CN114132904B - Hexagonal boron nitride porous microsphere with high oil absorption and whitening effects for cosmetics - Google Patents
Hexagonal boron nitride porous microsphere with high oil absorption and whitening effects for cosmetics Download PDFInfo
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- CN114132904B CN114132904B CN202111481314.4A CN202111481314A CN114132904B CN 114132904 B CN114132904 B CN 114132904B CN 202111481314 A CN202111481314 A CN 202111481314A CN 114132904 B CN114132904 B CN 114132904B
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/064—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with boron
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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/0241—Containing particulates characterized by their shape and/or structure
- A61K8/0279—Porous; Hollow
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- 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
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/10—General cosmetic use
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
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- C01P2006/19—Oil-absorption capacity, e.g. DBP values
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Abstract
The invention belongs to the technical field of functional material preparation, and particularly relates to a hexagonal boron nitride porous microsphere and a preparation method thereof. The preparation method comprises the following steps: adding water into boric acid, 2-methylimidazole and a template agent for full dissolution, and drying to obtain uniform precursor powder; carrying out high-temperature reaction on the precursor powder in an ammonia atmosphere to obtain hexagonal boron nitride powder filled with a template agent; immersing hexagonal boron nitride powder into water to dissolve a template agent, washing, filtering and drying to obtain hexagonal boron nitride porous microspheres. The method has simple process and equipment, and the average particle size of the prepared hexagonal boron nitride porous microsphere powder is 1-6 mu m, and the hexagonal boron nitride porous microsphere powder has high purity and whiteness, high porosity and large oil absorption, and is suitable for the oil control whitening additive of cosmetics.
Description
Technical Field
The invention relates to the field of functional materials, in particular to a hexagonal boron nitride porous microsphere and a preparation method thereof.
Background
The powder raw material has wide application in cosmetics, such as skin care, make-up, sun protection, and the like, and plays roles in concealing, brightening, adsorbing, improving skin feel, and the like. The powder raw materials are classified into various methods, namely, coloring powder, white powder, constitution powder and pearl powder, wherein the coloring powder is used for adjusting color tone, the white powder has the functions of covering, whitening and blocking ultraviolet rays, the constitution powder is various in types and mainly has the functions of adjusting the spreadability, skin adhesion, gloss, texture, formability and usability of the product, and the pearl powder can improve the gloss and texture of the product. The traditional powder film covering technology is used for instant whitening, and although flaws are perfectly covered, whiteness is improved, the powder film is too thick to prevent light refraction, so that the makeup looks dull and dull. Therefore, the powder is extremely important to select and match for use in order to achieve the transparent and natural whitening and brightening effects. With the continuous improvement of the life quality of people, the oil-absorbing, whitening and brightening cosmetic has huge market demands and wide development prospects, and consumers have more urgent demands on cosmetics which are convenient to use and obvious in effect, such as concealers, foundations, eye shadows, lipsticks, sun creams and the like.
Hexagonal boron nitride is a type of boron nitrideThe inorganic nonmetallic material with a graphite-like structure formed by boron nitride hexagonal network is formed by alternately arranging third main group boron and fifth main group nitrogen into bonds. The stronger B-N covalent bond is formed in the layer, the layers are connected by weaker Van der Waals force, and the theoretical density is 2.27g/cm 3 The mohs hardness is 2, the optical band gap is 6.0eV, and the appearance is white, so it is also called "white graphite". Hexagonal boron nitride is very stable in air, can resist 1270K high temperature, has good electrical insulation, thermal conductivity and lubricity, has radiation resistance, chemical corrosion resistance and oxidation resistance, and has excellent wave transmission and dielectric properties, so that the hexagonal boron nitride has good application in a plurality of important fields, such as high-temperature ceramics, electronic packaging materials, solid lubricants, aerospace, national defense, nuclear industry and the like. Specifically, hexagonal boron nitride can be used as a crucible for melting and evaporating metal, a boat, a liquid metal conveying pipe, a high-power device base, a pipeline for melting metal, a pump part, a cast steel mold and the like, and is used for manufacturing high-temperature parts such as a rocket combustion chamber lining, a corrosion-resistant part of a magneto-rheological generator, a high-temperature high-frequency high-pressure insulating heat-dissipating part and the like, and is sprayed on a surface layer of ceramics, metal and the like to be used in important fields such as high-temperature resistant lubricants and the like. In addition, hexagonal boron nitride has been widely used as a concealer, a whitening and oil control additive for cosmetics because of its excellent biocompatibility, lubricity and unique optical properties, and has excellent adhesion and concealer ability as well as oil absorption properties to reduce skin oiliness, and thus has been attracting attention as a powder raw material for cosmetics. The cosmetic can be added into cosmetics to enhance the comfort level of the skin feel of the cosmetics, weaken wrinkles and flaws, make the skin color more uniform, increase the lubricity and brightness, be easy to clean and remove, and rapidly increase the use in the cosmetics. However, the existing hexagonal boron nitride has a lamellar non-porous structure, has the problems of low oil absorption and the like, and has limited application in the field of cosmetics.
Therefore, it is necessary to provide hexagonal boron nitride having a porous structure with high oil absorption and a method for preparing the same.
Disclosure of Invention
The invention provides a hexagonal boron nitride porous microsphere and a preparation method thereof, and aims to solve the problem of low oil absorption caused by a non-porous structure of the existing hexagonal boron nitride and the problem of limited application of the hexagonal boron nitride porous microsphere in the field of cosmetics.
In order to achieve the above purpose, the present invention provides a preparation method of hexagonal boron nitride porous microspheres, the preparation method comprising the following steps:
adding water into boric acid, 2-methylimidazole and a template agent for full dissolution, and drying to obtain uniform precursor powder;
carrying out high-temperature reaction on the precursor powder in an ammonia atmosphere to obtain hexagonal boron nitride powder filled with a template agent;
immersing the hexagonal boron nitride powder into water to dissolve a template agent, and washing, filtering and drying to obtain the hexagonal boron nitride porous microspheres.
Further, the molar ratio of boric acid to 2-methylimidazole is in the range of 1:1 to 8:1, and the molar percentage of the template agent is 50% -80%.
Further, the template agent is NaCl.
Further, the high temperature reaction temperature is 800-1600 ℃.
Further, the reaction time is 0-5h.
The invention also provides a hexagonal boron nitride porous microsphere, the particle size of the hexagonal boron nitride porous microsphere is 1-6 mu m, and the pore diameter is up to 600nm.
Further, the purity of the hexagonal boron nitride porous microsphere is more than 99%, the whiteness is as high as 104, and the oil absorption is as high as 1064mL/100g.
The scheme of the invention has the following beneficial effects:
1. compared with common hexagonal boron nitride, the hexagonal boron nitride porous microsphere has high purity and whiteness, high porosity and large oil absorption, and is suitable for oil control and whitening additives of cosmetics.
2. The boron source, the nitrogen source and the template agent used in the preparation method are all cheap industrial raw materials, are beneficial to cost control, have simple preparation process and equipment, and are convenient to post-treat and purify, thereby being a method with great advantages.
3. In the invention, sodium chloride is used as a template agent, and is melted at high temperature to directly participate in the formation of boron nitride pore channels, so that the generation of high-purity boron nitride is facilitated, and the preparation method is simple and convenient in post-treatment removal, and can be completely removed through water washing.
Drawings
In order to more clearly illustrate the technical solutions of the present invention, the drawings that are required to be used in the description of the embodiments will be briefly described below, and it is obvious that the drawings described below are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an SEM image of hexagonal boron nitride porous microspheres prepared according to example 1 of the present invention;
FIG. 2 is a statistical chart of particle size distribution of hexagonal boron nitride porous microspheres prepared in example 1 of the present invention;
FIG. 3 is an infrared spectrum and an XRD pattern of hexagonal boron nitride porous microspheres prepared in example 1 of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantages to be solved more apparent, the following detailed description will be given with reference to the accompanying drawings and the detailed description.
Unless defined otherwise, the terms of art used in the present invention have the same meaning as commonly understood by one of ordinary skill in the art. The various raw materials, reagents, instruments, equipment and the like used in the present invention can be purchased commercially or prepared by existing methods.
Example 1
The preparation method of the hexagonal boron nitride porous microsphere comprises the following steps:
adding 0.02mol of boric acid, 0.015mol of 2-methylimidazole and 0.07mol of sodium chloride into a beaker filled with 130mL of deionized water, heating and stirring, setting the temperature of a heater to 90 ℃, the stirring speed to 450r/min, stopping heating and stirring until a completely clear and transparent solution is obtained, and spray-drying the obtained clear and transparent solution by a spray dryer, wherein the temperature of an air inlet is set to 180 ℃, and the feeding flow is 800mL/min, so as to prepare white precursor powder;
weighing 4g of the obtained white precursor powder, spreading the powder in a rectangular corundum porcelain boat, introducing ammonia gas into a tube furnace for high-temperature reaction, wherein the heating rate is 10 ℃/min, the reaction temperature is 1000 ℃, and the reaction time is 3 hours. Naturally cooling after the reaction to obtain 2.75g of hexagonal boron nitride microsphere powder filled with white sodium chloride;
dispersing the obtained hexagonal boron nitride microsphere powder with 150mL of deionized water, stirring and heating to enable the hexagonal boron nitride microsphere powder to be dispersed uniformly, carrying out suction filtration on the dispersion liquid through a 0.2 mu m filter membrane after the dispersion liquid is kept for 30min, washing the dispersion liquid through deionized water for a plurality of times, until the pH value of the filtrate is 7, and carrying out vacuum drying in a vacuum drying oven at 80 ℃ to obtain 0.3g of hexagonal boron nitride porous microspheres, wherein the reaction yield is 60% calculated by boron.
The obtained hexagonal boron nitride porous microspheres are subjected to scanning electron microscope analysis and particle size distribution statistical analysis, the results of which are shown in fig. 1 and 2, and the hexagonal boron nitride porous microspheres are mainly concentrated in a 1-6 μm interval in fig. 1, and the pore diameter is up to about 600nm; as shown in FIG. 2, the average particle size of the hexagonal boron nitride porous microspheres was 2.7. Mu.m.
The prepared hexagonal boron nitride porous microsphere powder is subjected to infrared spectrum and XRD characterization, and the result is shown in figure 3, wherein the purity of the hexagonal boron nitride is higher than 99%. The O-H vibration in the infrared spectrogram is caused by the trace amount of water adsorbed by the hexagonal boron nitride porous microspheres.
The oil absorption and whiteness of the prepared hexagonal boron nitride porous microsphere powder are measured according to the methods of GB/T5211.15-2014 and GB/T5950-2008 respectively, the results are shown in Table 1, and the oil absorption of the product is 613mL/100g or 552g/100g; the whiteness of the product was 98 degrees.
Examples 2, 3 and 4
The procedure of example 1 was repeated except that the amount of the 2-methylimidazole compound used in example 1 was changed to 0.02mol, 0.005mol and 0.0025 mol.
Example 5
The procedure of example 1 was repeated except that the high-temperature reaction temperature in example 1 was changed to 1200 ℃.
Examples 6, 7, 8 and 9
The procedure of example 1 was repeated except that the heat-retaining time was changed to 0, 1, 2, or 5 hours.
Examples 10, 11 and 12
The same operations as in example 1 were conducted except that the molar amount of sodium chloride added in example 1 was changed to 0.035, 0.05 and 0.08.
Examples 13, 14 and 15
The same procedure as in example 1 was repeated except that the high-temperature reaction temperature in example 9 was changed to 800℃and 1200℃and 1600 ℃.
TABLE 1
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that various modifications and adaptations can be made without departing from the principles of the present invention, and such modifications and adaptations are intended to be comprehended within the scope of the present invention.
Claims (4)
1. The preparation method of the hexagonal boron nitride porous microsphere is characterized by comprising the following steps of:
adding water into boric acid, 2-methylimidazole and a template agent for full dissolution, and drying to obtain uniform precursor powder;
carrying out high-temperature reaction on the precursor powder in an ammonia atmosphere to obtain hexagonal boron nitride powder filled with a template agent;
immersing the hexagonal boron nitride powder into water to dissolve a template agent, and washing, filtering and drying to obtain hexagonal boron nitride porous microspheres;
the molar ratio of the boric acid to the 2-methylimidazole is in the range of 1:1 to 8:1, and the molar percentage of the template agent is 50% -80%;
the template agent is NaCl.
2. The method of claim 1, wherein the high temperature reaction temperature is 800-1600 ℃.
3. Hexagonal boron nitride porous microspheres obtained by the process according to claim 1 or 2, wherein the hexagonal boron nitride porous microspheres have a particle size of 1-6 μm and a pore size of up to 600nm.
4. A hexagonal boron nitride porous microsphere according to claim 3, having a purity of >99%, a whiteness of up to 104 and an oil absorption of up to 1064mL/100g.
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| CN102976293A (en) * | 2012-12-20 | 2013-03-20 | 沈阳大学 | Method for preparing high-crystallinity spherical hexagonal boron nitride powder body |
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| CN105980298A (en) * | 2014-02-12 | 2016-09-28 | 电化株式会社 | Spherical boron nitride particles and production method thereof |
| CN111377742A (en) * | 2020-03-23 | 2020-07-07 | 河北工业大学 | Template-free synthesis method of three-dimensional porous hexagonal boron nitride |
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| JPS6058273B2 (en) * | 1983-04-07 | 1985-12-19 | 昭和電工株式会社 | Modification method of cubic BN abrasive grains |
| US6306358B1 (en) * | 1998-06-02 | 2001-10-23 | Osamu Yamamoto | Crystalline turbostratic boron nitride powder and method for producing same |
| CN104684844B (en) * | 2012-09-28 | 2016-11-09 | 水岛合金铁株式会社 | Hydrophily/high oil-absorbing boron nitride powder and manufacture method thereof and cosmetic preparation |
| WO2015080899A1 (en) * | 2013-11-27 | 2015-06-04 | Board Of Trustees Of Northern Illinois University | Boron nitride and method of producing boron nitride |
| CN104058372B (en) * | 2014-07-09 | 2016-03-30 | 河北工业大学 | A kind of preparation method of hexagonal boron nitride nanosheet |
| JP7066169B2 (en) * | 2018-02-01 | 2022-05-13 | 国立研究開発法人物質・材料研究機構 | Method for Producing Cubic or Hexagonal Boron Nitride |
| CN108483414B (en) * | 2018-04-16 | 2019-12-10 | 武汉科技大学 | Low-temperature synthesis diamond boron nitride powder based on molten salt growth method and preparation method thereof |
| CN113353898A (en) * | 2021-04-06 | 2021-09-07 | 沈阳工业大学 | Microwave molten salt method for preparing hexagonal boron nitride |
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| CN102976293A (en) * | 2012-12-20 | 2013-03-20 | 沈阳大学 | Method for preparing high-crystallinity spherical hexagonal boron nitride powder body |
| CN102976294A (en) * | 2012-12-20 | 2013-03-20 | 沈阳大学 | Method for preparing high-crystallinity spherical hexagonal boron nitride powder body by surface active agent mode |
| CN105980298A (en) * | 2014-02-12 | 2016-09-28 | 电化株式会社 | Spherical boron nitride particles and production method thereof |
| CN111377742A (en) * | 2020-03-23 | 2020-07-07 | 河北工业大学 | Template-free synthesis method of three-dimensional porous hexagonal boron nitride |
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