogenized and emulsified to obtain cosmetics; Among them, the mass concentration of chitosan supramolecular emulsifier powder in the entire cosmetic is 0.1-2%.

[0024] In one embodiment of the present invention, preservatives and some functional ingredients may be added at appropriate times as needed in the preparation method of cosmetics.

[0025] In one embodiment of the present invention, cosmetics include lotions, creams, and creases; different aqueous and oil phases can be selected as needed.

[0026] The fifth objective of this invention is to provide a method for improving the storage stability and multifunctionality of emulsions, which employs the chitosan-based supramolecular emulsifier powder described in this invention.

[0027] In one embodiment of the present invention, multifunctionality refers to enhancing properties such as moisturizing, sun protection, and antibacterial properties.

[0028] The technical effects of this invention are as follows: (1) The chitosan supramolecular emulsifier prepared by this invention has good emulsification stability, good environmental adaptability and good biocompatibility; it is simple to prepare, low in cost and suitable for industrial production; it can be used in the fields of medicine and cosmetics.

[0029] (2) The chitosan supramolecular emulsifier of the present invention has a particle size of 400-600 nm and an EAI index of 90 nm. 2 The emulsion has a concentration of ≥ / g, an ESI index of ≥80%, and a cell viability retention rate of ≥94%. The prepared emulsion is homogeneous and stable without stratification after being placed in a high temperature and high humidity environment for 1 month. It is also homogeneous and stable without stratification after a 1-month freeze-thaw cycle. Furthermore, the prepared cosmetic has excellent antibacterial properties and is homogeneous and stable without stratification after being placed in a high temperature and high humidity environment for 1 month. It is also homogeneous and stable without stratification after a 1-month freeze-thaw cycle. Attached Figure Description

[0030] Figure 1 The infrared spectrum is shown for the chitosan supramolecular emulsifier powder prepared in Example 1.

[0031] Figure 2 The images show actual samples from the stability tests of Examples 1-3, 13, 14, 15 and Comparative Examples 1 and 2.

[0032] Figure 3 The results are the antibacterial performance test results of the face creams of Example 15, Comparative Example 12, and Comparative Example 13. Detailed Implementation

[0033] The preferred embodiments of the present invention are described below. It should be understood that the embodiments are for better explanation of the present invention and are not intended to limit the present invention.

[0034] Test method: 1. Emulsifying activity and stability (EAI / ESI index) test: Add the emulsifier powder to water to prepare an emulsifier aqueous solution with a mass concentration of 1%; weigh the emulsifier aqueous solution and liquid paraffin at a mass ratio of 1:4, vortex mix for 5 minutes to form an emulsion; take 0.1 mL of the emulsion and dilute it with distilled water to 10 mL (dilution factor N=100).

[0035] After standing for 10 minutes, the absorbance A0 at 500 nm was measured using distilled water as a blank.

[0036] Substitute into the formula to calculate EAI; EAI(m) 2 / g)={(2×2.303) / [C×(1-φ)×10 4 ]}×A 500 × dilution factor; where φ is 0.2; Transfer the emulsion to centrifuge tubes and let it stand for 4 hours. Take 0.1 mL of the upper layer of emulsion each time, dilute it, and measure the absorbance A. t ; Calculate ESI using the formula:

[0037] The emulsion was subjected to accelerated aging tests under two conditions: a high temperature and high humidity (40℃ / 75% RH) constant temperature and humidity chamber and a freeze-thaw cycle (alternating between -20℃ and 25℃, with one cycle completed every 24 hours). After one month, the emulsion was observed to determine whether it was uniform and stable and whether it separated into layers.

[0038] 2. Antibacterial ability test: Using E. coli as an indicator bacterium, the antibacterial effects of Example 15, Comparative Example 12, and Comparative Example 13 were tested.

[0039] E. coli was evenly spread on LB solid medium (circular medium, 90 mm in diameter), with a bacterial concentration of 10. 6 CFU / mL; then, use a sterile syringe to draw 0.5 mL of face cream, gently spread it on the culture medium, and incubate at 37 ℃ for 12 h, observe and measure the diameter of the inhibition zone.

[0040] The antibacterial effect of face creams was evaluated by comparing face creams containing preservatives with face creams containing only chitosan oligosaccharides as control groups.

[0041] 3. Cell compatibility test: The MTT (3-(4,5-dimethylthiazolyl-2-yl)-2,5-diphenyltetrazolium bromide) method is a classic cell proliferation / toxicity assay that indirectly reflects cell number and viability by detecting the ability of mitochondrial dehydrogenases in living cells to reduce MTT to formazan.

[0042] Take fibroblasts in the logarithmic growth phase and adjust the density (1×10⁻⁶). 4 (cells / well, 96-well plate); add 100 μL of complete culture medium to each well and incubate for 24 h to allow the cells to adhere; Experimental Groups: Blank control group (culture medium only, no cells); Negative control group (untreated cells); Experimental group (0.5% emulsifier aqueous solution); Positive control group (10% PDGF stimulation); Add 10 μL of MTT solution (5 mg / mL, prepared in PBS) to each well (final concentration 0.5 mg / mL); incubate at 37 °C for 4 h, then discard the supernatant; add 150 μL of DMSO to each well and shake slowly for 10 min to dissolve the crystals; measure the absorbance at 490 nm using a microplate reader.

[0043] The formula for calculating cell viability retention rate is as follows: Cell viability (%) = (OD value of experimental group - OD value of blank group) / (OD value of control group - OD value of blank group) × 100% Raw materials used in the examples: Chitosan oligosaccharide: molecular weight <≈1 kDa, 97% Palmitoleic acid: 99%; Sodium palmitate: 99%; Palm oil alcohol: 98%; Hydroxypropyl chitosan: 99%; Cocolate acid: 99%; Carboxymethyl chitosan: degree of carboxylation ≥80%, Hydrogenated coconut oil acid: 99%; Sodium myristate: 98%; Cetearyl alcohol: 99%; Chitosan: BR, degree of deacetylation 95%, viscosity ≤200cps; Sodium lauryl var.: 97%; Polydimethylsiloxane alcohol: 99%; Hydroxyethyl chitosan: 99%; Docosahexaenoic acid: 99%; Sodium cocoate: 99%; Coconut oil alcohol: 99%; Acetylated chitosan: Fully acetylated chitosan, 98%; Eicosapentaenoic acid: 98%; Hydroxypropyl chitosan: 99%; Hexanoic acid: 99%; Sodium palmitate: 97%; Butyloctanol: 98%; Succinylated chitosan: 99%; Undecenoic acid: 99%; Sodium isostearate: 98%; Hexyldecyl alcohol: 99%; Sulfonated chitosan: 95%; Linolenic acid: 99%; Isostearyl alcohol: 99%.

[0044] Example 1 A method for preparing chitosan-based supramolecular emulsifiers includes the following steps: Chitosan oligosaccharide, palmitoleic acid, sodium palmitate, palmitole alcohol, and water were mixed in a mass ratio of 20:15:5:65:150. The mixture was first ultrasonically dispersed at 35℃ and 200W for 4 hours, then heated to 70℃ and stirred at 300rpm for 12 hours to obtain a suspension. Finally, the suspension was spray-dried at 200℃ and 0.4MPa for 8 hours to obtain chitosan supramolecular emulsifier powder.

[0045] Figure 1 The infrared spectrum of the chitosan-based supramolecular emulsifier powder prepared in Example 1. From... Figure 1 It can be seen that: in the emulsifier, chitosan oligosaccharide was originally at 1637 cm⁻¹ -1 With 1590 cm -1 The peaks at 2913 cm⁻¹ shifted to higher and lower wavenumbers, respectively, due to the change in electron cloud density caused by supramolecular interactions. These data all indicate the presence of numerous intermolecular forces. Furthermore, the peak at 2913 cm⁻¹ in the emulsifier... -1 With 2845 cm -1 The strong absorption peaks at the point indicate the stretching vibrations of the CH bonds in the carbon chain of the palmitic fatty acid raw material, and these data confirm the formation of the supramolecular system.

[0046] Example 2 In Example 1, the mass ratio of chitosan oligosaccharide, palmitoleic acid, sodium palmitate, palmitole alcohol, and water was adjusted to 1.5:5:0:45:150; all other parameters remained the same as in Example 1, resulting in a chitosan supramolecular emulsifier powder.

[0047] Example 3 In Example 1, the mass ratio of chitosan oligosaccharide, palmitoleic acid, sodium palmitate, palmitole alcohol, and water was adjusted to 25:20:10:93.5:150; all other parameters remained the same as in Example 1, resulting in a chitosan supramolecular emulsifier powder.

[0048] Example 4 In Example 1, the chitosan oligosaccharide was changed to hydroxypropyl chitosan, while other aspects remained the same as in Example 1, resulting in a chitosan supramolecular emulsifier powder.

[0049] Example 5 In Example 1, palmitic acid was replaced with coconut oil acid, while other aspects remained the same as in Example 1, resulting in a chitosan-based supramolecular emulsifier powder.

[0050] Example 6 A method for preparing chitosan-based supramolecular emulsifiers includes the following steps: Carboxymethyl chitosan, hydrogenated coconut oil acid, sodium myristate, cetearyl alcohol, and water were mixed in a mass ratio of 10:15:6:55:150. The mixture was first ultrasonically dispersed at 35°C and 200W for 4 hours, then heated to 70°C and stirred at 300rpm for 12 hours to obtain a suspension. Finally, the suspension was spray-dried at 200°C and 0.4MPa for 8 hours to obtain chitosan supramolecular emulsifier powder.

[0051] Example 7 A method for preparing chitosan-based supramolecular emulsifiers includes the following steps: Chitosan, coconut oil acid, sodium lauryl ether, polydimethylsiloxane alcohol, and water were mixed in a mass ratio of 20:10:8:65:150. The mixture was first ultrasonically dispersed at 35°C and 300W for 4 hours, then heated to 70°C and stirred at 300rpm for 12 hours to obtain a suspension. Finally, the suspension was spray-dried at 200°C and 0.4MPa for 8 hours to obtain chitosan-based supramolecular emulsifier powder.

[0052] Example 8 A method for preparing chitosan-based supramolecular emulsifiers includes the following steps: Hydroxyethyl chitosan, docosahexaenoic acid, sodium cocoate, coconut oil alcohol, and water were mixed in a mass ratio of 25:18:10:80:150. The mixture was first ultrasonically dispersed at 35°C and 200W for 4 hours, then heated to 70°C and stirred at 300rpm for 12 hours to obtain a suspension. Finally, the suspension was spray-dried at 200°C and 0.4MPa for 8 hours to obtain chitosan supramolecular emulsifier powder.

[0053] Example 9 A method for preparing chitosan-based supramolecular emulsifiers includes the following steps: Acetylated chitosan, eicosapentaenoic acid, sodium lauryl oleate, palmitole alcohol, and water were mixed in a mass ratio of 25:12:8:90:150. The mixture was first ultrasonically dispersed at 35°C and 200W for 4 hours, then heated to 70°C and stirred at 300rpm for 12 hours to obtain a suspension. Finally, the suspension was spray-dried at 200°C and 0.4MPa for 8 hours to obtain chitosan supramolecular emulsifier powder.

[0054] Example 10 A method for preparing chitosan-based supramolecular emulsifiers includes the following steps: Hydroxypropyl chitosan, hexanoic acid, sodium palmitate, butyl octanol, and water were mixed in a mass ratio of 5:8:3:60:150. The mixture was first ultrasonically dispersed at 35°C and 200W for 4 hours, then heated to 70°C and stirred at 300rpm for 12 hours to obtain a suspension. Finally, the suspension was spray-dried at 200°C and 0.4MPa for 8 hours to obtain chitosan supramolecular emulsifier powder.

[0055] Example 11 A method for preparing chitosan-based supramolecular emulsifiers includes the following steps: Succinylated chitosan, undecenoic acid, sodium isostearate, hexyldecyl alcohol, and water were dispersed by ultrasonication at 35°C and 200W for 4 hours in a mass ratio of 8:5:5:73:150. Then, the mixture was heated to 70°C and stirred at 300 rpm for 12 hours to obtain a suspension. Finally, the suspension was spray-dried at 200°C and 0.4 MPa for 8 hours to obtain chitosan supramolecular emulsifier powder.

[0056] Example 12 A method for preparing chitosan-based supramolecular emulsifiers includes the following steps: Sulfonated chitosan, linolenic acid, sodium oleate, isostearyl alcohol, and water were mixed in a mass ratio of 15:15:7:80:150. The mixture was first ultrasonically dispersed at 35°C and 200W for 4 hours, then heated to 70°C and stirred at 300rpm for 12 hours to obtain a suspension. Finally, the suspension was spray-dried at 200°C and 0.4MPa for 8 hours to obtain chitosan supramolecular emulsifier powder.

[0057] The obtained emulsifier was subjected to performance testing, and the test results are as follows: Table 1

[0058] Comparative Example 1: Ultrasonic dispersion only A method for preparing chitosan-based supramolecular emulsifiers includes the following steps: Chitosan oligosaccharide, palmitoleic acid, sodium palmitate, palmitole alcohol, and water were dispersed in a mass ratio of 20:15:5:65:150. The mixture was first ultrasonically dispersed at 35℃ and 200W for 16 hours to obtain a suspension. Finally, the suspension was spray-dried at 200℃ and 0.4MPa for 8 hours to obtain chitosan supramolecular emulsifier powder.

[0059] Comparative Example 2: Reaction only (stirred) A method for preparing chitosan-based supramolecular emulsifiers includes the following steps: Chitosan oligosaccharide, palmitoleic acid, sodium palmitate, palmitole alcohol, and water were mixed in a mass ratio of 20:15:5:65:150 and stirred at 70℃ and 300rpm for 16 hours to obtain a suspension. Finally, the suspension was spray-dried at 200℃ and 0.4MPa for 8 hours to obtain chitosan supramolecular emulsifier powder.

[0060] Comparative Example 3 In Example 1, the mass ratio of chitosan oligosaccharide, palmitoleic acid, sodium palmitate, palmitole alcohol, and water was adjusted to 20:0:5:65:150; all other parameters remained the same as in Example 1, resulting in a chitosan supramolecular emulsifier powder.

[0061] Comparative Example 4 The mass ratio of chitosan oligosaccharide, palmitoleic acid, sodium palmitate, palmitole alcohol, and water in Example 1 was adjusted to 20:45:5:0:150; all other parameters remained the same as in Example 1, resulting in a chitosan supramolecular emulsifier powder.

[0062] Comparative Example 5 In Example 1, palmitoleic acid was replaced with octanoic acid, while other aspects remained the same as in Example 1, resulting in a chitosan-based supramolecular emulsifier powder.

[0063] Comparative Example 6 In Example 1, sodium palmitate was replaced with sodium talloate, while other aspects remained the same as in Example 1, resulting in a chitosan-based supramolecular emulsifier powder.

[0064] Comparative Example 7 In Example 1, palm oil alcohol was replaced with lanosterol, while other aspects remained the same as in Example 1, resulting in a chitosan-based supramolecular emulsifier powder.

[0065] Comparative Example 8 In Example 1, the water was adjusted to be a 50% (w / w) aqueous solution of ethanol, while other parameters remained the same as in Example 1, resulting in a chitosan supramolecular emulsifier powder.

[0066] Comparative Example 9 A method for preparing chitosan-based supramolecular emulsifiers includes the following steps: Chitosan oligosaccharide, palmitoleic acid, sodium palmitate, palmitole alcohol, and water were reacted at a mass ratio of 20:15:5:65:150. The mixture was first stirred at 70℃ and 300rpm for 12h, then cooled to 35℃ and ultrasonically dispersed at 200W for 4h to obtain a suspension. Finally, the suspension was spray-dried at 200℃ and 0.4MPa for 8h to obtain chitosan supramolecular emulsifier powder.

[0067] Comparative Example 10 In Example 1, the spray drying was changed to freeze drying (freeze drying at -60℃ for 8 hours), while other steps remained the same as in Example 1, resulting in chitosan supramolecular emulsifier powder.

[0068] Comparative Example 11 In Example 1, the chitosan oligosaccharide was changed to hydroxybutyl chitosan, while other aspects remained the same as in Example 1, resulting in a chitosan supramolecular emulsifier powder.

[0069] The obtained emulsifier was subjected to performance testing, and the test results are as follows: Table 2

[0070] Example 13 A method for preparing an emulsion based on chitosan-based supramolecular emulsifiers of Example 1 includes the following steps: Cetyl ethylhexanoate (7506), caprylic / capric triglyceride (gtcc), squalane, and polydimethylsiloxane were added to an oil pan and heated and stirred at 85°C and 350 rpm until completely dissolved. Chitosan supramolecular emulsifier powder from Example 1 was added, mixed evenly, and kept warm to obtain the oil phase. Add glycerin, 980 (carbomer), and water to an emulsifying vessel, heat at 85°C and 600 rpm and stir until completely dissolved to obtain the aqueous phase; Add the oil phase to the aqueous phase, homogenize at 3000 rpm for 5 min, and keep warm at 85℃ for 20 min; Then, the temperature was lowered to 55°C, arginine was added, and stirring and cooling continued. When the temperature reached 40°C, preservative (PE9010) was added. After the temperature dropped to room temperature, the finished emulsion was obtained. The emulsion contains, by mass percentage, 4% cetyl ethylhexanoate (7506), 3% caprylic / capric triglyceride (GTCC), 3% squalane, 1% polydimethylsiloxane, 5% glycerol, 0.3% 980 (carbomer), 1% chitosan supramolecular emulsifier powder from Example 1, 0.3% arginine, 0.5% preservatives, and the remainder is water.

[0071] The obtained emulsion was subjected to performance testing, and the test results are as follows: Table 3

[0072] Example 14 A method for preparing a cream based on chitosan supramolecular emulsifier powder from Example 1 includes the following steps: Cetyl ethylhexanoate (7506), caprylic / capric triglyceride (gtcc), squalane, cetearyl alcohol, and polydimethylsiloxane were added to an oil pan and heated and stirred at 85°C and 350 rpm until completely dissolved. Chitosan supramolecular emulsifier powder from Example 1 was added, mixed evenly, and kept warm to obtain the oil phase. Add glycerin and water to an emulsifying pot, heat and stir at 85°C and 600 rpm until completely dissolved to obtain the aqueous phase; Add the oil phase to the aqueous phase, homogenize at 2500 rpm for 2 min, add Clariant Aristoflex AVC, homogenize at 1200 rpm for 5 min, and keep warm at 85℃ for 20 min. Then, the temperature is lowered to 40°C, preservatives (PE9010) are added, and the finished cream is obtained after the temperature drops to room temperature. The cream contains, by weight percentage, 10% cetyl ethylhexanoate (7506), 7% caprylic / capric triglyceride (GTCC), 4.5% squalane, 1.5% hexadecyl alcohol, 2% polydimethylsiloxane, 3% glycerin, 0.5% Clariant Aristoflex AVC, 1.5% chitosan supramolecular emulsifier powder from Example 1, 0.5% preservatives, and the remainder is water.

[0073] The obtained cream was subjected to performance testing, and the test results are as follows: Table 4

[0074] Example 15 A method for preparing a face cream based on chitosan supramolecular emulsifier powder from Example 1 includes the following steps: Add meadowfoam seed oil, caprylic / capric triglyceride (gtcc), squalane, cetearyl alcohol, polydimethylsiloxane, and shea butter to an oil pan, heat and stir at 85°C and 400 rpm until completely dissolved, add chitosan supramolecular emulsifier powder from Example 1, mix evenly, keep warm, and obtain the oil phase; Add glycerin and water to an emulsifying pot, heat and stir at 85°C and 500 rpm until completely dissolved to obtain the aqueous phase; Add the oil phase to the aqueous phase, homogenize at 3000 rpm for 2 min, add Clariant Aristoflex AVC, homogenize at 1200 rpm for 5 min, and keep warm at 85℃ for 20 min. Once the temperature drops to room temperature, the finished face cream is obtained. The face cream contains, by weight percentage, 5% meadowfoam seed oil, 8% caprylic / capric triglyceride (GTCC), 3% squalane, 2.5% cetearyl alcohol, 2% polydimethylsiloxane, 3% shea butter, 3% glycerin, 0.8% Clariant Aristoflex AVC, 0.5% chitosan supramolecular emulsifier powder from Example 1, and the remainder is water.

[0075] The obtained frost was subjected to performance testing, and the test results are as follows: Table 5

[0076] Comparative Example 12 In Example 15, the chitosan supramolecular emulsifier powder obtained in Example 1 was modified to chitosan oligosaccharide, while other aspects remained the same as in Example 15, to obtain a face cream.

[0077] Comparative Example 13 In Example 15, the chitosan supramolecular emulsifier powder obtained in Example 1 was modified to a preservative (PE9010), with an addition amount of 0.5%. All other aspects remained the same as in Example 15, resulting in a face cream.

[0078] The antibacterial ability of the face creams obtained in Example 15, Comparative Example 12, and Comparative Example 13 was tested, and the test results are as follows: Figure 3 The results show the antibacterial performance test results of the face creams from Example 15, Comparative Example 12, and Comparative Example 13. Figure 3 It can be seen that inhibition zones appeared in Comparative Examples 12, 13, and 15. The diameter of the inhibition zone in Comparative Example 12 was 5.56 mm; the diameter of the inhibition zone in Comparative Example 13 was 16.84 mm; and the diameter of the inhibition zone in Example 15 was 20.12 mm. The results show that the emulsifier in Example 1 has antibacterial activity and retains its antimicrobial ability after being added to the face cream.

[0079] Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Anyone skilled in the art can make various modifications and alterations without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention should be determined by the claims.

Claims

1. A method for preparing chitosan-based supramolecular emulsifiers, characterized in that, Includes the following steps: Chitosan, fatty acids, sodium fatty acids, alcohol, and solvent are dispersed at 25-50℃ for 2-6 hours in a mass ratio of 1.5-25:5-20:0-10:45-93.5:

150. Then, the mixture is heated to 60-80℃ and stirred for 8-15 hours to obtain a suspension. Finally, the suspension is dried to obtain chitosan supramolecular emulsifier powder.

2. The method according to claim 1, characterized in that, Chitosans include one or more of the following: chitosan, chitosan oligosaccharides, carboxymethyl chitosan, hydroxyethyl chitosan, acetylated chitosan, hydroxypropyl chitosan, succinylated chitosan, and sulfonated chitosan; fatty acids include one or more of the following: undecenoic acid, linolenic acid, stearic acid, linoleic acid, palmitoleic acid, myristic acid, tall oil acid, oleic acid, hydrogenated coconut oil acid, coconut oil acid, decanoic acid, lauric acid, palmitic acid, stearic acid, isostearic acid, butyloctanoic acid, docosahexaenoic acid, eicosapentaenoic acid, and hexanoic acid.

3. The method according to claim 1, characterized in that, Sodium fatty acids are one or more of sodium stearate, sodium linoleate, sodium palmitate, sodium myristate, sodium oleate, sodium cocoate, sodium laurate, sodium palmitate, and sodium isostearate; alcohols are one or more of butyloctanol, decanol, decyltetradecylol, arachidonicol, hexyldecylol, cetyl alcohol, cetearyl alcohol, polydimethylsiloxane alcohol, myristol, behenol, octyldodecyl alcohol, lanolin alcohol, cocoyl alcohol, isocetyl alcohol, isostearyl alcohol, stearyl alcohol, oleyl alcohol, lauryl alcohol, and palm oil alcohol.

4. The method according to claim 1, characterized in that, The stirring speed is 300-800 rpm.

5. The method according to claim 1, characterized in that, The dispersion is ultrasonic dispersion, with an ultrasonic power of 50-500W.

6. The method according to claim 1, characterized in that, The solvent is water; the drying method is spray drying, specifically spray drying at a temperature of 180-220℃ and a pressure of 0.3-0.5MPa for 6-12 hours.

7. The chitosan supramolecular emulsifier powder prepared by the method according to any one of claims 1-6.

8. The chitosan supramolecular emulsifier powder according to claim 7 is used in the preparation of pharmaceuticals or cosmetics.

9. A cosmetic product, characterized in that, The chitosan-based supramolecular emulsifier powder described in claim 7 was used.

10. A method for improving the storage stability and multifunctionality of emulsions, characterized in that, The chitosan-based supramolecular emulsifier powder described in claim 7 was used.

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