WO2025035956A1 - 一种天然材质基Janus颗粒及其制备方法 - Google Patents

一种天然材质基Janus颗粒及其制备方法 Download PDF

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WO2025035956A1
WO2025035956A1 PCT/CN2024/100540 CN2024100540W WO2025035956A1 WO 2025035956 A1 WO2025035956 A1 WO 2025035956A1 CN 2024100540 W CN2024100540 W CN 2024100540W WO 2025035956 A1 WO2025035956 A1 WO 2025035956A1
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particles
acid
natural material
functional substance
natural
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French (fr)
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杨振忠
孙大吟
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Tsinghua University
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Tsinghua University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H99/00—Subject matter not provided for in other groups of this subclass, e.g. flours, kernels
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/25—Silicon; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/27—Zinc; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/36—Carboxylic acids; Salts or anhydrides thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/36—Carboxylic acids; Salts or anhydrides thereof
    • A61K8/361—Carboxylic acids having more than seven carbon atoms in an unbroken chain; Salts or anhydrides thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/41—Amines
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/44—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/64—Proteins; Peptides; Derivatives or degradation products thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C1/00—Crushing or disintegrating by reciprocating members
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C19/00—Other disintegrating devices or methods
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/04—Compounds of zinc
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/04—Compounds of zinc
    • C09C1/043—Zinc oxide
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    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3009—Physical treatment, e.g. grinding; treatment with ultrasonic vibrations
    • C09C1/3018—Grinding
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3063—Treatment with low-molecular organic compounds
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    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/309—Combinations of treatments provided for in groups C09C1/3009 - C09C1/3081
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    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/40—Compounds of aluminium
    • C09C1/405—Compounds of aluminium containing combined silica, e.g. mica
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/04—Physical treatment, e.g. grinding or treatment with ultrasonic vibrations
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/04—Physical treatment, e.g. grinding or treatment with ultrasonic vibrations
    • C09C3/041—Grinding
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; OIL DRYING AGENTS, i.e. SICCATIVES; TURPENTINE
    • C09F1/00—Obtaining purification, or chemical modification of natural resins, e.g. oleo-resins
    • C09F1/04—Chemical modification, e.g. esterification
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer

Definitions

  • the invention relates to natural material-based Janus particles, belonging to the field of composite materials.
  • particles used in industrial applications 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.
  • 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.
  • 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.
  • the subject of the present invention is to provide a natural material-based Janus particle and a preparation method thereof.
  • 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.
  • the present invention solves the problem of the present invention through the following solutions.
  • 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 ⁇ m.
  • 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.
  • 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.
  • 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.
  • 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.
  • steps (b) and (d) are carried out in a solvent
  • 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.
  • 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.
  • the word “may” means both performing a certain process and not performing a certain process.
  • 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.
  • the elements may be combined in various embodiments in any suitable manner.
  • 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.
  • the temperature when “normal temperature” or “room temperature” is used, the temperature may be 10-40°C.
  • 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 50 ⁇ m.
  • 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.
  • 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.
  • 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.
  • 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.
  • natural material means a material that comes from nature and has not been processed or has only been physically processed.
  • 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%.
  • the natural material constituting the natural material-based particles which can be any suitable natural material.
  • 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.
  • the natural material is one or more of materials derived from organisms and natural inorganic substances.
  • the natural material derived from organisms may be one or more materials derived from plants or animals.
  • 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
  • the animal-derived material is one or more of animal tissues, cells, blood, milk or dairy products, bones, pearls, shells, and carapaces.
  • animal tissues, cells, blood, milk or dairy products, bones, pearls, shells, and carapaces 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.
  • the material derived from natural inorganic substances is one or more of clay and ore.
  • 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,ixie lava clay, fuller's earth, Haiermu clay, etc.
  • 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 Real estate, 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, zi
  • the natural material is a natural organic matter, more preferably a polysaccharide macromolecular colloid, and further preferably selected from peach gum and gum.
  • the natural material is plant powder.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the phosphonic acid can be selected from aliphatic phosphonic acid, alicyclic phosphonic acid, aromatic phosphonic acid, and heterocyclic phosphonic acid.
  • the aliphatic phosphonic acid may be a linear or branched, saturated or unsaturated aliphatic phosphonic acid.
  • 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.
  • 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.
  • Polyols are organic compounds that have two or more hydroxyl groups in one molecule.
  • 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.
  • 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.
  • 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 H
  • 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:
  • 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 natural material is ground into powder to form a coarse natural material with a particle size of 1 to 100 ⁇ m.
  • These particles are modified with composite substance A to obtain natural material particles with a primary larger particle size and the outer surface of which is modified with functional substance A.
  • the equipment parameters are changed, and the natural material is crushed into powder by mechanical crushing to form fine natural material with a particle size of 100 nm to 50 ⁇ m. Some areas on the surface of these particles are areas that have been modified with composite substance A before.
  • the particles are broken into smaller pieces, and fresh parts that have not been modified with substance A are exposed at the broken parts. These particles are further modified with composite substance B to obtain natural material particles with a smaller particle size and the outer surface of which is modified with functional substance B.
  • Functional substance A and functional substance B can be solid or liquid independently.
  • 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.
  • 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.
  • 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.
  • the ball mill used is a planetary ball mill, PM2L
  • the grinding conditions are 220V, 50Hz, 0.75KW
  • the API nano ball mill used is FRITSCH/Germany PULVERISETTE 7 enhanced type.
  • 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.
  • the natural material particles prepared by the above process in multiple stages have Janus structural characteristics, and thus are natural material-based Janus particles.
  • Embodiment 2 is a diagrammatic representation of Embodiment 1:
  • 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 ⁇ m. 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.
  • Embodiment 3 is a diagrammatic representation of Embodiment 3
  • 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 100 ⁇ m.
  • 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 ⁇ m. 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.
  • Embodiment 4 is a diagrammatic representation of Embodiment 4:
  • 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.
  • Embodiment 5 is a diagrammatic representation of Embodiment 5:
  • the above granular powder was dispersed in water with a solid content of 50%. After 10 min of crushing, fine particles were obtained with an average particle size of 1 ⁇ m. These fine particles were smaller in size than the coarse particles, except that part of the outer surface was modified by histidine, and fresh parts were exposed at the crushing and breaking sites through further crushing and breaking.
  • the natural material-based Janus particles of the present invention can be widely used in the fields of cosmetics, industrial additives, medical treatment, etc.

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Abstract

本发明涉及一种天然材质基Janus颗粒及其制备方法。本发明的天然材质基Janus颗粒包括天然材质基颗粒，和修饰在所述天然材质基颗粒表面的、彼此不同的功能物质A和功能物质B；其中，所述天然材质基颗粒的平均直径为100nm～50μm。本发明利用多级次制备方法实现程序化的多尺度颗粒多级次制备及其相应的顺序改性，进而得到负载更多功能物质的天然材质颗粒。

Description

一种天然材质基Janus颗粒及其制备方法
相关申请的引用
本申请要求申请日为2023年8月17日、申请号为202311037170.2，发明名称为“一种天然材质基Janus颗粒及其制备方法”的在中国递交的在先发明专利申请的优先权，该在先申请的全部内容通过引用合并于此。
技术领域
本发明涉及一种天然材质基Janus颗粒，属于复合材料领域。
背景技术
目前工业应用的颗粒，特别是传统意义上的颗粒多呈圆形，其通常由同一物质组成，其颗粒表面和内部组成完全相同，无差异化的单一结构只能应用于简单的使用场景，对于复杂体系，特别是对于多尺度复杂体系将难以发挥作用。
Janus颗粒通常是指一个颗粒兼具不同的两种组成或结构，且这两部分具有明确的分区。这种各向异性显著的颗粒不同于传统均质颗粒，能在乳化、研磨、润滑、功能物质递送等方面起到独特作用。此外，Janus颗粒还有望作为功能制剂载体实现更加复杂环境下的应用。
目前，天然材质的材料已经被当作主体材料、工业助剂、装饰物品、日化产品、功能材料等广泛应用到我们的生产生活中，并发挥了清洁、吸附、美容、保健、治疗等诸多功能，特别是在人体复杂环境中发挥了积极作用，这其中将它们粉化成颗粒是最突出的使用途径。
发明内容
发明要解决的问题
然而，目前将天然材质破碎粉化成颗粒也只是通过简单的粉碎过程，后 续改性多为均质表面改性，其功能物质改性与复合受到了极大的限制。这主要表现在：1.天然材质破碎成粉状颗粒后直接粗犷使用；2.普遍以溶剂提取天然材料所蕴含的有效成分作为功能应用渠道；3.未多尺度开发功能化天然材质且使用方式非常局限。因此，非常有必要突破传统，利用前沿技术对天然材质进行物理和化学改造，以促进功能拓展和行业发展。
因此，本发明的课题在于，提供一种天然材质基Janus颗粒及其制备方法。
用于解决问题的方案
本发明人在研究中发现，天然材质通过不同的机械破碎工艺和过程可以得到不同尺度的粉体块状天然材质颗粒，根据这一技术特点，可以利用多级次制备方法实现程序化的多尺度颗粒多级次制备及其相应的顺序改性，进而得到负载更多功能物质的天然材质颗粒，由此完成了本发明。
具体地，本发明通过以下方案解决本发明的问题。
[1]一种天然材质基Janus颗粒，其包括天然材质基颗粒，和修饰在所述天然材质基颗粒表面的、彼此不同的功能物质A和功能物质B；其中，所述天然材质基颗粒的平均直径为100nm～50μm。
[2]根据[1]所述的颗粒，其中，所述天然材质基颗粒为由天然材质构成的颗粒，其中天然材质的含量为80质量％以上；所述天然材质为源于生物体、天然无机物的材料中的一种或多种，所述天然材质优选为天然有机物，更优选为多糖类大分子胶体，进一步优选选自桃胶、树胶。
[3]根据[2]所述的颗粒，其中，所述源于生物体的材料为源于植物、动物的材料中的一种或多种；所述源于植物的材料优选为源于植物的根、茎、叶、种子、花粉的材料中的一种或多种，更优选为植物粉末；所述源于动物的材料为选自细胞、血液、奶或奶制品、骨骼、珍珠、贝壳、甲壳中的一种或多种，优选选自紫虫胶、珍珠粉。
[4]根据[2]所述的颗粒，其中，所述源于天然无机物的材料为粘土、矿石中的一种或多种，优选选自云母、硅石、氧化锌。
[5]根据[1]至[4]中任一项所述的颗粒，其中，所述功能物质A和功能物 质B通过化学键与天然材质基颗粒连接，优选地，所述功能物质A和功能物质B彼此独立地选自具有羧基、磺酸基、磷酸基、氨基、咪唑基、吡啶基以及它们的盐中的一种或多种官能团的化合物；所述功能物质A修饰的表面区域与所述功能物质B修饰的表面区域的面积比为(10～1)：1。
[6]根据[5]所述的颗粒，其中，所述功能物质A和功能物质B彼此独立地选自羧酸及其衍生物、氨基酸及其衍生物、磺酸及其衍生物、多羟基化合物及其衍生物、磷酸及其衍生物、有机胺及其衍生物、咪唑及其衍生物、吡啶及其衍生物、有机硅烷。
[7][1]～[6]中任一项所述的颗粒的制备方法，其包括以下步骤：
(a)将天然材质破碎为平均直径为1-100μm的粗级颗粒；
(b)使所述粗级颗粒与功能物质A接触，得到表面修饰有功能物质A的表面修饰粗级颗粒；
(c)对所述表面修饰粗级颗粒进行破碎，得到细级颗粒；
(d)使所述细级颗粒与所述功能物质B接触，得到所述天然材质基Janus颗粒。
[8]根据[7]所述的制备方法，其中，所述功能物质A和功能物质B为固体，并且所述步骤(b)和(d)中不使用溶剂。
[9]根据[7]所述的制备方法，其中，所述步骤(b)和(d)在溶剂中进行，所述溶剂优选为选自水、醇类、酮类、醚类、烃类、亚砜类溶剂中的一种或多种，更优选选自水、甲醇、乙醇、酒精、丙二醇、丙三醇、泛醇、丙酮、THF、DMSO、正己烷、环己烷、异十六烷、C7-16异链烷烃中的一种或多种。
[10]根据[7]或[8]所述的制备方法，其中，所述步骤(a)和(c)中的破碎为机械破碎，更优选在研钵、高速搅拌器、高速剪切机、球磨、高速气流破碎、高压气流破碎、高温高压崩解、飞水破碎、超细研磨机、超细粉碎机、纳米研磨机、纳米粉碎机或冷冻破碎机中进行。
发明的效果
本发明的天然材质基Janus颗粒将天然材质颗粒复合更多功能物质并构建了Janus结构，本发明的天然材质基Janus颗粒具备多种功能，结构上突出的各向异性能够为分散体系带来新的流变行为，发挥更多更独特的作用，例如清洁作用、研磨作用、渗透作用、透皮作用、防护作用、修饰作用、美化作用、保养作用等。
具体实施方式
以下将详细说明本发明的各种示例性实施例、特征和方面。在这里专用的词“示例性”意为“用作例子、实施例或说明性”。这里作为“示例性”所说明的任何实施例不必解释为优于或好于其它实施例。
另外，为了更好地说明本发明，在下文的具体实施方式中给出了众多的具体细节。本领域技术人员应当理解，没有某些具体细节，本发明同样可以实施。在另外一些实例中，对于本领域技术人员熟知的方法、手段、器材和步骤未作详细描述，以便于凸显本发明的主旨。
如无特殊声明，本说明书中所使用的单位均为国际标准单位，并且本发明中出现的数值，数值范围，均应当理解为包含了工业生产中所不可避免的系统性误差。
本说明书中，使用“可以”表示的含义包括了进行某种处理以及不进行某种处理两方面的含义。
本说明书中，所提及的“一些具体/优选的实施方案”、“另一些具体/优选的实施方案”、“实施方案”等是指所描述的与该实施方案有关的特定要素(例如，特征、结构、性质和/或特性)包括在此处所述的至少一种实施方案中，并且可存在于其它实施方案中或者可不存在于其它实施方案中。另外，应理解，所述要素可以任何合适的方式组合在各种实施方案中。
本说明书中，使用“数值A～数值B”表示的数值范围是指包含端点数值A、B的范围。
本说明书中，使用“常温”、“室温”时，其温度可以是10-40℃。
<天然材质基Janus颗粒>
本发明的一个目的是提供一种天然材质基Janus颗粒，其包括天然材质基颗粒，和修饰在所述天然材质基颗粒表面的、彼此不同的功能物质A和功能物质B；其中，所述天然材质基颗粒的平均直径为100nm～50μm。
基于Janus颗粒固有的特性，本领域技术人员能够理解，功能物质A和功能物质B在天然材质基颗粒表面具有严格分区。即Janus颗粒表面具有功能物质A修饰的表面区域和功能物质B修饰的表面区域，其中功能物质A修饰的表面区域中，功能物质A在所有表面修饰物质中的比例为80质量％以上，优选为90质量％以上；功能物质B修饰的表面区域中，功能物质B在所有表面修饰物质中的比例为80质量％以上，优选为90质量％以上。
在一个实施方案中，功能物质A修饰的表面区域与所述功能物质B修饰的表面区域的面积比为(10～1)：1。
功能物质A和功能物质B可通过化学键或物理相互作用与天然材质基颗粒相连。其中，物理相互作用可以为氢键、范德华力、静电力等，化学键可以是共价键、离子键、金属键等。功能物质A和功能物质B优选通过化学键相连。
以下分别详细描述本发明的Janus颗粒的各个组成部分。
天然材质基颗粒
本说明书中，“天然材质”意指来自自然界，没有经过加工或仅经过物理加工的材质。
本说明书中，“天然材质基颗粒”是指由天然材质构成的颗粒，其中天然材质的含量为80质量％以上，例如90质量％以上，又例如95质量％以上，也可以为100％。
本发明中，对于构成天然材质基颗粒的天然材质没有特别限制，其可以为任何合适的天然材质。特别地，本发明中使用的天然材质颗粒为国家药监局化妆品司发布的INCI化妆品原料名录中的天然材质。
在一个实施方案中，天然材质为源于生物体、天然无机物的材料中的一种或多种。
源于生物体的天然材质可以为源于植物、动物的材料中的一种或多种。
源于植物的材料为源于植物的根、茎、叶、种子、花粉的材料中的一种或多种。其实例包括但不限于：勃那特螺旋藻粉、中药材粉体、粮食粉体、植物粉体、植物根粉、植物叶粉、茶叶、茶叶粉、赤糖糊粉、大麦粉、大麦叶粉、大麦籽细粉、淡竹叶粉、稻壳粉、稻米粉、花粉、冬虫夏草菌丝粉、儿茶胶、儿茶叶粉、儿茶木粉、茯苓粉、茯苓菌核粉、淀粉、木薯淀粉、改性马铃薯淀粉、改性玉米淀粉、米类粉体、柑橘果皮粉、果皮粉、广西沙柑果皮粉、果胶、海藻籽、植物籽、水果籽、小烛树蜡、褐藻、胡桃壳粉、琥珀粉、花粉、花生细粉、树皮、树皮粉、咖啡粉、可可壳粉、明胶、纳托胶、桃胶、树胶、阿拉伯树胶、瓜儿胶、鸭皂树胶、茉莉花瓣、花瓣粉、牡蛎壳粉、纤维素、微晶纤维素、纤维素胶、木质素、松花粉、松香、小麦麸、小麦胚芽粉、小麦仁细粉、亚麻籽细粉、燕麦淀粉、燕麦麸皮粉、燕麦仁粗粉、燕麦仁细粉、银杏叶粉、油茶叶粉、葡萄籽粉、黄瓜籽粉、鹿角霜、竹炭等
所述源于动物的材料为动物组织、细胞、血液、奶或奶制品、骨骼、珍珠、贝壳、甲壳中的一种或多种。其实例包括但不限于贝壳硬蛋白粉、奶粉、蜂蜜、蜂花粉、蜂胶、蜂胶蜡、蜂花粉、蜂蜡、蜂王浆、蜂王浆粉、干蛋黄、干乳酪、蝉蜕、蚕丝、水解蚕丝、季铵盐-79水解蚕丝、血液、马鹿血粉、奶、奶粉、酸乳粉、虫胶、紫虫胶、紫虫胶蜡、动物骨、骨粉、珍珠、水牛角、羚羊角、土鳖虫、胭脂虫、珍珠、珍珠粉、珍珠母、珍珠母粉、珍珠母贝粉等。
源于天然无机物的材料为粘土、矿石中的一种或多种。其中粘土的实例包括但不限于北海道阿寒粘土、高岭土、黄土、活性白土、火山灰、火山泥、膨润土、季铵盐-18膨润土、加拿大皂土、曼尼古根冰河泥、蒙脱土、摩洛哥熔岩粘土、漂白土、海尔木粘土等。
矿石可以为金属矿、金属氧化物矿等，其实例包括但不限于胆石、蛋白石粉、电气石、方解石、沸石、浮石、硅镁土、硅石、硅藻土、海淤泥、滑石粉、黄赭石、火山砂、甲硅烷基化硅石、明矾、钾明矾、金、金刚粉、金 礞石、孔雀石、蓝宝石粉、菱锰矿、菱锌矿、硫磺、硫磺粉、硫酸钡、硫酸钙、硫酸钙水合物、硫酸银、炉甘石、铝、铝粉、铝克洛沙、氯化银、氯氧化铋、麦饭石、硼砂、羟基磷灰石、氢氧化钙、氢氧化铝、氢氧化铬绿、石英、碳酸钙、碳酸锌、铁粉、铜粉、氧化锆、五氯羟铝锆、细砂、响岩、盐矿泥浆、氧化钙、氧化钙铈、氧化铬绿、氧化钴铝、氧化铝、氧化镁、氧化钠、氧化铈、氧化钛钴、氧化钛铁、氧化铁类、氧化铁类/二氧化钛烧结物、氧化锡、氧化锌、氧化银、叶蜡石、伊利水云母、银、云母、陨石粉、珍珠岩、膨胀珍珠岩、紫石英粉、青铜粉等。
在优选的实施方案中，天然材质为天然有机物，更优选为多糖类大分子胶体，进一步优选选自桃胶、树胶。
在优选的实施方案中，天然材质为植物粉末。
功能物质A/功能物质B
本发明中，对于功能物质A和功能物质B的具体种类没有特别限制，其可以为能够对天然材质颗粒表面进行修饰，从而赋予其特定功能的任何合适物质。
在一个实施方案中，功能物质A和功能物质B彼此独立地选自具有羧基、磺酸基、磷酸基、氨基、咪唑基、吡啶基以及它们的盐中的一种或多种官能团的化合物。
在一个实施方案中，功能物质A和功能物质B彼此独立地选自羧酸及其衍生物、氨基酸及其衍生物、磺酸及其衍生物、多羟基化合物及其衍生物、膦酸及其衍生物、有机胺及其衍生物、咪唑、咪唑烷基脲、吡啶及其衍生物、有机硅烷等。
羧酸可以选自脂肪族羧酸、脂环族羧酸、芳香族羧酸、杂环羧酸。其中，脂肪族羧酸可以为直链或支链的、饱和或不饱和的脂肪族羧酸。
磺酸可以选自脂肪族磺酸、脂环族磺酸、芳香族磺酸、杂环磺酸。其中，脂肪族磺酸可以为直链或支链的、饱和或不饱和的脂肪族磺酸。
膦酸可以选自脂肪族膦酸、脂环族膦酸、芳香族膦酸、杂环膦酸。其中， 脂肪族膦酸可以为直链或支链的、饱和或不饱和的脂肪族膦酸。
羧酸、磺酸、膦酸或氨基酸的衍生物可以分别为羧酸、磺酸、膦酸或氨基酸的盐、酯、酰胺等形式，也可以为其中除了羧基、磺酸基团、膦酸基团以外的部分被取代基取代而成的衍生物。其中，盐可以为碱金属盐(例如锂、钠、钾等)或碱土金属盐(例如钙、镁等)。酯可以为羧酸、磺酸、膦酸或氨基酸与脂肪醇、脂环醇或芳香醇反应得到的酯，其中醇可以为一元醇或多元醇，可以为饱和或不饱和的。酰胺可以为羧酸、磺酸、膦酸或氨基酸与胺反应得到的，所述胺可以为脂肪胺或芳香胺，可以为一元胺也可以为多元胺。取代基可以为羟基、巯基、任选具有官能团的聚合物链段等。
多羟基化合物是指一分子内具有两个以上羟基的有机化合物。
有机胺可以为脂肪族胺、脂环族胺、芳香族胺、杂环胺。有机胺的衍生物可以为除了氨基以外的有机基团被取代基取代而成的衍生物或有机胺的硫酸盐等。其中，取代基可以为羟基、具有氧亚烷基重复单元的链段等。
吡啶的衍生物是指吡啶环被取代基取代而成的衍生物，其中取代基包括但不限于羧基、氨基、羟基以及被羧基、氨基或羟基取代的烷基等。
在一个具体的实施方案中，功能物质A和功能物质B彼此独立地选自月桂酸、月桂酸钠、酒石酸、酒石酸二钠、2-磺基月桂酸二钠、硬脂酸、硬脂酸钠、焦磷酸四钠、4-氨基-3-羟基丁酸、油酸、油酸钠、磷酸、磷酸二氢钠、磷酸三钠、苯磺酸钠、3-氨基丙烷磺酸、木质素磺酸钠、C12-15烷醇聚醚-3硫酸钠、C12-15烷醇聚醚-7羧酸钠、C12-15烷醇聚醚硫酸钠、C12-15烷基硫酸钠、C14-16烯烃磺酸钠、4-羟基苯甲酸、C4-12烯烃/马来酸共聚物钠、EDTA(盐)、HEDTA三钠、10-羟基癸酸、肌酸、酒石酸、酒石酸(盐)、聚β-氨基丙酸、聚γ-谷氨酸钠、聚氨丙基双胍硬脂酸盐、聚丙酸、聚丙酸(盐)、聚丙烯酰胺基甲基丙烷磺酸、聚丙烯酰基二甲基牛磺酸铵、己基癸酸、2,6-二羧基吡啶、2-氨基-3-羟基吡啶、2-邻-乙基抗坏血酸、C8-16异烷基琥珀酰大豆磺酸钠、C8-16异烷基琥珀酰乳球蛋白磺酸钠、对氨基苯酚硫酸盐、吡咯烷酮羧酸、藻酸、藻酸钠、2-羟乙基苦氨酸、酪蛋白酸(盐)、乳酸杆菌、 氨基酸包括甘氨酸、丙氨酸、缬氨酸、亮氨酸、异亮氨酸、甲硫氨酸(蛋氨酸)、脯氨酸、色氨酸、丝氨酸、酪氨酸、半胱氨酸、苯丙氨酸、天冬酰胺、谷氨酰胺、苏氨酸、天冬氨酸、谷氨酸、赖氨酸、精氨酸、组氨酸、硒半胱氨酸、吡咯赖氨酸、鲸蜡基苯基醚二磺酸二钠、2,6-二羧基吡啶、2-邻-乙基抗坏血酸、磷酸腺苷、绿原酸、马来酸、咪唑、咪唑烷基脲、迷迭香酸、米糠酸、脒基脯氨酸、木质素磺酸钠、柠檬酸、牛奶氨基酸类、皮肤素硫酸钠、苹果酸、苹果酸(盐)、葡糖酸、葡糖醛酸、羟苯甲酸钠、羟丙基淀粉磷酸钠、羟丙基三甲基氯化铵透明质酸、羟基肉桂酸、羟基硬脂酸、羟乙基乙二胺三乙酸、巯基乙酸、巯基乙酸(盐)、巯基丙酸、去甲二氢愈创木酸、肉豆蔻酸、肉豆蔻酸(盐)、肉豆蔻酰肌氨酸、肉桂酸、乳清酸、乳酸、乳糖酸、软骨素硫酸钠、噻唑基丙氨酸、噻吩甲酰蛋氨酸、三聚亚油酸、山梨酸、山梨酸(盐)、山嵛酸、山嵛酸(盐)、十八碳烯二酸、十二烷基苯磺酸、十二烷基苯磺酸(盐)、透明质酸、水解透明质酸、水杨酸、水杨酸(盐)、脱羧肌肽盐酸盐、脱氧核糖核酸、脱乙酰壳多糖乳酸盐、脱乙酰壳多糖甘醇酸盐、脱乙酰壳多糖乳酸盐、妥尔油酸、五肽-34三氟乙酸盐、西门木炔酸、亚油酸、亚油酸(盐)、羊毛脂酸、椰油酸、椰油酸(盐)、椰油酰肌氨酸、椰油酰肌氨酸(盐)、叶酸、吲哚乙酸、硬脂酸、油酸、油酸(盐)、月桂酸、月桂酸(盐)、月桂氨基丙酸、月桂氨基丙酸(盐)、植酸、植酸(盐)、2-氨基-3-羟基吡啶、2-氨基-4-羟乙氨基茴香醚硫酸盐、PEG-9硬脂酰胺羧酸、扁桃酸、淀粉辛烯基琥珀酸(盐)、聚二羟基吲哚、聚甲基丙烯酰基赖氨酸、聚赖氨酸、聚萘磺酸钠、聚天冬氨酸钠、咖啡酸、咖啡因羧酸、抗坏血酸、抗坏血酸多肽、可可脂酰两性基乙酸钠、枯烯磺酸钠、苦氨酸(盐)、蜡酸、酪蛋白酸(盐)、吡啶二羧酸、吡咯烷酮羧酸、联苯乙烯二苯基二磺酸二钠、硬脂胺、对氨基苯酚、对苯二胺硫酸盐、氨基丙二醇、氨基丁酸、氨基三(亚甲基膦酸)五钠、氨基双丙基聚二甲基硅氧烷、氨基乙烷亚磺酸、氨基酯类-1、氨甲基丙醇、氨甲基丙二醇、氨乙基氨丙基聚二甲基硅氧烷、氨丙基聚二甲硅氧烷、氨丙基三乙氧基硅烷、氨丙基生育酚磷酸酯、氨丁三醇、氨端 聚二甲基硅氧烷、氨基丙醇抗坏血酸磷酸酯、氨基丙醇曲酸磷酸酯、氨基三(亚甲基膦酸)五钠、氨基双丙基聚二甲基硅氧烷、氨基乙烷亚磺酸、氨乙基氨丙基聚二甲基硅氧烷、氨乙基次膦酸、二棕榈基胺、甲氧丙基葡糖酰胺、金刚烷基二羟基苯甲酰胺、壳聚糖、壳糖胺、壳糖胺盐酸盐、2-氨基-3-羟基吡啶、2-氨基-4-羟乙氨基茴香醚、2-氨基-4-羟乙氨基茴香醚硫酸盐、2-氨基-6-氯-4-硝基苯酚、3-氨基丙烷磺酸、4-氨基-2-羟基甲苯、4-氨基-3-羟基丁酸、4-氨基-3-硝基苯酚、4-氨基间甲酚、C5-20烯烃磺酸钠、C8-16异烷基琥珀酰大豆磺酸钠、C8-16异烷基琥珀酰乳球蛋白磺酸钠、PEG-15牛脂基聚胺、PEG-15椰油胺、PEG-15椰油基甲基氯化铵、PEG-15椰油基聚胺、PEG-2大豆胺、PEG-2硬脂胺、PEG-2油胺、对苯二胺、氨丙基聚二甲硅氧烷、氨丙基三乙氧基硅烷、氨丙基生育酚磷酸酯、氨丁三醇、氨端聚二甲基硅氧烷、氨基丙醇抗坏血酸磷酸酯、氨基丙醇曲酸磷酸酯、氨基丙二醇、氨基丁酸、氨基三(亚甲基膦酸)五钠、氨基双丙基聚二甲基硅氧烷、氨基乙烷亚磺酸、氨基酯类-1、氨甲基丙醇、氨甲基丙二醇、氨乙基氨丙基聚二甲基硅氧烷、氨乙基丙二醇、氨乙基次膦酸、对氨基苯甲酸、二氨基嘧啶氧化物、水解葡糖氨基聚糖、羧乙基氨基丁酸、2,6-二氨基吡啶等及其衍生物。
<制备方法>
本发明的另一个目的是提供本发明的天然材质基Janus颗粒的制备方法，其包括以下步骤
(a)将天然材质破碎为平均直径为1-100μm的粗级颗粒；
(b)使所述粗级颗粒与功能物质A接触，得到表面修饰有功能物质A的表面修饰粗级颗粒；
(c)对所述表面修饰粗级颗粒进行破碎，得到细级颗粒；
(d)使所述细级颗粒与所述功能物质B接触，得到所述天然材质基Janus颗粒。
本发明的方法中，物质A和B是间歇顺序修饰的，该间歇顺序修饰过程与机械破碎过程交替进行。设置设备参数，利用机械破碎将天然材质破碎成 粉，形成粗天然材质，该天然材质的粒径在1～100μm，将这些颗粒改性复合物质A，得到初级较大粒径外表面修饰了功能物质A的天然材质颗粒。进一步地，改变设备参数，利用机械破碎将天然材质破碎成粉，形成细天然材质，该天然材质的粒径在100nm～50μm，这些颗粒表面部分区域是之前已经修饰复合物质A的区域，经过第二次机械破碎的精细加工过程后，颗粒断裂成尺寸更小的片，在断裂处暴露出未经物质A修饰的新鲜部分，将这些颗粒进一步改性复合物质B，得到更小粒径外表面修饰了功能物质B的天然材质颗粒。
功能物质A和功能物质B可以独立地为固体或者液体。在一个实施方案中，功能物质A和功能物质B为固体，并且所述步骤(b)和(d)中不使用溶剂。即，使功能物质A和功能物质B直接以固态与天然材质颗粒接触，对天然材质颗粒表面进行修饰。
在一个实施方案中，所述步骤(b)和(d)在溶剂中进行。所述溶剂优选为选自水、醇类、酮类、醚类、烃类、亚砜类溶剂中的一种或多种。所述溶剂更优选为选自水、甲醇、乙醇、酒精、丙二醇、丙三醇、泛醇、丙酮、THF、DMSO、正己烷、环己烷、异十六烷、C7-16异链烷烃中的一种或多种。
在一个实施方案中，所述步骤(a)和(c)中的破碎为机械破碎，更优选在研钵、高速搅拌器、高速剪切机、球磨、高速气流破碎、高压气流破碎、高温高压崩解、飞水破碎、超细研磨机、超细粉碎机、纳米研磨机、纳米粉碎机或冷冻破碎机中进行。
实施例1
以下实施例中，使用的球磨机为行星式球磨机，PM2L，研磨条件为220V，50Hz，0.75KW，使用的API纳米球磨机为FRITSCH/德国飞驰，PULVERISETTE 7加强型。
实施例1
将100g珍珠粉放入行星式球磨机，设定球磨机档位为1档，持续研磨30min。粗级研磨结束后，将1.0g硬脂酸粉末加入上述粉体中，在1档研磨条 件下持续研磨30min，得到颗粒外表面修饰硬脂酸的天然材质颗粒，平均粒径为1μm。
重新设定球磨机档位为2档，持续研磨30min，得到细级颗粒，平均粒径为500nm。这些细级颗粒比粗级颗粒的尺寸更小，除了外表面部分区域被硬脂酸改性，通过进一步破碎断裂，在破碎断裂处暴露出新鲜的部分。
将1.0g组氨酸加入上述细级颗粒中，在2档研磨条件下持续研磨30min，得到新鲜部分被组氨酸修饰且剩余部分被硬脂酸修饰的天然材质颗粒。通过上述过程多级次制备得到的天然材质颗粒具备Janus结构特征，因此是天然材质基Janus颗粒。
实施例2：
将100g天然云母放入行星式球磨机，设定球磨机档位为1档，持续研磨30min。粗级研磨结束后，将1.0g硬脂酸粉末加入上述粉体中，在1档研磨条件下持续研磨30min，得到颗粒外表面修饰透明质酸的天然材质颗粒，平均粒径为2μm。
重新设定球磨机档位为2档，持续研磨30min，得到细级颗粒，平均粒径为1μm。这些细级颗粒比粗级颗粒的尺寸更小，除了外表面部分区域被透明质酸改性，通过进一步破碎断裂，在破碎断裂处暴露出新鲜的部分。
将1.0g谷氨酸肽加入上述细级颗粒中，在2档研磨条件下持续研磨30min，得到新鲜部分被谷氨酸肽修饰且剩余部分被透明质酸修饰的天然材质颗粒。通过上述过程多级次制备得到的天然材质颗粒具备Janus结构特征，因此得到天然材质基Janus颗粒。
实施例3：
将100g紫虫胶放入行星式球磨机，设定球磨机档位为1档，持续研磨30min。粗级研磨结束后，将上述粉体分散在水中，升温至40℃后并伴随60rpm/min的搅拌。将1.0g硬脂酸钠粉末加入到上述粉体的分散液中，改性过程持续30min，通过过滤和干燥，得到颗粒外表面修饰硬脂酸的天然材质颗粒，平均粒径为100μm。
重新设定球磨机档位为2档，持续研磨30min，得到细级颗粒，平均粒径为50μm。这些细级颗粒比粗级颗粒的尺寸更小，除了外表面部分区域被硬脂酸改性，通过进一步破碎断裂，在破碎断裂处暴露出新鲜的部分。
将1.0g组氨酸加入上述细级颗粒中，在2档研磨条件下持续研磨30min，得到新鲜部分被组氨酸修饰且剩余部分被硬脂酸修饰的天然材质颗粒。通过上述过程多级次制备得到的天然材质颗粒具备Janus结构特征，因此得到天然材质基Janus颗粒。
实施例4：
将100g硅石放入API纳米球磨机，设定API纳米球磨机档位为1档，持续破碎10min，得到粗级天然材质颗粒。将上述粉体分散在水中，升温至40℃后并伴随60rpm/min的搅拌，并将1.0g硬脂酸粉末加入到上述粉体的分散液中，改性过程持续30min，通过过滤和干燥，得到颗粒外表面修饰硬脂酸的天然材质颗粒，平均粒径为800nm。
重新设定API纳米球磨机档位为2档，持续破碎10min，得到细级颗粒，平均粒径为400nm。这些细级颗粒比粗级颗粒的尺寸更小，除了外表面部分区域被硬脂酸改性，通过进一步破碎断裂，在破碎断裂处暴露出新鲜的部分。
将1.0g组氨酸加入上述细级颗粒中，在2档飞水破碎条件下持续研磨10min，得到新鲜部分被组氨酸修饰且剩余部分被硬脂酸修饰的天然材质颗粒。通过上述过程多级次制备得到的天然材质颗粒具备Janus结构特征，因此得到天然材质基Janus颗粒。
实施例5：
将100g氧化锌放入API纳米球磨机，设定API纳米球磨机档位为1档，持续破碎10min，得到粗级天然材质颗粒。将上述粉体分散在水中，升温至40℃后并伴随60rpm/min的搅拌，并将1.0g组氨酸末加入到上述粉体的分散液中，改性过程持续30min，通过过滤和干燥，得到颗粒外表面修饰硬脂酸的天然材质颗粒，平均粒径为3μm。
将上述颗粒粉末分散到水中，固含量为50％，利用API纳米球磨机持续 破碎10min，得到细级颗粒，平均粒径为1μm。这些细级颗粒比粗级颗粒的尺寸更小，除了外表面部分区域被组氨酸改性，通过进一步破碎断裂，在破碎断裂处暴露出新鲜的部分。
将1.0g谷氨酸肽加入上述细级颗粒中，在上述条件下持续研磨10min，得到新鲜部分被谷氨酸肽修饰且剩余部分被谷氨酸肽修饰的天然材质颗粒。通过上述过程多级次制备得到的天然材质颗粒具备Janus结构特征，因此得到天然材质基Janus颗粒。
需要说明的是，尽管以具体实例介绍了本发明的技术方案，但本领域技术人员能够理解，本发明应不限于此。
以上已经描述了本发明的各实施例，上述说明是示例性的，并非穷尽性的，并且也不限于所披露的各实施例。在不偏离所说明的各实施例的范围和精神的情况下，对于本技术领域的普通技术人员来说许多修改和变更都是显而易见的。本文中所用术语的选择，旨在最好地解释各实施例的原理、实际应用或对市场中的技术改进，或者使本技术领域的其它普通技术人员能理解本文披露的各实施例。
产业上的可利用性
本发明的天然材质基Janus颗粒可以广泛用于化妆品、工业添加剂、医疗等领域。

Claims (10)

  1. 一种天然材质基Janus颗粒，其特征在于，包括天然材质基颗粒，和修饰在所述天然材质基颗粒表面的、彼此不同的功能物质A和功能物质B；其中，所述天然材质基颗粒的平均直径为100nm～50μm。
  2. 根据权利要求1所述的颗粒，其特征在于，所述天然材质基颗粒为由天然材质构成的颗粒，其中天然材质的含量为80质量％以上；所述天然材质为源于生物体、天然无机物的材料中的一种或多种，所述天然材质优选为天然有机物，更优选为多糖类大分子胶体，进一步优选选自桃胶、树胶。
  3. 根据权利要求2所述的颗粒，其特征在于，所述源于生物体的材料为源于植物、动物的材料中的一种或多种；所述源于植物的材料优选为源于植物的根、茎、叶、种子、花粉的材料中的一种或多种，更优选为植物粉末；所述源于动物的材料为选自细胞、血液、奶或奶制品、骨骼、珍珠、贝壳、甲壳中的一种或多种，优选选自紫虫胶、珍珠粉。
  4. 根据权利要求2所述的颗粒，其特征在于，所述源于天然无机物的材料为粘土、矿石中的一种或多种，优选选自云母、硅石、氧化锌。
  5. 根据权利要求1至4中任一项所述的颗粒，其特征在于，所述功能物质A和功能物质B通过化学键与天然材质基颗粒连接，优选地，所述功能物质A和功能物质B彼此独立地选自具有羧基、磺酸基、磷酸基、氨基、咪唑基、吡啶基以及它们的盐中的一种或多种官能团的化合物；所述功能物质A修饰的表面区域与所述功能物质B修饰的表面区域的面积比为(10～1)：1。
  6. 根据权利要求5所述的颗粒，其特征在于，所述功能物质A和功能物质B彼此独立地选自羧酸及其衍生物、氨基酸及其衍生物、磺酸及其衍生物、多羟基化合物及其衍生物、磷酸及其衍生物、有机胺及其衍生物、咪唑及其衍生物、吡啶及其衍生物、有机硅烷。
  7. 权利要求1～6中任一项所述的颗粒的制备方法，其特征在于，包括以下步骤：
    (a)将天然材质破碎为平均直径为1-100μm的粗级颗粒；
    (b)使所述粗级颗粒与功能物质A接触，得到表面修饰有功能物质A的 表面修饰粗级颗粒；
    (c)对所述表面修饰粗级颗粒进行破碎，得到细级颗粒；
    (d)使所述细级颗粒与所述功能物质B接触，得到所述天然材质基Janus颗粒。
  8. 根据权利要求7所述的制备方法，其特征在于，所述功能物质A和功能物质B为固体，并且所述步骤(b)和(d)中不使用溶剂。
  9. 根据权利要求7所述的制备方法，其特征在于，所述步骤(b)和(d)在溶剂中进行，所述溶剂优选为选自水、醇类、酮类、醚类、烃类、亚砜类溶剂中的一种或多种，更优选选自水、甲醇、乙醇、酒精、丙二醇、丙三醇、泛醇、丙酮、THF、DMSO、正己烷、环己烷、异十六烷、C7-16异链烷烃中的一种或多种。
  10. 根据权利要求7或8所述的制备方法，其特征在于，所述步骤(a)和(c)中的破碎为机械破碎，更优选在研钵、高速搅拌器、高速剪切机、球磨、高速气流破碎、高压气流破碎、高温高压崩解、飞水破碎、超细研磨机、超细粉碎机、纳米研磨机、纳米粉碎机或冷冻破碎机中进行。
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