Natural material-based Janus particle and preparation method thereof

Abstract

The invention relates to a natural material based Janus particle and a preparation method thereof. The natural material-based Janus particle comprises a natural material-based particle, a functional substance A and a functional substance B, wherein the functional substance A and the functional substance B are modified on the surface of the natural material-based particle and are different from each other; wherein the average diameter of the natural material base particles is 100 nanometers to 50 micrometers. Multi-stage preparation and corresponding sequential modification of programmed multi-scale particles are realized by utilizing a multi-stage preparation method, so that natural material particles loaded with more functional substances are obtained.

Description

Technical Field

[0001] The invention relates to natural material-based Janus particles, belonging to the field of composite materials. Background Art

[0002] Currently, particles used in industrial applications, especially particles in the traditional sense, are mostly round in shape. They are usually composed of the same substance, and their particle surface and internal composition are exactly the same. The undifferentiated single structure can only be applied to simple usage scenarios, and will have difficulty in functioning for complex systems, especially multi-scale complex systems.

[0003] Janus particles usually refer to a particle with two different components or structures, and the two parts have clear partitions. This type of particle with significant anisotropy is different from traditional homogeneous particles and can play a unique role in emulsification, grinding, lubrication, and functional substance delivery. In addition, Janus particles are expected to be used as functional preparation carriers in more complex environments.

[0004] At present, materials made of natural materials have been widely used in our production and life as main materials, industrial additives, decorative items, daily chemical products, functional materials, etc., and have played many functions such as cleaning, adsorption, beauty, health care, and treatment. Especially in the complex environment of the human body, they have played a positive role. Among them, pulverizing them into particles is the most prominent way of use. Summary of the invention

[0005] Problem that the invention aims to solve

[0006] However, currently, natural materials are crushed and pulverized into particles only through a simple crushing process, and the subsequent modification is mostly homogeneous surface modification, which greatly limits the modification and compounding of functional substances. This is mainly manifested in: 1. Natural materials are directly used roughly after being crushed into powder particles; 2. Solvents are generally used to extract the effective ingredients contained in natural materials as functional application channels; 3. Functional natural materials have not been developed on multiple scales and their use methods are very limited. Therefore, it is very necessary to break through tradition and use cutting-edge technologies to physically and chemically transform natural materials to promote functional expansion and industry development.

[0007] Therefore, the subject of the present invention is to provide a natural material-based Janus particle and a preparation method thereof.

[0008] Solutions for solving problems

[0009] The inventors discovered during their research that natural materials can be used to obtain powdery and blocky natural material particles of different sizes through different mechanical crushing techniques and processes. Based on this technical feature, a multi-stage preparation method can be used to achieve programmed multi-scale particle multi-stage preparation and its corresponding sequential modification, thereby obtaining natural material particles loaded with more functional substances, thereby completing the present invention.

[0010] Specifically, the present invention solves the problem of the present invention through the following solutions.

[0011] [1] A natural material-based Janus particle, comprising a natural material-based particle, and functional substances A and B that are different from each other and modified on the surface of the natural material-based particle; wherein the average diameter of the natural material-based particle is 100 nm to 50 μm.

[0012] [2] The particles according to [1], wherein the natural material-based particles are particles composed of natural materials, wherein the content of natural materials is 80% by mass or more; the natural materials are one or more materials derived from organisms and natural inorganic substances, and the natural materials are preferably natural organic substances, more preferably polysaccharide macromolecular colloids, and further preferably selected from peach gum and gum.

[0013] [3] The particles according to [2], wherein the material derived from an organism is one or more of materials derived from plants or animals; the material derived from plants is preferably one or more of materials derived from roots, stems, leaves, seeds, and pollen of plants, and more preferably plant powder; the material derived from animals is one or more selected from cells, blood, milk or dairy products, bones, pearls, shells, and crustaceans, and preferably selected from shellac and pearl powder.

[0014] [4] The particles according to [2], wherein the material derived from natural inorganic substances is one or more of clay and minerals, preferably selected from mica, silica, and zinc oxide.

[0015] [5] The particles according to any one of [1] to [4], wherein the functional substance A and the functional substance B are connected to the natural material-based particles by chemical bonds, and preferably, the functional substance A and the functional substance B are independently selected from compounds having one or more functional groups selected from carboxyl, sulfonic acid, phosphoric acid, amino, imidazole, pyridine and their salts; and the area ratio of the surface area modified by the functional substance A to the surface area modified by the functional substance B is (10-1):1.

[0016] [6] The particles according to [5], wherein the functional substance A and the functional substance B are independently selected from carboxylic acids and their derivatives, amino acids and their derivatives, sulfonic acids and their derivatives, polyhydroxy compounds and their derivatives, phosphoric acid and its derivatives, organic amines and their derivatives, imidazoles and their derivatives, pyridine and its derivatives, and organosilanes.

[0017] [7] The method for preparing particles according to any one of [1] to [6], comprising the following steps:

[0018] (a) crushing natural materials into coarse particles with an average diameter of 1-100 μm;

[0019] (b) contacting the coarse particles with a functional substance A to obtain surface-modified coarse particles whose surfaces are modified with the functional substance A;

[0020] (c) crushing the surface-modified coarse particles to obtain fine particles;

[0021] (d) contacting the fine particles with the functional substance B to obtain the natural material-based Janus particles.

[0022] [8] The preparation method according to [7], wherein the functional substance A and the functional substance B are solid, and no solvent is used in the steps (b) and (d).

[0023] [9] The preparation method according to [7], wherein steps (b) and (d) are carried out in a solvent, and the solvent is preferably selected from one or more of water, alcohols, ketones, ethers, hydrocarbons, and sulfoxide solvents, and more preferably selected from one or more of water, methanol, ethanol, alcohol, propylene glycol, glycerol, panthenol, acetone, THF, DMSO, n-hexane, cyclohexane, isohexadecane, and C7-16 isoparaffin.

[0024]

[10] The preparation method according to [7] or [8], wherein the crushing in steps (a) and (c) is mechanical crushing, and is more preferably carried out in a mortar, a high-speed stirrer, a high-speed shearing machine, a ball mill, a high-speed air flow crushing, a high-pressure air flow crushing, a high-temperature and high-pressure disintegration, a water-jet crushing, an ultrafine grinder, an ultrafine pulverizer, a nano grinder, a nano pulverizer or a freeze crusher.

[0025] Effects of the Invention

[0026] The natural material-based Janus particles of the present invention compound more functional substances with natural material particles and construct a Janus structure. The natural material-based Janus particles of the present invention have multiple functions, and the prominent anisotropy in the structure can bring new rheological behaviors to the dispersed system and play more and more unique roles, such as cleaning, grinding, penetration, transdermal, protective, modifying, beautifying, and maintenance. DETAILED DESCRIPTION

[0027] Various exemplary embodiments, features and aspects of the present invention will be described in detail below. The word "exemplary" used here means "used as an example, embodiment or illustrative". Any embodiment described here as "exemplary" is not necessarily interpreted as being superior or better than other embodiments.

[0028] In addition, in order to better illustrate the present invention, numerous specific details are provided in the following specific embodiments. It should be understood by those skilled in the art that the present invention can be implemented without certain specific details. In other examples, methods, means, equipment and steps well known to those skilled in the art are not described in detail in order to highlight the subject matter of the present invention.

[0029] Unless otherwise stated, the units used in this specification are all international standard units, and the numerical values ​​and numerical ranges appearing in the present invention should be understood to include the inevitable systematic errors in industrial production.

[0030] In this specification, the word "may" means both performing a certain process and not performing a certain process.

[0031] In this specification, the references to "some specific / preferred embodiments", "other specific / preferred embodiments", "embodiments", etc., mean that the specific elements (e.g., features, structures, properties and / or characteristics) described in connection with the embodiments are included in at least one embodiment described herein, and may or may not exist in other embodiments. In addition, it should be understood that the elements may be combined in various embodiments in any suitable manner.

[0032] In this specification, the numerical range expressed using "a numerical value A to a numerical value B" means a range including the endpoints numerical values ​​A and B.

[0033] In this specification, when "normal temperature" or "room temperature" is used, the temperature may be 10-40°C.

[0034] <Natural material based Janus particles>

[0035] An object of the present invention is to provide a natural material-based Janus particle, which includes a natural material-based particle, and functional substances A and functional substances B that are different from each other and modified on the surface of the natural material-based particle; wherein the average diameter of the natural material-based particle is 100nm to 50μm.

[0036] Based on the inherent characteristics of Janus particles, those skilled in the art can understand that functional substance A and functional substance B are strictly divided on the surface of natural material-based particles. That is, the surface of Janus particles has a surface area modified by functional substance A and a surface area modified by functional substance B, wherein in the surface area modified by functional substance A, the proportion of functional substance A in all surface-modified substances is 80% by mass or more, preferably 90% by mass or more; in the surface area modified by functional substance B, the proportion of functional substance B in all surface-modified substances is 80% by mass or more, preferably 90% by mass or more.

[0037] In one embodiment, the area ratio of the surface area modified by the functional substance A to the surface area modified by the functional substance B is (10-1):1.

[0038] Functional substance A and functional substance B can be connected to the natural material-based particles through chemical bonds or physical interactions. The physical interactions can be hydrogen bonds, van der Waals forces, electrostatic forces, etc., and the chemical bonds can be covalent bonds, ionic bonds, metallic bonds, etc. Functional substance A and functional substance B are preferably connected through chemical bonds.

[0039] The various components of the Janus particles of the present invention are described in detail below.

[0040] Natural material based particles

[0041] In this specification, "natural material" means a material that comes from nature and has not been processed or has only been physically processed.

[0042] In this specification, "natural material-based particles" refer to particles composed of natural materials, wherein the content of natural materials is 80 mass % or more, for example, 90 mass % or more, for example, 95 mass % or more, or 100%.

[0043] In the present invention, there is no particular limitation on the natural material constituting the natural material-based particles, which can be any suitable natural material. In particular, the natural material particles used in the present invention are natural materials listed in the INCI cosmetic raw material list issued by the Cosmetics Department of the State Food and Drug Administration.

[0044] In one embodiment, the natural material is one or more of materials derived from organisms and natural inorganic substances.

[0045] The natural material derived from organisms may be one or more materials derived from plants or animals.

[0046] The plant-derived material is one or more of the materials derived from the root, stem, leaf, seed, and pollen of the plant. Examples thereof include, but are not limited to: Bonat Spirulina powder, Chinese medicinal material powder, grain powder, plant powder, plant root powder, plant leaf powder, tea, tea powder, brown sugar paste powder, barley powder, barley leaf powder, barley seed powder, light bamboo leaf powder, rice husk powder, rice powder, pollen, cordyceps mycelium powder, catechu gum, catechu leaf powder, catechu wood powder, Poria powder, Poria sclerotium powder, starch, cassava starch, modified potato starch, modified corn starch, rice powder, citrus peel powder, peel powder, Guangxi sand orange peel powder, pectin, seaweed seeds, plant seeds, fruit seeds, Candelilla wax, brown algae, walnut shell powder, amber powder, pollen, peanut powder, bark, bark powder, coffee powder, cocoa shell powder, gelatin, natto gum, peach gum, gum, gum arabic, guar gum, duck soap gum, jasmine petals, petal powder, oyster shell powder, cellulose, microcrystalline cellulose, cellulose gum, lignin, pine pollen, rosin, wheat bran, wheat germ powder, wheat kernel powder, flax seed powder, oat starch, oat bran powder, oat kernel coarse powder, oat kernel powder, ginkgo leaf powder, tea leaf powder, grape seed powder, cucumber seed powder, deer antler cream, bamboo charcoal, etc.

[0047] The animal-derived material is one or more of animal tissues, cells, blood, milk or dairy products, bones, pearls, shells, and carapaces. Examples thereof include, but are not limited to, conchiolin powder, milk powder, honey, bee pollen, propolis, propolis wax, bee pollen, beeswax, royal jelly, royal jelly powder, dried egg yolk, dried cheese, cicada molt, silk, hydrolyzed silk, quaternary ammonium salt-79 hydrolyzed silk, blood, red deer blood meal, milk, milk powder, yogurt powder, shellac, purple shellac, purple shellac wax, animal bones, bone meal, pearls, buffalo horns, antelope horns, earthworms, cochineal, pearls, pearl powder, mother-of-pearl, mother-of-pearl powder, mother-of-pearl oyster powder, etc.

[0048] The material derived from natural inorganic substances is one or more of clay and ore. Examples of clay include, but are not limited to, Hokkaido Akan clay, kaolin, loess, activated clay, volcanic ash, volcanic mud, bentonite, quaternary ammonium salt-18 bentonite, Canadian bentonite, Manigogen glacial mud, montmorillonite, Moroccan lava clay, fuller's earth, Haiermu clay, etc.

[0049] The ore may be a metal ore, a metal oxide ore, etc., examples of which include, but are not limited to, gallstones, opal powder, tourmaline, calcite, zeolite, pumice, attapulgite, silica, diatomaceous earth, sea silt, talc, yellow ochre, volcanic sand, silica silylate, alum, potassium alum, gold, diamond powder, gold ore, malachite, sapphire powder, rhodochrosite, smithsonite, sulfur, sulfur powder, barium sulfate, calcium sulfate, calcium sulfate hydrate, silver sulfate, calamine, aluminum, aluminum powder, aluminum closa, silver chloride, bismuth oxychloride, medical stone, borax, Hydroxyapatite, calcium hydroxide, aluminum hydroxide, chromium hydroxide green, quartz, calcium carbonate, zinc carbonate, iron powder, copper powder, zirconium oxide, aluminum zirconium pentachlorohydrate, fine sand, phonolite, salt mine mud, calcium oxide, calcium cerium oxide, chromium oxide green, cobalt aluminum oxide, aluminum oxide, magnesium oxide, sodium oxide, cerium oxide, titanium cobalt oxide, titanium iron oxide, iron oxides, iron oxides / titanium dioxide sintered, tin oxide, zinc oxide, silver oxide, pyrophyllite, illite, silver, mica, meteorite powder, perlite, expanded perlite, purple quartz powder, bronze powder, etc.

[0050] In a preferred embodiment, the natural material is a natural organic matter, more preferably a polysaccharide macromolecular colloid, and further preferably selected from peach gum and gum.

[0051] In a preferred embodiment, the natural material is plant powder.

[0052] Functional substance A / Functional substance B

[0053] In the present invention, there is no particular limitation on the specific types of the functional substance A and the functional substance B, which may be any suitable substance that can modify the surface of natural material particles to impart specific functions thereto.

[0054] In one embodiment, the functional substance A and the functional substance B are independently selected from compounds having one or more functional groups selected from carboxyl group, sulfonic acid group, phosphoric acid group, amino group, imidazole group, pyridyl group and salts thereof.

[0055] In one embodiment, functional substance A and functional substance B are independently selected from carboxylic acids and their derivatives, amino acids and their derivatives, sulfonic acids and their derivatives, polyhydroxy compounds and their derivatives, phosphonic acids and their derivatives, organic amines and their derivatives, imidazoles, imidazolidinyl ureas, pyridine and its derivatives, organosilanes, etc.

[0056] The carboxylic acid may be selected from aliphatic carboxylic acids, alicyclic carboxylic acids, aromatic carboxylic acids, and heterocyclic carboxylic acids, wherein the aliphatic carboxylic acid may be a straight-chain or branched, saturated or unsaturated aliphatic carboxylic acid.

[0057] The sulfonic acid can be selected from aliphatic sulfonic acid, alicyclic sulfonic acid, aromatic sulfonic acid, and heterocyclic sulfonic acid. The aliphatic sulfonic acid can be a linear or branched, saturated or unsaturated aliphatic sulfonic acid.

[0058] The phosphonic acid can be selected from aliphatic phosphonic acid, alicyclic phosphonic acid, aromatic phosphonic acid, and heterocyclic phosphonic acid, wherein the aliphatic phosphonic acid can be a straight-chain or branched, saturated or unsaturated aliphatic phosphonic acid.

[0059] The derivatives of carboxylic acid, sulfonic acid, phosphonic acid or amino acid can be in the form of salt, ester, amide or the like of carboxylic acid, sulfonic acid, phosphonic acid or amino acid, respectively, or can be derivatives in which the part other than carboxyl, sulfonic acid group and phosphonic acid group is substituted by a substituent. Among them, the salt can be an alkali metal salt (such as lithium, sodium, potassium, etc.) or an alkaline earth metal salt (such as calcium, magnesium, etc.). The ester can be an ester obtained by reacting carboxylic acid, sulfonic acid, phosphonic acid or amino acid with a fatty alcohol, alicyclic alcohol or aromatic alcohol, wherein the alcohol can be a monohydric alcohol or a polyhydric alcohol, and can be saturated or unsaturated. The amide can be obtained by reacting carboxylic acid, sulfonic acid, phosphonic acid or amino acid with an amine, and the amine can be a fatty amine or an aromatic amine, and can be a monoamine or a polyamine. The substituent can be a hydroxyl, a sulfhydryl, a polymer segment optionally having a functional group, etc.

[0060] Polyols are organic compounds that have two or more hydroxyl groups in one molecule.

[0061] The organic amine may be an aliphatic amine, an alicyclic amine, an aromatic amine, or a heterocyclic amine. The derivative of the organic amine may be a derivative in which an organic group other than an amino group is substituted by a substituent or a sulfate of the organic amine, etc. The substituent may be a hydroxyl group, a segment having an oxyalkylene repeating unit, etc.

[0062] The derivatives of pyridine refer to derivatives in which the pyridine ring is substituted by a substituent, wherein the substituent includes but is not limited to carboxyl, amino, hydroxyl, and alkyl substituted by carboxyl, amino or hydroxyl.

[0063] In a specific embodiment, functional substance A and functional substance B are independently selected from lauric acid, sodium laurate, tartaric acid, disodium tartrate, disodium 2-sulfolaurate, stearic acid, sodium stearate, tetrasodium pyrophosphate, 4-amino-3-hydroxybutyric acid, oleic acid, sodium oleate, phosphoric acid, sodium dihydrogen phosphate, trisodium phosphate, sodium benzenesulfonate, 3-aminopropanesulfonic acid, sodium ligninsulfonate, sodium C12-15 polyether-3 sulfate, sodium C12-15 polyether-7 carboxylate, sodium C12-15 polyether sulfate, sodium C12-15 alkyl sulfate, sodium C14-16 olefin sulfonate, 4-hydroxybenzoic acid, sodium C4-12 olefin / maleic acid copolymer, EDTA (salt), trisodium HEDTA, 10-hydroxydecanoic acid, creatine, alcohol Tartaric acid, tartaric acid (salt), poly-β-alanine, sodium poly-γ-glutamate, polyaminopropyl biguanide stearate, polypropionic acid, polypropionic acid (salt), polyacrylamidomethylpropane sulfonic acid, ammonium polyacryloyldimethyl taurate, hexyldecanoic acid, 2,6-dicarboxypyridine, 2-amino-3-hydroxypyridine, 2-o-ethyl ascorbic acid, sodium C8-16 isoalkyl succinyl soybean sulfonate, sodium C8-16 isoalkyl succinyl lactoglobulin sulfonate, p-aminophenol sulfate, pyrrolidone carboxylic acid, alginic acid, sodium alginate, 2-hydroxyethyl picrine, caseinate (salt), lactobacillus, amino acids including glycine, alanine, valine, leucine, isoleucine, methionine (methionine), proline, tryptophan, serine, tyrosine, cysteine, Phenylalanine, asparagine, glutamine, threonine, aspartic acid, glutamic acid, lysine, arginine, histidine, selenocysteine, pyrrolysine, disodium cetyl phenyl ether disulfonate, 2,6-dicarboxypyridine, 2-o-ethyl ascorbic acid, adenosine phosphate, chlorogenic acid, maleic acid, imidazole, imidazolidinyl urea, rosmarinic acid, rice furan acid, amidinoproline, sodium lignin sulfonate, citric acid, milk amino acids, sodium dermatan sulfate, malic acid, malic acid (salt), gluconic acid, glucuronic acid, sodium hydroxybenzoate, sodium hydroxypropyl starch phosphate, hydroxypropyltrimonium chloride hyaluronic acid, hydroxycinnamic acid, hydroxystearic acid, hydroxyethylethylenediaminetriacetic acid, thioglycolic acid, thioglycolic acid (salt), mercaptopropionic acid, nordihydroguaiaretic acid, myristic acid, Myristic acid (salt), myristoyl sarcosine, cinnamic acid, orotic acid, lactic acid, lactobionic acid, sodium chondroitin sulfate, thiazolyl alanine, thenoyl methionine, trimerized linoleic acid, sorbic acid, sorbic acid (salt), behenic acid, behenic acid (salt), octadecenedioic acid, dodecylbenzenesulfonic acid, dodecylbenzenesulfonic acid (salt), hyaluronic acid, hydrolyzed hyaluronic acid, salicylic acid, salicylic acid (salt), decarboxylated carnosine hydrochloride, deoxyribonucleic acid, chitosan lactate, chitosan glycolate, chitosan lactate, tall oil acid, pentapeptide-34 trifluoroacetate, ximenynic acid, linoleic acid, linoleic acid (salt), lanolin acid, coconut acid, coconut acid (salt), cocoyl sarcosine, cocoyl sarcosine (salt), folic acid, indoleacetic acid,Stearic acid, oleic acid, oleic acid (salt), lauric acid, lauric acid (salt), lauryl propionic acid, lauryl propionic acid (salt), phytic acid, phytic acid (salt), 2-amino-3-hydroxypyridine, 2-amino-4-hydroxyethylaminoanisole sulfate, PEG-9 stearamide carboxylic acid, mandelic acid, starch octenylsuccinate (salt), polydihydroxyindole, polymethacryloyl lysine, polylysine, sodium polynaphthalene sulfonate, sodium polyaspartate, caffeic acid, caffeine carboxylic acid, ascorbic acid, ascorbic acid polypeptide, sodium cocoylamphoacetate, sodium cumene sulfonate, picramic acid (salt), cerotic acid, casein acid (salt), pyridine dicarboxylic acid, pyrrolidone carboxylic acid, disodium distyryl diphenyl disulfonate, stearylamine, p-amino Phenol, p-phenylenediamine sulfate, aminopropanediol, aminobutyric acid, aminotris(methylenephosphonic acid) pentasodium, aminobispropyl dimethicone, aminoethanesulfinic acid, aminoesters-1, aminomethyl propanol, aminomethyl propanediol, aminoethylaminopropyl dimethicone, aminopropyl dimethicone, aminopropyl triethoxysilane, aminopropyl tocopheryl phosphate, tromethamine, amodimethicone, aminopropanol ascorbyl phosphate, aminopropanol kojic acid phosphate, aminotris(methylenephosphonic acid) pentasodium, aminobispropyl dimethicone, aminoethanesulfinic acid, aminoethylaminopropyl dimethicone, aminoethylphosphinic acid, dipalmitylamine, methoxypropyl glucamide, adamantyl dihydroxybenzene Formamide, chitosan, chitosan, chitosan hydrochloride, 2-amino-3-hydroxypyridine, 2-amino-4-hydroxyethylaminoanisole, 2-amino-4-hydroxyethylaminoanisole sulfate, 2-amino-6-chloro-4-nitrophenol, 3-aminopropane sulfonic acid, 4-amino-2-hydroxytoluene, 4-amino-3-hydroxybutyric acid, 4-amino-3-nitrophenol, 4-amino-m-cresol, sodium C5-20 olefin sulfonate, sodium C8-16 isoalkyl succinyl soybean sulfonate, sodium C8-16 isoalkyl succinyl lactoglobulin sulfonate, PEG-15 tallow polyamine, PEG-15 coconut amine, PEG-15 coconut methyl ammonium chloride, PEG-15 coconut polyamine, PEG-2 Soyamine, PEG-2 stearylamine, PEG-2 oleylamine, p-phenylenediamine, aminopropyl dimethicone, aminopropyl triethoxysilane, aminopropyl tocopherol phosphate, tromethamine, amino-terminated dimethicone, aminopropanol ascorbyl phosphate, aminopropanol kojic acid phosphate, aminopropylene glycol, aminobutyric acid, aminotris(methylenephosphonic acid) pentasodium, aminobispropyl dimethicone, aminoethanesulfinic acid, aminoesters-1, aminomethyl propanol, aminomethyl propanediol, aminoethyl aminopropyl dimethicone, aminoethyl propanediol, aminoethyl phosphinic acid, p-aminobenzoic acid, diaminopyrimidine oxide, hydrolyzed glucosaminoglycan, carboxyethylaminobutyric acid, 2,6-diaminopyridine, etc. and their derivatives.

[0064] <Preparation method>

[0065] Another object of the present invention is to provide a method for preparing the natural material-based Janus particles of the present invention, which comprises the following steps:

[0066] (a) crushing natural materials into coarse particles with an average diameter of 1-100 μm;

[0067] (b) contacting the coarse particles with a functional substance A to obtain surface-modified coarse particles whose surfaces are modified with the functional substance A;

[0068] (c) crushing the surface-modified coarse particles to obtain fine particles;

[0069] (d) contacting the fine particles with the functional substance B to obtain the natural material-based Janus particles.

[0070] In the method of the present invention, substances A and B are modified intermittently and sequentially, and the intermittent and sequential modification process is performed alternately with the mechanical crushing process. The equipment parameters are set, and the natural material is crushed into powder by mechanical crushing to form a coarse natural material, and the particle size of the natural material is 1 to 100 μm. These particles are modified into composite substance A to obtain natural material particles with a primary larger particle size and the outer surface modified with functional substance A. Further, the equipment parameters are changed, and the natural material is crushed into powder by mechanical crushing to form fine natural material, and the particle size of the natural material is 100nm to 50μm. Some areas on the surface of these particles are areas that have been modified with composite substance A before. After the second fine processing process of mechanical crushing, the particles are broken into smaller pieces, and the fresh part that has not been modified by substance A is exposed at the fracture. These particles are further modified into composite substance B to obtain natural material particles with a smaller particle size and the outer surface modified with functional substance B.

[0071] Functional substance A and functional substance B can be solid or liquid independently. In one embodiment, functional substance A and functional substance B are solid, and no solvent is used in the steps (b) and (d). That is, functional substance A and functional substance B are directly contacted with natural material particles in a solid state to modify the surface of the natural material particles.

[0072] In one embodiment, the steps (b) and (d) are carried out in a solvent. The solvent is preferably one or more selected from water, alcohols, ketones, ethers, hydrocarbons, and sulfoxide solvents. The solvent is more preferably one or more selected from water, methanol, ethanol, alcohol, propylene glycol, glycerol, panthenol, acetone, THF, DMSO, n-hexane, cyclohexane, isohexadecane, and C7-16 isoparaffin.

[0073] In one embodiment, the crushing in steps (a) and (c) is mechanical crushing, more preferably carried out in a mortar, a high-speed blender, a high-speed shearing machine, a ball mill, a high-speed air flow crushing, a high-pressure air flow crushing, a high-temperature and high-pressure disintegration, a water-jet crushing, an ultrafine grinder, an ultrafine pulverizer, a nano grinder, a nano pulverizer or a freezing crusher.

[0074] Example 1

[0075] In the following examples, the ball mill used is a planetary ball mill, PM2L, the grinding conditions are 220V, 50Hz, 0.75KW, and the API nano ball mill used is FRITSCH / Germany PULVERISETTE 7 enhanced type.

[0076] Example 1

[0077] 100g of pearl powder was put into a planetary ball mill, and the ball mill was set to gear 1, and the grinding was continued for 30 minutes. After the coarse grinding, 1.0g of stearic acid powder was added to the above powder, and the grinding was continued for 30 minutes under the grinding condition of gear 1 to obtain natural material particles with stearic acid modified on the outer surface of the particles, with an average particle size of 1μm.

[0078] The ball mill was reset to gear 2 and the grinding was continued for 30 minutes to obtain fine particles with an average particle size of 500 nm. These fine particles were smaller in size than the coarse particles, except that part of the outer surface was modified by stearic acid, and further broken and fractured to expose fresh parts at the broken and fractured parts.

[0079] 1.0 g of histidine was added to the fine particles, and the particles were ground for 30 minutes at the second grinding level to obtain natural material particles in which the fresh part was modified with histidine and the remaining part was modified with stearic acid. The natural material particles prepared by the above process in multiple stages have Janus structural characteristics, and thus are natural material-based Janus particles.

[0080] Embodiment 2:

[0081] 100g of natural mica was put into a planetary ball mill, and the ball mill was set to gear 1, and the grinding was continued for 30 minutes. After the coarse grinding, 1.0g of stearic acid powder was added to the above powder, and the grinding was continued for 30 minutes under the grinding condition of gear 1 to obtain natural material particles with hyaluronic acid modified on the outer surface of the particles, with an average particle size of 2μm.

[0082] The ball mill was reset to gear 2 and the grinding was continued for 30 minutes to obtain fine particles with an average particle size of 1 μm. These fine particles were smaller in size than the coarse particles, except that part of the outer surface was modified by hyaluronic acid, and further broken and fractured to expose fresh parts at the broken and fractured parts.

[0083] 1.0 g of glutamic acid peptide was added to the above-mentioned fine particles, and the grinding was continued for 30 minutes under the second grinding condition to obtain natural material particles whose fresh part was modified by glutamic acid peptide and the remaining part was modified by hyaluronic acid. The natural material particles prepared by the above process in multiple stages have Janus structural characteristics, thus obtaining natural material-based Janus particles.

[0084] Embodiment 3:

[0085] 100g of shellac was placed in a planetary ball mill, and the ball mill was set to gear 1, and the grinding was continued for 30 minutes. After the coarse grinding was completed, the above powder was dispersed in water, heated to 40°C and stirred at 60rpm / min. 1.0g of sodium stearate powder was added to the dispersion of the above powder, and the modification process lasted for 30 minutes. After filtering and drying, natural material particles with stearic acid modified on the outer surface of the particles were obtained, and the average particle size was 100μm.

[0086] The ball mill was reset to gear 2 and the grinding was continued for 30 minutes to obtain fine particles with an average particle size of 50 μm. These fine particles were smaller in size than the coarse particles, except that part of the outer surface was modified by stearic acid, and further broken and fractured to expose fresh parts at the broken and fractured parts.

[0087] 1.0 g of histidine was added to the above-mentioned fine particles, and the grinding was continued for 30 minutes under the second grinding condition to obtain natural material particles in which the fresh part was modified with histidine and the remaining part was modified with stearic acid. The natural material particles prepared by the above process in multiple stages have Janus structural characteristics, thus obtaining natural material-based Janus particles.

[0088] Embodiment 4:

[0089] 100g of silica was put into API nano ball mill, and the gear of API nano ball mill was set to gear 1, and crushing was continued for 10min to obtain coarse natural material particles. The above powder was dispersed in water, heated to 40°C and stirred at 60rpm / min, and 1.0g of stearic acid powder was added to the dispersion of the above powder, and the modification process lasted for 30min. After filtering and drying, natural material particles with stearic acid modified on the outer surface of the particles were obtained, and the average particle size was 800nm.

[0090] The API nano ball mill was reset to gear 2 and crushed for 10 minutes to obtain fine particles with an average particle size of 400 nm. These fine particles are smaller than the coarse particles, except that some areas of the outer surface are modified by stearic acid, and further crushing and breaking exposes fresh parts at the crushing and breaking sites.

[0091] 1.0 g of histidine was added to the above-mentioned fine particles, and the particles were ground continuously for 10 minutes under the second-speed water crushing condition to obtain natural material particles in which the fresh part was modified with histidine and the remaining part was modified with stearic acid. The natural material particles prepared by the above process in multiple stages have Janus structural characteristics, thus obtaining natural material-based Janus particles.

[0092] Embodiment 5:

[0093] 100g of zinc oxide was placed in an API nano ball mill, and the API nano ball mill was set to gear 1, and the crushing was continued for 10 minutes to obtain coarse natural material particles. The above powder was dispersed in water, heated to 40°C and stirred at 60rpm / min, and 1.0g of histidine powder was added to the dispersion of the above powder. The modification process lasted for 30 minutes. After filtering and drying, natural material particles with stearic acid modified on the outer surface of the particles were obtained, and the average particle size was 3μm.

[0094] The above-mentioned particle powder was dispersed in water with a solid content of 50%, and crushed for 10 minutes using an API nano ball mill to obtain fine particles with an average particle size of 1 μm. These fine particles are smaller in size than the coarse particles, except that part of the outer surface area is modified by histidine, and further crushed and broken, exposing fresh parts at the crushed and broken parts.

[0095] 1.0 g of glutamic acid peptide is added to the above-mentioned fine particles, and grinding is continued for 10 minutes under the above-mentioned conditions to obtain natural material particles whose fresh part is modified by glutamic acid peptide and whose remaining part is modified by glutamic acid peptide. The natural material particles prepared by the above-mentioned process in multiple stages have Janus structural characteristics, thus obtaining natural material-based Janus particles.

[0096] It should be noted that, although the technical solution of the present invention is introduced with specific examples, those skilled in the art will appreciate that the present invention should not be limited thereto.

[0097] The embodiments of the present invention have been described above, and the above description is exemplary, not exhaustive, and is not limited to the disclosed embodiments. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments. The selection of terms used herein is intended to best explain the principles of the embodiments, practical applications, or technical improvements in the market, or to enable other persons of ordinary skill in the art to understand the embodiments disclosed herein.

[0098] Industrial Applicability

[0099] The natural material-based Janus particles of the present invention can be widely used in the fields of cosmetics, industrial additives, medical treatment, etc.

Claims

1. A natural material-based Janus particle, characterized in that: It comprises natural material-based particles, and functional substances A and B which are different from each other and modified on the surface of the natural material-based particles; wherein the average diameter of the natural material-based particles is 100nm-50μm.

2. The particle according to claim 1, characterized in that The natural material-based particles are particles composed of natural materials, wherein the content of natural materials is more than 80% by mass; the natural materials are one or more materials derived from organisms and natural inorganic substances, and the natural materials are preferably natural organic substances, more preferably polysaccharide macromolecular colloids, and further preferably selected from peach gum and gum.

3. The particle according to claim 2, characterized in that The material derived from an organism is one or more of materials derived from plants and animals; the material derived from plants is preferably one or more of materials derived from roots, stems, leaves, seeds, and pollen of plants, and more preferably plant powder; the material derived from animals is one or more selected from cells, blood, milk or dairy products, bones, pearls, shells, and crustaceans, and preferably selected from shellac and pearl powder.

4. The particle according to claim 2, characterized in that The material derived from natural inorganic substances is one or more of clay and ore, preferably selected from mica, silica and zinc oxide.

5. The particle according to any one of claims 1 to 4, characterized in that The functional substance A and the functional substance B are connected to the natural material-based particles through chemical bonds. Preferably, the functional substance A and the functional substance B are independently selected from compounds having one or more functional groups of carboxyl, sulfonic acid, phosphoric acid, amino, imidazole, pyridine and their salts; the area ratio of the surface area modified by the functional substance A to the surface area modified by the functional substance B is (10~1):

1.

6. The particle according to claim 5, characterized in that The functional substance A and the functional substance B are independently selected from carboxylic acids and their derivatives, amino acids and their derivatives, sulfonic acids and their derivatives, polyhydroxy compounds and their derivatives, phosphoric acid and their derivatives, organic amines and their derivatives, imidazoles and their derivatives, pyridine and their derivatives, and organic silanes.

7. The method for preparing particles according to any one of claims 1 to 6, characterized in that: The following steps are involved: (a) crushing natural materials into coarse particles with an average diameter of 1-100 μm; (b) contacting the coarse particles with a functional substance A to obtain surface-modified coarse particles whose surfaces are modified with the functional substance A; (c) crushing the surface-modified coarse particles to obtain fine particles; (d) contacting the fine particles with the functional substance B to obtain the natural material-based Janus particles.

8. The preparation method according to claim 7, characterized in that: The functional substance A and the functional substance B are solid, and no solvent is used in the steps (b) and (d).

9. The preparation method according to claim 7, characterized in that: The steps (b) and (d) are carried out in a solvent, and the solvent is preferably selected from one or more of water, alcohols, ketones, ethers, hydrocarbons, and sulfoxide solvents, and more preferably selected from one or more of water, methanol, ethanol, alcohol, propylene glycol, glycerol, panthenol, acetone, THF, DMSO, n-hexane, cyclohexane, isohexadecane, and C7-16 isoparaffin.

10. The preparation method according to claim 7 or 8, characterized in that: The crushing in steps (a) and (c) is mechanical crushing, and is more preferably carried out in a mortar, a high-speed stirrer, a high-speed shearing machine, a ball mill, a high-speed air flow crushing, a high-pressure air flow crushing, a high-temperature and high-pressure disintegration, a water-jet crushing, an ultrafine grinder, an ultrafine pulverizer, a nano grinder, a nano pulverizer or a freezing crusher.