A quaternary ammonium oil-control composite powder, a preparation method thereof and application thereof in oil-control cosmetics

Abstract

The application relates to a kind of quaternary ammonium oil control composite powder and its preparation method and application in oil control cosmetics.The application belongs to the field of cosmetics.The application solves the problems of existing oil control cosmetics in adsorbing human body secreted oil while also adsorbing oily nutrient ingredients in cosmetics and short makeup time.The quaternary ammonium oil control composite powder of the application is obtained by modifying and compounding porous minerals.The surface of the quaternary ammonium oil control composite powder prepared in the experiment is rough and has mesopores, which can selectively adsorb unsaturated fatty acids and fix them in the porous structure of the quaternary ammonium oil control composite powder through the electrostatic interaction between the quaternary ammonium salt grafted on the porous minerals and carboxylate groups.The application also has the characteristics of rapidly flocculating and solidifying oil, which can make makeup more durable.The quaternary ammonium oil control composite powder of the application also shows hydrophobic and hydrophilic properties, and suitable quaternary ammonium oil control composite powder can be selected according to the needs of different cosmetics when used.

Description

Technical Field

[0001] This invention belongs to the field of cosmetics, specifically relating to a quaternized oil-controlling composite powder, its preparation method, and its application in oil-controlling cosmetics. Background Technology

[0002] Human skin naturally secretes oil, especially in summer. Excessive sebum can cause makeup to smudge and affect its finish, thus requiring oil-controlling properties in cosmetics. Commonly used oil-controlling cosmetics utilize porous powders, such as porous silica and porous polymethyl methacrylate. However, these porous powders have limitations. One reason is their lack of selective absorption; while absorbing sebum, they also absorb oily nutrients from the cosmetics. Another reason is their inability to flocculate and solidify oil, resulting in short-lasting makeup effects.

[0003] Therefore, developing an oil-controlling powder that can selectively absorb unsaturated fatty acids (the main oil component of human sweat) and has good makeup-holding effect without safety risks is of great significance for oil-controlling cosmetics. Summary of the Invention

[0004] The purpose of this invention is to solve the problems of existing oil-control cosmetics, which absorb both sebum secreted by the body and oily nutrients in the cosmetic, and have a short makeup-holding time. This invention provides a quaternized oil-control composite powder, its preparation method, and its application in oil-control cosmetics.

[0005] The technical solution of the present invention is as follows:

[0006] One objective of this invention is to provide a method for preparing a quaternized oil-controlling composite powder, wherein the method includes:

[0007] S1: Add porous minerals, surfactants, dispersants and water to the reactor, stir evenly, add metal salts, continue stirring, then add ammonium bicarbonate aqueous solution dropwise, continue the reaction, then wash and filter twice, dry, calcine in a muffle furnace to obtain modified mineral composite powder;

[0008] S2: Disperse the modified mineral composite powder of S1 in toluene, add silane coupling agent and polymerization inhibitor, after the reaction is complete, filter and wash, then filter and dry to obtain modified mineral composite powder with double bonds.

[0009] S3: Under nitrogen protection, the modified mineral composite powder with double bonds in S2, the polymer monomer and toluene are mixed and stirred evenly. Then, an initiator is added to react. After the reaction is completed, the mixture is washed, filtered and dried to obtain the polymer-modified mineral composite powder.

[0010] S4: Under stirring conditions, S3 polymer-modified mineral composite powder and toluene are mixed and dropped into a haloalkanes toluene solution to carry out a quaternization reaction. After the reaction is completed, the mixture is filtered, washed, dried, and ball-milled at 30 rpm to obtain quaternized oil-controlling composite powder.

[0011] Further specifying, the porous mineral in S1 is diatomaceous earth or zeolite, the surfactant is hexadecyltrimethylammonium bromide, sodium dodecylbenzenesulfonate, or Tween, the dispersant is polyethylene glycol 200 or polyethylene glycol 400, and the metal salt is zinc sulfate, aluminum sulfate, zinc nitrate, aluminum nitrate, zinc acetate, or zinc chloride. The mass ratio of surfactant to porous mineral in S1 is 1-5:100, the mass ratio of dispersant to porous mineral is 1-5:100, the mass ratio of metal salt to porous mineral is 1:1-10, and the molar ratio of ammonium bicarbonate to metal salt is 1-8: 1; The silane coupling agent of S2 is vinyltrimethoxysilane, vinyltriethoxysilane, vinyl-tris(2-methoxyethoxy)silane or γ-(methacryloyloxy)propyltrimethoxysilane, and the polymerization inhibitor is catechol. The mass ratio of modified mineral composite powder of S2 to silane coupling agent is 5-20:1, and the mass ratio of polymerization inhibitor to silane coupling agent is 1:50-200. The halogenated hydrocarbon of S4 is chlorooctadecane, chlorohexadecane, bromohexadecane or bromooctadecane. The mass ratio of polymer modified mineral composite powder of S4 to halogenated hydrocarbon is 20:1-4.

[0012] Further specified, diatomaceous earth has a silica content greater than 75%, a particle size of 5-50 μm, and a porosity of 30-150 μm. 2 / g; zeolite particle size is 5-50μm, porosity is 150-300μm 2 / g.

[0013] Further specifying, the monomers of S3 are a mixture of divinyl polydimethylsiloxane, vinyl-terminated polyoxyethylene ether, and dimethylaminoethyl methacrylate, the initiator is an azo initiator, the mass ratio of the modified mineral composite powder with double bonds in S3 to the monomers is 5-20:1, and the mass ratio of the initiator to the monomers is 1:10-50.

[0014] Further specified, the azo initiator is azobisisobutyronitrile or azobisisoheptanenitrile, and the mass ratio of divinyl polydimethylsiloxane, vinyl-terminated polyoxyethylene ether and dimethylaminoethyl methacrylate is 0.1-2:0.1-5:1.

[0015] Further specified: S1 stirring time 0.5-2h, continued stirring time 0.5-2h, continued reaction temperature 50-80℃, continued reaction time 5-10h, drying temperature 80-120℃, drying time 6-12h, calcination temperature 350-500℃, calcination time 2-6h; S2 reaction temperature 50-100℃, reaction time 4-8h, drying temperature 50-80℃, drying time 3-6h; S3 stirring time 0.1-2h, reaction temperature 50-80℃, reaction time 4-8h; S4 reaction temperature 80-100℃, reaction time 4-8h.

[0016] The second objective of this invention is to provide a hydrophobic quaternized oil-controlling composite powder prepared by the above preparation method, wherein the content of divinyl polydimethylsiloxane in the polymer monomer of the hydrophobic quaternized oil-controlling composite powder is ≥20wt.%.

[0017] The third objective of this invention is to provide a hydrophilic quaternized oil-controlling composite powder prepared by the above preparation method, wherein the content of divinyl polydimethylsiloxane in the polymer monomer of the hydrophilic quaternized oil-controlling composite powder is <20 wt.%.

[0018] The fourth objective of this invention is to provide an application of the above-mentioned hydrophobic quaternized oil-controlling composite powder in oil-soluble oil-controlling cosmetics.

[0019] The fifth objective of this invention is to provide an application of the above-mentioned hydrophilic quaternized oil-controlling composite powder in water-soluble oil-controlling cosmetics.

[0020] Compared with the prior art, the specific advantages of the present invention are as follows:

[0021] The quaternized oil-controlling composite powder provided by this invention is suitable for the directional adsorption of oils. This invention uses porous inorganic minerals as a carrier, grafting quaternized polymers onto the porous minerals to form a structurally stable quaternized oil-controlling composite powder. This composite powder fully utilizes the porous structure of the minerals and the electrostatic interaction between the quaternary ammonium salt and carboxyl groups to adsorb and fix unsaturated fatty acids secreted by the human body within the porous structure of the minerals, and rapidly flocculates and solidifies the unsaturated fatty acids. Furthermore, by modifying the structure of the comonomer, the hydrophilicity and hydrophobicity of the quaternized oil-controlling composite powder can be controlled, thereby meeting the application needs of various oil-controlling cosmetics. Attached Figure Description

[0022] Figure 1 The infrared spectrum of the quaternized oil-controlling composite powder prepared in Example 1;

[0023] Figure 2 This is a scanning electron microscope image of the quaternized oil-controlling composite powder prepared in Example 1;

[0024] Figure 3The image shows the contact angle test results of the quaternized oil-controlling composite powder prepared in Example 1. Detailed Implementation

[0025] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.

[0026] Unless otherwise specified, the experimental methods used in the following examples are conventional methods. Unless otherwise specified, the materials, reagents, methods, and instruments used are all conventional materials, reagents, methods, and instruments in the art, and can be obtained commercially by those skilled in the art.

[0027] The terms “comprising,” “including,” “having,” “containing,” or any other variations thereof, as used in the following embodiments, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that includes the listed elements is not necessarily limited to those elements, but may include other elements not expressly listed or elements inherent to such a composition, step, method, article, or apparatus.

[0028] When a quantity, concentration, or other value or parameter is expressed as a range, a preferred range, or a range defined by a series of upper and lower preferred values, this should be understood as specifically disclosing all ranges formed by any pair of any upper or preferred value with any lower or preferred value, regardless of whether the range is disclosed individually. For example, when the range “1 to 5” is disclosed, the described range should be interpreted as including ranges “1 to 4”, “1 to 3”, “1 to 2”, “1 to 2 and 4 to 5”, “1 to 3 and 5”, etc. When numerical ranges are described herein, unless otherwise stated, the range is intended to include its endpoints and all integers and fractions within that range. In this specification and claims, range definitions may be combined and / or interchanged, unless otherwise stated, these ranges include all subranges contained therein.

[0029] The indefinite articles “a” and “an” preceding an element or component of this invention do not impose any limitation on the quantity (i.e., number of times) of the element or component. Therefore, “an” or “a” should be interpreted as including one or at least one, and the singular form of an element or component also includes the plural form, unless the quantity clearly refers only to the singular form.

[0030] In this invention, "an embodiment" or "embodiment" refers to a specific feature, structure, or characteristic that may be included in at least one implementation of the invention. The phrase "in one embodiment" appearing in different places in this specification does not necessarily refer to the same embodiment, nor is it a single or selective embodiment that excludes other embodiments.

[0031] The endpoints and any values ​​of the ranges disclosed in this invention are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0032] Example 1:

[0033] S1: Weigh 50g of diatomaceous earth with a particle size of 10μm, 2g of hexadecyltrimethylammonium bromide, 2g of polyethylene glycol 400 and 500mL of water and add them to the reactor and stir for 1h. Weigh 25g of zinc sulfate and add it to the reactor and stir for 1h. Then weigh 25g of ammonium bicarbonate and dissolve it in 50g of water to form an ammonium bicarbonate aqueous solution. Under stirring conditions, add the ammonium bicarbonate aqueous solution dropwise into the reactor. After the addition is complete, react at 60℃ for 6h. Then filter and wash. Add the obtained filter cake and 500mL of anhydrous ethanol to the reactor and stir for 1h. Then filter again. Dry the obtained solid powder in an oven at 100℃ for 8h. Then calcine it in a muffle furnace at 400℃ for 4h to obtain modified diatomaceous earth composite powder.

[0034] S2: Weigh 50g of modified diatomaceous earth composite powder and 500mL of toluene and add them to the reactor. Then add 5g of vinyltrimethoxysilane and 0.05g of catechol. React at 80℃ for 6h. Then filter, wash with ethanol, filter again, and dry the sample in an oven at 60℃ for 5h to obtain modified diatomaceous earth composite powder with double bonds.

[0035] S3: Under nitrogen protection, 50g of modified diatomaceous earth composite powder with double bonds, 1g of divinyl polydimethylsiloxane, 2g of vinyl-terminated polyoxyethylene ether, 2g of dimethylaminoethyl methacrylate and 500g of toluene were added to a reactor and stirred for 0.5h. Then 0.24g of azobisisobutyronitrile was added and the reaction was continued at 60℃ for 6h. After filtration, washing and drying, polymer-modified diatomaceous earth composite powder was obtained.

[0036] S4: Weigh 50g of polymer-modified diatomaceous earth composite powder and 500g of toluene and add them to the reactor. Weigh 3.6g of chlorooctadecane and dissolve it in 10mL of toluene to form a chlorooctadecane toluene solution. Under stirring conditions, add the chlorooctadecane toluene solution dropwise to the reactor and reflux at 90℃ for 6h to carry out the quaternization reaction. After the reaction is completed, filter, wash, dry, and then ball mill at 30rpm to obtain the quaternized oil-controlling composite powder.

[0037] Example 2:

[0038] S1: Weigh 50g of diatomaceous earth with a particle size of 20μm, 2g of hexadecyltrimethylammonium bromide, 2g of polyethylene glycol 400 and 500mL of water and add them to the reactor and stir for 1h. Weigh 25g of zinc sulfate and add it to the reactor and stir for 1h. Then weigh 30g of ammonium bicarbonate and dissolve it in 50g of water to form an ammonium bicarbonate aqueous solution. Under stirring conditions, add the ammonium bicarbonate aqueous solution dropwise to the reactor. After the addition is complete, react at 60℃ for 6h, then filter and wash. Add the obtained filter cake and 500ml of anhydrous ethanol to the reactor and stir for 1h, then filter again. Dry the obtained solid powder in an oven at 100℃ for 8h, and then calcine it in a muffle furnace at 400℃ for 4h to obtain modified diatomaceous earth composite powder.

[0039] S2: Weigh 50g of modified diatomaceous earth composite powder and 500ml of toluene and add them to the reactor. Then add 3.0g of γ-(methacryloyloxy)propyltrimethoxysilane and 0.05g of catechol. React at 80℃ for 6h. Then filter, wash with ethanol, filter again, and dry the obtained sample in an oven at 60℃ for 5h to obtain modified diatomaceous earth composite powder with double bonds.

[0040] S3: Under nitrogen protection, 50g of modified diatomaceous earth composite powder with double bonds, 1g of divinyl polydimethylsiloxane, 7.5g of vinyl-terminated polyoxyethylene ether, 1.5g of dimethylaminoethyl methacrylate and 500g of toluene were added to a reactor and mechanically stirred for 0.5h. Then, 0.24g of azobisisobutyronitrile was added, and the reaction was continued at 60℃ for 6h. After filtration, washing and drying, polymer-modified diatomaceous earth composite powder was obtained.

[0041] S4: Weigh 50g of polymer-modified diatomaceous earth composite powder and 500g of toluene and add them to the reactor. Weigh 4g of octadecane and dissolve it in 10ml of toluene to form a toluene solution of octadecane. Under stirring, add the toluene solution of octadecane dropwise to the reactor and reflux at 90℃ for 6h to carry out the quaternization reaction. After the reaction is completed, filter, wash, dry, and then ball mill at 30rpm to obtain the quaternized oil-controlling composite powder.

[0042] Example 3:

[0043] S1: Weigh 50g of diatomaceous earth with a particle size of 50μm, 2g of hexadecyltrimethylammonium bromide, 2g of polyethylene glycol 400 and 500mL of water and add them to the reactor and stir for 1h. Weigh 40g of zinc sulfate and add it to the reactor and stir for 1h. Then weigh 50g of ammonium bicarbonate and dissolve it in 50g of water to form an ammonium bicarbonate aqueous solution. Under stirring conditions, add the ammonium bicarbonate aqueous solution dropwise to the reactor. After the addition is complete, react at 60℃ for 6h, then filter and wash. Add the obtained filter cake and 500ml of anhydrous ethanol to the reactor and stir for 1h, then filter again. Dry the obtained solid powder in an oven at 100℃ for 10h, and then calcine it in a muffle furnace at 400℃ for 4h to obtain modified diatomaceous earth composite powder.

[0044] S2: Weigh 50g of modified diatomaceous earth composite powder and 500ml of toluene and add them to the reactor. Then add 8.0g of γ-(methacryloyloxy)propyltrimethoxysilane and 0.05g of catechol. React at 80℃ for 6h. Then filter, wash with ethanol, filter again, and dry the obtained sample in an oven at 60℃ for 5h to obtain modified diatomaceous earth composite powder with double bonds.

[0045] S3: Under nitrogen protection, 50g of modified diatomaceous earth composite powder with double bonds, 3.5g of divinyl polydimethylsiloxane, 0.5g of vinyl-terminated polyoxyethylene ether, 4g of dimethylaminoethyl methacrylate and 500g of toluene were added to a reactor and mechanically stirred for 0.5h. Then, 0.24g of azobisisobutyronitrile was added and the reaction was continued at 60℃ for 6h. The reaction solution was then filtered, washed and dried to obtain polymer-modified diatomaceous earth composite powder.

[0046] S4: Weigh 50g of polymer-modified diatomaceous earth composite powder and 500g of toluene and add them to the reactor. Weigh 4g of hexadecane and dissolve it in 10ml of toluene to form a hexadecane-toluene solution. Under stirring, add the hexadecane-toluene solution dropwise to the reactor and reflux at 90℃ for 6h to carry out the quaternization reaction. After the reaction is complete, filter, wash, dry, and then ball mill at 30rpm to obtain the quaternized oil-controlling composite powder.

[0047] Example 4:

[0048] S1: Weigh 50g of diatomaceous earth with a particle size of 10μm, 2g of hexadecyltrimethylammonium bromide, 2g of polyethylene glycol 400 and 500mL of water and add them to the reactor and stir for 1h. Weigh 6g of zinc sulfate and add it to the reactor and stir for 1h. Then weigh 8g of ammonium bicarbonate and dissolve it in 50g of water to form an ammonium bicarbonate aqueous solution. Under stirring conditions, add the ammonium bicarbonate aqueous solution dropwise into the reactor. After the addition is complete, react at 60℃ for 6h. Then filter and wash. Add the obtained filter cake and 500ml of anhydrous ethanol to the reactor and stir for 1h. Then filter again. Dry the obtained solid powder in an oven at 100℃ for 10h. Then calcine it in a muffle furnace at 400℃ for 4h to obtain modified diatomaceous earth composite powder.

[0049] S2: Weigh 50g of modified diatomaceous earth composite powder and 500ml of toluene and add them to the reactor. Then add 3.5g of γ-(methacryloyloxy)propyltriethoxysilane and 0.05g of catechol. React at 80℃ for 6h. Then filter, wash with ethanol, filter again, and dry the obtained sample in an oven at 60℃ for 5h to obtain modified diatomaceous earth composite powder with double bonds.

[0050] S3: Under nitrogen protection, 50g of modified diatomaceous earth composite powder with double bonds, 0.5g of divinyl polydimethylsiloxane, 0.5g of vinyl-terminated polyoxyethylene ether, 5g of dimethylaminoethyl methacrylate and 500g of toluene were added to a reactor and mechanically stirred for 0.5h. Then, 0.24g of azobisisobutyronitrile was added and the reaction was continued at 60℃ for 6h. After filtration, washing and drying, polymer-modified diatomaceous earth composite powder was obtained.

[0051] S4: Weigh 50g of polymer-modified diatomaceous earth composite powder and 500g of toluene and add them to the reactor. Weigh 6.5g of hexadecane and dissolve it in 10ml of toluene to form a hexadecane toluene solution. Under stirring, add the hexadecane toluene solution dropwise into the reactor and reflux at 90℃ for 6h to carry out the quaternization reaction. After the reaction is completed, filter, wash, dry, and then ball mill at 30rpm to obtain the quaternized oil-controlling composite powder.

[0052] Example 5:

[0053] S1: Weigh 50g of zeolite powder with a particle size of 10μm, 2g of hexadecyltrimethylammonium bromide, 2g of polyethylene glycol 400 and 500mL of water and add them to the reactor and stir for 1h. Weigh 25g of zinc nitrate and add it to the reactor and stir for 1h. Then weigh 30g of ammonium bicarbonate and dissolve it in 50g of water to form an ammonium bicarbonate aqueous solution. Under stirring conditions, add the ammonium bicarbonate aqueous solution dropwise to the reactor. After the addition is complete, react at 60℃ for 6h. Then filter and wash. Add the obtained filter cake and 500ml of anhydrous ethanol to the reactor and stir for 1h. Then filter again. Dry the obtained solid powder in an oven at 100℃ for 8h. Then calcine it in a muffle furnace at 400℃ for 4h to obtain modified zeolite composite powder.

[0054] S2: Weigh 50g of modified zeolite composite powder and 500ml of toluene and add them to the reactor. Then add 3.0g of vinyl-tris(2-methoxyethoxy)silane and 0.05g of catechol. React at 80℃ for 6h. Then filter, wash with ethanol, filter again, and dry the obtained sample in an oven at 60℃ for 5h to obtain modified zeolite composite powder with double bonds.

[0055] S3: Under nitrogen protection, 50g of modified zeolite composite powder with double bonds, 1g of divinyl polydimethylsiloxane, 7.5g of vinyl-terminated polyoxyethylene ether, 1.5g of dimethylaminoethyl methacrylate and 500g of toluene were added to a reactor and mechanically stirred for 0.5h. Then, 0.24g of azobisisobutyronitrile was added and the reaction was continued at 60℃ for 6h. After filtration, washing and drying, polymer-modified zeolite composite powder was obtained.

[0056] S4: Weigh 50g of polymer-modified zeolite composite powder and 500g of toluene and add them to the reactor. Weigh 4g of bromooctadecane and dissolve it in 10ml of toluene to form a bromooctadecane toluene solution. Under stirring conditions, add the bromooctadecane toluene solution dropwise into the reactor and reflux at 90℃ for 6h to carry out the quaternization reaction. After the reaction is completed, filter, wash, dry, and then ball mill at 30rpm to obtain the quaternized oil-controlling composite powder.

[0057] Example 6:

[0058] S1: Weigh 50g of zeolite powder with a particle size of 20μm, 2g of hexadecyltrimethylammonium bromide, 2g of polyethylene glycol 400 and 500mL of water and add them to the reactor and stir for 1h. Weigh 40g of aluminum sulfate and add it to the reactor and stir for 1h. Then weigh 60g of ammonium bicarbonate and dissolve it in 50g of water to form an ammonium bicarbonate aqueous solution. Under stirring conditions, add the ammonium bicarbonate aqueous solution dropwise to the reactor. After the addition is complete, react at 60℃ for 6h. Then filter and wash. Add the obtained filter cake and 500ml of anhydrous ethanol to the reactor and stir for 1h. Then filter again. Dry the obtained solid powder in an oven at 100℃ for 8h. Then calcine it in a muffle furnace at 400℃ for 4h to obtain modified zeolite composite powder.

[0059] S2: Weigh 50g of modified zeolite composite powder and 500ml of toluene and add them to the reactor. Then add 8.0g of γ-(methacryloyloxy)propyltrimethoxysilane and 0.05g of catechol. React at 80℃ for 6h. Then filter, wash with ethanol, filter again, and dry the obtained sample in an oven at 60℃ for 5h to obtain modified zeolite composite powder with double bonds.

[0060] S3: Under nitrogen protection, 50g of modified zeolite composite powder with double bonds, 3.5g of divinyl polydimethylsiloxane, 0.5g of vinyl-terminated polyoxyethylene ether, 4g of dimethylaminoethyl methacrylate and 500g of toluene were added to a reactor and mechanically stirred for 0.5h. Then, 0.24g of azobisisobutyronitrile was added and the reaction was continued at 60℃ for 6h. After filtration, washing and drying, polymer-modified zeolite composite powder was obtained.

[0061] S4: Weigh 50g of polymer-modified zeolite composite powder and 500g of toluene and add them to the reactor. Weigh 4g of hexadecane and dissolve it in 10ml of toluene to form a hexadecane-toluene solution. Under stirring, add the hexadecane-toluene solution dropwise into the reactor and reflux at 90℃ for 6h to carry out the quaternization reaction. After the reaction is complete, filter, wash, dry, and then ball mill at 30rpm to obtain the quaternized oil-controlling composite powder.

[0062] Comparative Example 1:

[0063] The difference between Comparative Example 1 and Example 1 is that step 1 is omitted, and 5g of ZnO and 35g of diatomaceous earth with a particle size of 10μm are blended together to replace the modified diatomaceous earth composite powder.

[0064] Comparative Example 2:

[0065] The difference between Comparative Example 2 and Example 1 is that step 4 is omitted and quaternization treatment is not performed.

[0066] Comparative Example 3:

[0067] The difference between Comparative Example 3 and Example 1 is that 10μm solid silica microspheres were used instead of diatomaceous earth.

[0068] Figure 1 The image shows the infrared spectrum of the quaternized oil-controlling composite powder prepared in Example 1. It can be seen from the image that at 2800 cm⁻¹... -1 The presence of characteristic peaks of quaternary ammonium groups indicates that the polymer on the surface of the composite powder has been successfully quaternized.

[0069] Figure 2The image shows a scanning electron microscope (SEM) image of the quaternized oil-controlling composite powder prepared in Example 1. The image reveals that the quaternized oil-controlling composite powder has a rough surface and mesopores, demonstrating that the series of operations in this experiment did not block the porous structure of the diatomaceous earth itself. The electrostatic interaction between the quaternary ammonium salt grafted onto the diatomaceous earth and the carboxyl group can be utilized to adsorb and fix unsaturated fatty acids secreted by the human body into the porous structure of the diatomaceous earth, achieving the effect of oil adsorption.

[0070] Oil absorption test:

[0071] 4g of the final oil-controlling powder was weighed from Examples 1-6 and Comparative Examples 1-3, and mixed evenly with 40g of oleic acid and 40g of silicone oil (10cst). The mixture was allowed to stand at room temperature for 18h, then 100ml of petroleum ether was added, and the mixture was mixed for 30min. The mixture was then rinsed and filtered. The residue was calcined at 500℃ to determine the heat loss. The results are detailed in Table 1.

[0072] Flocculation and solidification test:

[0073] 2g of the final oil-controlling powder was weighed from Examples 1-6 and Comparative Examples 1-3, and 6g of water and 12g of oleic acid were added to each. The mixture was placed in a glass bottle to prepare simulated artificial sebum. The bottle was shaken vigorously up and down more than 20 times. Then it was left to stand. The glass bottle was gently inverted to observe its fluidity and the solidification time of the system was recorded. The results are detailed in Table 1.

[0074] Water absorption test:

[0075] 4g of the final oil-controlling powder was weighed from Examples 1-6 and Comparative Examples 1-3, and mixed evenly with 40g of water. The mixture was left to stand at room temperature for 18h, then filtered. The residue was calcined at 500℃ to determine the heat loss. The results are detailed in Table 1.

[0076] Table 1: Experimental results of oil absorption, contact angle and flocculation solidification of Examples 1-6 and Comparative Examples 1-3

[0077]

[0078]

[0079] As shown in Table 1, the quaternized oil-controlling composite powder prepared by this experimental method has high adsorption capacity for oleic acid and can quickly flocculate and solidify artificial sebum, achieving effective oil control and makeup maintenance in cosmetics. Moreover, the hydrophilicity and hydrophobicity of the surface of the quaternized oil-controlling composite powder prepared by this experimental method can be controlled by adjusting the proportion of the three polymer monomers added. When the quaternized oil-controlling composite powder exhibits hydrophilicity, it can be added to water-soluble oil-controlling cosmetics; when it exhibits hydrophobicity, it can be added to non-water-soluble oil-controlling cosmetics. Thus, the quaternized oil-controlling composite powder prepared in this experiment can meet different application scenarios.

[0080] Selective adsorption test:

[0081] Weigh 0.1g of different types of oils and dissolve them in 100mL of n-hexane, mixing thoroughly. Weigh 0.5g of the quaternized oil-controlling composite powder prepared in Example 1 into an Erlenmeyer flask, add 50mL of n-hexane containing oils, seal the flask, shake for 1 hour, filter, and then analyze by GCMS. The results are shown in Table 2.

[0082] Table 2: Selective adsorption test results of the quaternized oil-controlling composite powder prepared in Example 1

[0083] Types of oils Adsorption capacity (%) Oleic acid 46.1 White oil 1.1 silicone oil 1.6 Caprylic / Capric Triglyceride 2.1 squalane 0.4

[0084] As shown in Table 2, the quaternized oil-controlling composite powder prepared by this invention can selectively adsorb oleic acid secreted by the human body, without absorbing skin-protecting oily substances such as white oil, silicone oil, caprylic / capric triglycerides, and squalane added to cosmetics. This indicates that the experiment successfully prepared an oil-controlling composite powder with selective adsorption, which is of great significance to the development and production of oil-controlling composite powder cosmetics.

[0085] The above description is merely a preferred embodiment of the present invention. These specific embodiments are different implementations based on the overall concept of the present invention, and the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A method for preparing a quaternized oil-controlling composite powder, characterized in that, The method described: S1: Add porous minerals, surfactants, dispersants and water to the reactor, stir evenly, add metal salts, continue stirring, then add ammonium bicarbonate aqueous solution dropwise, continue the reaction, then wash and filter twice, dry, calcine in a muffle furnace to obtain modified mineral composite powder; S2: Disperse the modified mineral composite powder of S1 in toluene, add silane coupling agent and polymerization inhibitor, after the reaction is complete, filter and wash, then filter and dry to obtain modified mineral composite powder with double bonds. S3: Under nitrogen protection, the modified mineral composite powder with double bonds in S2, the polymer monomer and toluene are mixed and stirred evenly. Then, an initiator is added to react. After the reaction is completed, the mixture is washed, filtered and dried to obtain the polymer-modified mineral composite powder. S4: Under stirring conditions, S3 polymer-modified mineral composite powder and toluene are mixed and added dropwise to a haloalkanes toluene solution to carry out a quaternization reaction. After the reaction is completed, the mixture is filtered, washed, dried, and ball-milled at 30 rpm to obtain quaternized oil-controlling composite powder. The porous minerals are diatomite or zeolite, and the metal salts are zinc sulfate, aluminum sulfate, zinc nitrate, aluminum nitrate, zinc acetate, or zinc chloride.

2. The method according to claim 1, characterized in that, The surfactant in S1 is hexadecyltrimethylammonium bromide, sodium dodecylbenzenesulfonate, or Tween; the dispersant is polyethylene glycol 200 or polyethylene glycol 400; the mass ratio of surfactant to porous mineral in S1 is 1-5:100; the mass ratio of dispersant to porous mineral is 1-5:100; the mass ratio of metal salt to porous mineral is 1:1-10; and the molar ratio of ammonium bicarbonate to metal salt is 1-8:

1. The silane coupling agent in S2 is vinyltrimethoxysilane, ethyl... The polymer is modified with alkenyltriethoxysilane, vinyl-tris[2-methoxyethoxy]silane or γ-methacryloyloxypropyltrimethoxysilane, and the polymerization inhibitor is catechol. The mass ratio of the modified mineral composite powder to the silane coupling agent in S2 is 5-20:1, and the mass ratio of the polymerization inhibitor to the silane coupling agent is 1:50-200. The halogenated hydrocarbon in S4 is chlorooctadecane, chlorohexadecane, bromohexadecane or bromooctadecane, and the mass ratio of the polymer modified mineral composite powder to the halogenated hydrocarbon in S4 is 20:1-4.

3. The method according to claim 2, characterized in that, Diatomaceous earth has a silica content greater than 75%, a particle size of 5-50 μm, and a porosity of 30-150 μm. 2 / g; zeolite particle size is 5-50μm, porosity is 150-300μm 2 / g.

4. The method according to claim 1, characterized in that, The monomers of S3 are a mixture of divinyl polydimethylsiloxane, vinyl-terminated polyoxyethylene ether, and dimethylaminoethyl methacrylate. The initiator is an azo initiator. The mass ratio of S3 modified mineral composite powder with double bonds to the monomers is 5-20:1, and the mass ratio of initiator to monomers is 1:10-50.

5. The method according to claim 4, characterized in that, The azo initiator is azobisisobutyronitrile or azobisisoheptanenitrile, and the mass ratio of divinyl polydimethylsiloxane, vinyl-terminated polyoxyethylene ether and dimethylaminoethyl methacrylate is 0.1-2:0.1-5:

1.

6. The method according to claim 1, characterized in that, S1: Stirring time 0.5-2h, continued stirring time 0.5-2h, continued reaction temperature 50-80℃, continued reaction time 5-10h, drying temperature 80-120℃, drying time 6-12h, calcination temperature 350-500℃, calcination time 2-6h; S2: Reaction temperature 50-100℃, reaction time 4-8h, drying temperature 50-80℃, drying time 3-6h; S3: Stirring time 0.1-2h, reaction temperature 50-80℃, reaction time 4-8h; S4: Reaction temperature 80-100℃, reaction time 4-8h.

7. The hydrophobic quaternized oil-controlling composite powder prepared by the method according to any one of claims 1-6, characterized in that, The content of divinyl polydimethylsiloxane in the polymer monomer is ≥20 wt.%.

8. The hydrophilic quaternized oil-controlling composite powder prepared by the method according to any one of claims 1-6, characterized in that, The content of divinylpolydimethylsiloxane in the polymer monomer is <20 wt.

9. The application of the hydrophobic quaternized oil-controlling composite powder according to claim 7 in oil-soluble cosmetics.

10. The application of the hydrophilic quaternized oil-controlling composite powder according to claim 8 in water-soluble cosmetics.

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