A special phenyl silicone oil for cosmetics and preparation method thereof

Abstract

The present invention provides a special phenyl silicone oil for cosmetics and a preparation method thereof, which belongs to the technical field of materials chemistry. The preparation method comprises: using raw materials including trimethyltriphenylcyclotrisiloxane, diphenyl double head, and solid catalyst to carry out prepolymerization and ring-opening copolymerization to obtain a copolymer; vacuum distilling the copolymer to obtain a special phenyl silicone oil; wherein the solid catalyst is obtained by the following steps: preparing a magnetic core material containing an anionic polymer; coating the magnetic core material with an organic matter containing a cationic polymer to obtain magnetic particles; using raw materials including magnetic particles to prepare a porous silica carrier; and loading ammonium dihydrogen phosphate on the porous silica carrier to obtain an acidic solid catalyst. The present invention uses a catalyst with good catalytic effect and easy recovery and recycling, thereby improving the environmental friendliness of phenyl silicone oil production and reducing production costs.

Description

Technical Field

[0001] The present invention relates to the technical field of daily chemical materials, and in particular to a special phenyl silicone oil for cosmetics and a preparation method thereof. Background Art

[0002] Phenyl silicone oil has good compatibility with cosmetic ingredients, is relatively stable to heat and ultraviolet rays, and has a unique glossiness. Therefore, it is widely used in related fields of cosmetic products.

[0003] In cosmetics, phenyl silicone oil can be used as an emulsifier and stabilizer. It can form a uniform emulsion between the water and oil phases, help maintain the stability of cosmetics, make cosmetics easier to apply, maintain the uniformity and texture of the product, and lock in moisture, effectively preventing skin moisture loss.

[0004] The preparation of phenyl silicone oil usually uses silane monomer and end-capping agent as raw materials, adds acid catalyst, and obtains the finished product through prepolymerization and ring-opening copolymerization reaction.

[0005] Acid catalysts can generally be inorganic or organic acids. Acid catalysts can be either liquid or solid. Liquid acid catalysts participate in chemical reactions in molecular form, making them difficult to separate from the product in industrial production and making continuous use difficult. In contrast, the active sites of solid acids are attached to the solid material, allowing for direct separation by filtration after the reaction and reuse. Therefore, solid acid catalysts are a preferred choice for the preparation of phenyl silicone oils.

[0006] Solid acid catalysts are required to have a high specific surface area, a three-dimensional interconnected pore structure, and a high density of active sites. A high density of active sites can increase the reaction rate, while a high specific surface area can provide a suitable spatial structure for the diffusion of reactants and the conduct of the reaction. In addition, solid catalysts also need to be easy to recycle and recycle. Solid catalysts that meet the above conditions help to increase the reaction rate and yield, reduce production costs, and improve the environmental friendliness of the production process.

[0007] Porous solid catalysts in powder or granular form typically have a large specific surface area and high mass transfer rates, resulting in high catalytic activity. To facilitate the recovery of powder or granular solid catalysts, existing technologies have opted to imbue the solid catalyst with magnetic properties by loading it with magnetic materials containing iron, thereby enabling separation of the solid catalyst from the reaction system.

[0008] For example, Chinese patent with authorization publication number CN113663710B provides a method for preparing a magnetic solid acid catalyst, and Chinese patent with authorization publication number CN114100634B provides a method for preparing a magnetic multi-component catalyst.

[0009] The above analysis demonstrates that powdered or granular porous solid catalysts that can be separated and recovered using magnetic response properties offer numerous technical advantages. However, the prior art, including the aforementioned patents, suffers from a limitation in that it can only achieve a blended composite of magnetic materials and catalysts within a carrier material, but struggles to achieve a dense coating of the magnetic material. This is particularly true for porous materials, where the need for dense coating of the magnetic material conflicts with the need to increase the carrier's specific surface area and porosity.

[0010] Although the addition of magnetic materials has no effect on some reaction systems, for the preparation process of phenyl silicone oil, the transition metal iron element contained in the magnetic material will interfere with the ring-opening copolymerization reaction of phenyl silicone oil.

[0011] Therefore, how to use magnetic materials to improve the recovery convenience of powdered or granular porous solid catalysts, and avoid exposing the magnetic materials to the reaction system to affect the ring-opening copolymerization reaction required for the preparation of phenylene silicone oil, and ensure the reaction yield, is a technical problem that technicians in this field need to solve. Summary of the Invention

[0012] One of the problems solved by the present invention is how to provide an acidic solid catalyst for the production of phenyl silicone oil that is easy to recycle and has a long service life, thereby reducing the production cost of phenyl silicone oil and improving the environmental friendliness of its production process.

[0013] To solve at least one of the above problems, the present invention provides a method for preparing a special phenyl silicone oil for cosmetics, the preparation method comprising:

[0014] S110, performing a prepolymerization reaction using raw materials including trimethyltriphenylcyclotrisiloxane, diphenyl double end cap, and a solid catalyst to obtain a prepolymer;

[0015] S120, adding diphenyl double end cap to the prepolymer again to carry out a ring-opening copolymerization reaction to obtain a copolymer;

[0016] S130, distilling the copolymer under reduced pressure to remove low-boiling-point substances to obtain special phenyl silicone oil;

[0017] Wherein, the solid catalyst is prepared by the following steps:

[0018] S210, preparing a magnetic core material containing anionic polymer;

[0019] S220, coating the surface of the magnetic core material with an organic substance containing a cationic polymer to obtain magnetic particles;

[0020] S230, preparing a porous silica carrier using a raw material including magnetic particles;

[0021] S240, loading ammonium dihydrogen phosphate on a porous silica carrier to obtain an acidic solid catalyst.

[0022] In any of the above technical solutions, the mass ratio is trimethyltriphenylcyclotrisiloxane:diphenyl double head:solid catalyst = (80-100): (2-6): (1-3).

[0023] In any of the above technical solutions, S110 specifically includes:

[0024] S111, adding dehydrated trimethyltriphenylcyclotrisiloxane and a solid catalyst to the first reaction device, heating to 50° C. to 60° C. and stirring evenly;

[0025] S112. Add 40% to 60% of the total amount of diphenyl double-end, raise the temperature to 70° C. to 75° C., and stir and react for 2 h to 3 h to perform a prepolymerization reaction to obtain a prepolymer.

[0026] In any of the above technical solutions, S120 specifically includes:

[0027] S121. Under inert gas protection, transfer the prepolymer and solid catalyst to a second reaction apparatus, add the remaining diphenyl double end cap, raise the temperature to 100° C. to 105° C., and stir the reaction for 3 to 4 hours to allow the prepolymer to undergo a ring-opening copolymerization reaction;

[0028] S122. After the ring-opening copolymerization reaction is completed, the pH value is adjusted to neutral, and the solid catalyst is recovered to obtain a copolymer.

[0029] In any of the above technical solutions, S130 specifically includes:

[0030] S131, allowing the copolymer to stand and separate into layers;

[0031] S132. Distill the copolymer under reduced pressure at 200° C. to 210° C. under a vacuum condition of -0.08 MPa to -0.05 MPa to remove low-boiling point substances, thereby obtaining a special phenyl silicone oil.

[0032] In any of the above technical solutions, S210 specifically includes:

[0033] S211. Evenly mix aminopropyltriethoxysilane, xanthan gum, ethanol, and water in a mass ratio of aminopropyltriethoxysilane:xanthan gum:ethanol:water = (1-2):(2-4):(5-10):100, gradually add ferric nitrate and stir until the pH reaches 5 to obtain an iron salt solution;

[0034] S212, 1,4-diaminobenzene is mixed uniformly in ethanol in a mass ratio of 1,4-diaminobenzene: sodium hydroxide: ethanol: water = (2-4): (8-10): (10-20): 100, sodium hydroxide and water are added and mixed uniformly again to obtain an alkaline solution;

[0035] S213, adding an alkaline solution dropwise to the iron salt solution and continuing stirring until the pH value reaches 9. After the addition is complete, stirring the iron salt solution at a temperature of 85° C. to 95° C. and evaporating it in a water bath to dryness to obtain an iron sol;

[0036] S214. The iron sol is fed into a reactor and subjected to a hydrothermal treatment for 2.5 to 3 hours under a pressure of 3 MPa to 5 MPa and a temperature of 180°C to 190°C. After the hydrothermal treatment, the solid matter is separated and filtered, washed, and dried to obtain a magnetic core material.

[0037] In any of the above technical solutions, S220 specifically includes:

[0038] S221. Mix 1,4-benzenedicaldehyde, azo(2-amidinopropane) dihydrochloride, methacryloyloxyethyltrimethylammonium chloride, acrylamide, and water in a mass ratio of ammonium sulfate: 1,4-benzenedicaldehyde: azo(2-amidinopropane) dihydrochloride: methacryloyloxyethyltrimethylammonium chloride: acrylamide: magnetic core material: water = (0.2-0.3): (0.4-1.2): (1-2): (6-8): (6-8): (20-25): 100, heat to 45° C. to 50° C., add ammonium persulfate and the magnetic core material, maintain the temperature, and mix again to obtain a first mixture;

[0039] S222, heating the first mixture to 55° C. to 60° C., and irradiating the first mixture with ultraviolet light for 1.5 to 2 hours using an ultraviolet light source with a wavelength of 254 to 365 nm and a power of 600 to 800 W while simultaneously stirring and keeping the mixture warm;

[0040] S223. After the heating treatment and the ultraviolet irradiation treatment are completed, the solid matter is separated and filtered, washed, and dried to obtain magnetic particles.

[0041] In any of the above technical solutions, S230 specifically includes:

[0042] S231. Mix magnetic particles, ethyl orthosilicate, ethanol, and water in a mass ratio of magnetic particles: ethyl orthosilicate: ethanol: water = (10-15): (30-50): (30-50): 100 to obtain a silicon source suspension.

[0043] S232, by adding sulfuric acid aqueous solution to the silicon source suspension and stirring, adjusting the pH value of the silicon source suspension to 4 to 5, and continuing to stir for 2.5 hours to 3 hours to obtain a silica sol containing magnetic particles;

[0044] S233, soaking the silica sol in anhydrous ethanol and aging it for 20 to 24 hours to obtain a silica gel containing magnetic particles;

[0045] S234. Using carbon dioxide as a medium, supercritically drying the silica gel at a temperature of 31° C. to 33° C. and a pressure of 7.3 MPa to 7.5 MPa to obtain a porous carrier.

[0046] In any of the above technical solutions, S240 specifically includes:

[0047] S241. Dissolve ammonium dihydrogen phosphate in water at a mass ratio of ammonium dihydrogen phosphate: porous carrier: water = (25-30): (30-35): 100, add the porous carrier, and disperse uniformly by ultrasonication to obtain a catalyst suspension;

[0048] S242, evaporating the catalyst suspension to dryness, washing and drying the solid matter to obtain a solid catalyst.

[0049] The present invention also provides a special phenyl silicone oil for cosmetics, which is obtained by using the preparation method of any of the above schemes.

[0050] Beneficial effects

[0051] The present invention provides a method for preparing a special phenyl silicone oil for cosmetics. The preparation method uses raw materials including trimethyltriphenylcyclotrisiloxane, diphenyl double head, and solid catalyst to carry out prepolymerization and ring-opening copolymerization to obtain a copolymer, and then the copolymer is distilled under reduced pressure to obtain a special phenyl silicone oil. For the purpose of reducing the production cost of phenyl silicone oil and improving the environmental friendliness of its production process, the present invention uses a solid catalyst to promote and catalyze the above-mentioned reaction. In order to facilitate the recovery and recycling of the solid catalyst, the present invention prepares a catalyst with magnetic response characteristics, and by coating an organic film layer on the surface of the magnetic response material, the magnetic response material is prevented from contacting the reaction system and interfering with the reaction. Through electrostatic adsorption, the film layer containing the cationic polymer is evenly and densely coated on the surface of the magnetic core material containing the anionic polymer. In addition, the present invention loads the coated magnetic response material and catalyst on a porous carrier, and utilizes the characteristics of the porous carrier with a high specific surface area and rich pore structure to load the magnetic response material and catalyst, thereby ensuring catalytic activity, reaction efficiency, and the convenience of catalyst recovery. The porous silica support can maintain good mechanical strength and chemical stability in an acidic environment, making it an excellent acidic catalyst support. Thus, the present invention, by using an improved solid catalyst, improves the environmental friendliness of the phenyl silicone oil preparation process and reduces its production cost. DETAILED DESCRIPTION

[0052] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, the following is a detailed description of the specific embodiments of the present invention.

[0053] Unless otherwise specified, the reagents and raw materials used in the present invention can be purchased from commercial sources. Experimental methods in the following examples where specific conditions are not specified were performed according to conventional methods and conditions, or selected according to the product specifications.

[0054] The present invention provides a method for preparing a special phenyl silicone oil for use in cosmetics, the preparation method comprising:

[0055] S110, performing a prepolymerization reaction using raw materials including trimethyltriphenylcyclotrisiloxane, diphenyl double end cap, and a solid catalyst to obtain a prepolymer;

[0056] S120, adding diphenyl double end cap to the prepolymer again to carry out a ring-opening copolymerization reaction to obtain a copolymer;

[0057] S130, distilling the copolymer under reduced pressure to remove low-boiling-point substances to obtain special phenyl silicone oil.

[0058] In the above steps, diphenyl bis(phenyl)ene capping agent is used as an end-capping agent. The solid catalyst is specifically an acidic solid catalyst. The mass ratio of trimethyltriphenylcyclotrisiloxane: diphenyl bis(phenyl)ene capping agent: solid catalyst is (80-100): (2-6): (1-3).

[0059] The purpose of S110 is to allow the raw materials to undergo a prepolymerization reaction, and S110 specifically includes:

[0060] S111, adding dehydrated trimethyltriphenylcyclotrisiloxane and a solid catalyst to the first reaction device, heating to 50° C. to 60° C. and stirring evenly;

[0061] S112. Add 40% to 60% of the total amount of diphenyl double-end, raise the temperature to 70° C. to 75° C., and stir and react for 2 h to 3 h to perform a prepolymerization reaction to obtain a prepolymer.

[0062] After the prepolymerization reaction is completed, the raw materials need to be subjected to a ring-opening copolymerization reaction, and S120 specifically includes:

[0063] S121. Under inert gas protection, transfer the prepolymer and solid catalyst to a second reaction apparatus, add the remaining diphenyl double end cap, raise the temperature to 100° C. to 105° C., and stir the reaction for 3 to 4 hours to allow the prepolymer to undergo a ring-opening copolymerization reaction;

[0064] S122. After the ring-opening copolymerization reaction is completed, the pH value is adjusted to neutral, and the solid catalyst is recovered to obtain a copolymer.

[0065] After the ring-opening copolymerization reaction is completed, vacuum distillation is required to remove low-boiling point substances. S130 specifically includes:

[0066] S131, allowing the copolymer to stand and separate into layers;

[0067] S132. Distill the copolymer under reduced pressure at 200° C. to 210° C. under a vacuum condition of -0.08 MPa to -0.05 MPa to remove low-boiling point substances, thereby obtaining a special phenyl silicone oil.

[0068] By the above steps, phenyl silicone oil can be obtained. The present invention adopts a porous acidic solid catalyst to promote the reaction. In order to facilitate the recovery and recycling of the catalyst adopted in the above reaction, the present invention loads the magnetic response material in the porous solid catalyst. In order to avoid the magnetic response material from contacting the reaction system, the present invention carries out an organic coating process on the magnetic core material that plays the magnetic response effect. Thus, a catalyst that is easy to recycle and has good catalytic activity can be obtained, thereby improving the environmental friendliness of the production of phenyl silicone oil and reducing its production cost.

[0069] Specifically, the solid catalyst is prepared by the following steps:

[0070] S210, preparing a magnetic core material containing anionic polymer;

[0071] S220, coating the surface of the magnetic core material with an organic substance containing a cationic polymer to obtain magnetic particles;

[0072] S230, preparing a porous silica carrier using a raw material including magnetic particles;

[0073] S240, loading ammonium dihydrogen phosphate on a porous silica carrier to obtain an acidic solid catalyst.

[0074] In the above steps, powders or particles of, for example, ferric oxide and / or ferrosoferric oxide can be used as the magnetic core material. The magnetic core material can be commercially purchased, or it can be obtained from raw materials such as ferric nitrate or ferric sulfate by methods such as sol-gel and hydrothermal methods. It is understood that nanoscale magnetic core materials with uniform particle size distribution prepared by methods such as sol-gel and hydrothermal methods have good magnetic response properties and are the preferred embodiment of the present invention.

[0075] In some embodiments of the present invention, S210 specifically includes:

[0076] S211. Evenly mix aminopropyltriethoxysilane, xanthan gum, ethanol, and water in a mass ratio of aminopropyltriethoxysilane:xanthan gum:ethanol:water = (1-2):(2-4):(5-10):100, gradually add ferric nitrate and stir until the pH reaches 5 to obtain an iron salt solution;

[0077] S212, 1,4-diaminobenzene is mixed uniformly in ethanol in a mass ratio of 1,4-diaminobenzene: sodium hydroxide: ethanol: water = (2-4): (8-10): (10-20): 100, sodium hydroxide and water are added and mixed uniformly again to obtain an alkaline solution;

[0078] S213, adding an alkaline solution dropwise to the iron salt solution and continuing stirring until the pH value reaches 9. After the addition is complete, stirring the iron salt solution at a temperature of 85° C. to 95° C. and evaporating it in a water bath to dryness to obtain an iron sol;

[0079] S214. The iron sol is fed into a reactor and subjected to a hydrothermal treatment for 2.5 to 3 hours under a pressure of 3 MPa to 5 MPa and a temperature of 180°C to 190°C. After the hydrothermal treatment, the solid matter is separated and filtered, washed, and dried to obtain a magnetic core material.

[0080] In the above steps, S211 utilizes water-soluble ferric nitrate and water as the solvent to prepare an iron salt solution. Aminopropyltriethoxysilane is used as a silane coupling agent to reduce the surface energy of the subsequently formed magnetic core material and enhance its coupling with the organic matter. Xanthan gum, as an anionic modifier, is also used to enhance the tightness and uniformity of the bond between the organic matter in the magnetic core material. In water, some of the carboxyl groups in xanthan gum lose hydrogen ions, becoming anionic groups, thus possessing anionic properties. Compared to other anionic polymers such as sodium alginate and sodium hydroxymethyl cellulose, the present invention uses xanthan gum because it is relatively insensitive to pH. Its wide pH adaptability makes xanthan gum's viscosity virtually unaffected within the pH range of 5 to 10, exhibiting a high degree of stability. Even under extreme conditions of pH values ​​below 4 and above 11, the viscosity of xanthan gum changes only slightly, allowing xanthan gum to be evenly dispersed in the iron salt solution and iron sol. In an alkaline environment, the iron ions in the iron salt solution combine with hydroxyl groups to form iron hydroxide colloids. The purpose of S212 is to prepare an alkaline solution for reaction with the iron salt solution. It should be noted that alkaline solutions such as aqueous sodium hydroxide solution, aqueous potassium hydroxide solution, and aqueous ammonia can all be used to react with the iron salt solution. The present invention uses a mixed solution of sodium hydroxide in ethanol and water, to which 1,4-diaminobenzene is added. The purpose of using ethanol in S212 is to dissolve the weakly alkaline 1,4-diaminobenzene so that it can be evenly dispersed in the mixed solution of ethanol and water. The purpose of S213 is to prepare an iron hydroxide sol containing xanthan gum and 1,4-diaminobenzene. After obtaining this sol, the present invention converts the iron hydroxide into iron oxide through a hydrothermal method under heating and pressure. While it is understood that heat treatment above 500°C can also achieve the conversion of iron hydroxide into iron oxide, the present invention selects a hydrothermal treatment at no more than 200°C to protect the xanthan gum and 1,4-diaminobenzene. In summary, through the above steps, iron oxide doped with xanthan gum and 1,4-diaminobenzene can be obtained, which the present invention uses as the magnetic core material.

[0081] The purpose of S220 is to coat the surface of the magnetic core material with an organic material containing a cationic polymer, thereby preventing the magnetic core material from coming into contact with the phenyl silicone oil reaction system. It is understood that a uniform, dense, and relatively thin film layer is the preferred embodiment of the present invention. To achieve a uniform, dense organic film layer, the magnetic core material can be coated with an organic polymer, or an organic monomer can be mixed with the magnetic core material and coated by initiating a polymerization reaction.

[0082] In some embodiments of the present invention, S220 specifically includes:

[0083] S221. Mix 1,4-benzenedicaldehyde, azo(2-amidinopropane) dihydrochloride, methacryloyloxyethyltrimethylammonium chloride, acrylamide, and water in a mass ratio of ammonium sulfate: 1,4-benzenedicaldehyde: azo(2-amidinopropane) dihydrochloride: methacryloyloxyethyltrimethylammonium chloride: acrylamide: magnetic core material: water = (0.2-0.3): (0.4-1.2): (1-2): (6-8): (6-8): (20-25): 100, heat to 45° C. to 50° C., add ammonium persulfate and the magnetic core material, maintain the temperature, and mix again to obtain a first mixture;

[0084] S222, heating the first mixture to 55° C. to 60° C., and irradiating the first mixture with ultraviolet light for 1.5 to 2 hours using an ultraviolet light source with a wavelength of 254 to 365 nm and a power of 600 to 800 W while stirring and keeping the mixture warm;

[0085] S223. After the heating treatment and the ultraviolet irradiation treatment are completed, the solid matter is separated and filtered, washed, and dried to obtain magnetic particles.

[0086] In the above steps, the purpose of S221 is to mix the ammonium persulfate initiator, methacryloyloxyethyl trimethylammonium chloride with trimethylammonium groups, and acrylamide with the magnetic core material in an aqueous solvent system to obtain a first mixture in a suspended state. Under heating conditions of 55°C to 60°C, the above monomers undergo a polymerization reaction, and the positively charged amino groups in the above organic matter chemically adsorb with the anionic xanthan gum dopant in the magnetic core material, thereby uniformly coating the polymer on the surface of the magnetic core material. In addition, methacryloyloxyethyl trimethylammonium chloride generates free radicals under ultraviolet light irradiation and the action of azo (2-amidinopropane) dihydrochloride photoinitiator, thereby catalyzing the condensation reaction of the amino group of 1,4-diaminobenzene in the magnetic core material with the aldehyde group of 1,4-benzenedicarboxaldehyde to form an imide group. The imide group with good stability can realize the chemical bond between iron oxide and organic matter, improve the uniformity and density of the organic coating on the magnetic core material, and improve the chemical stability and thermal stability of the organic film layer, ensuring that under the ring-opening equilibrium reaction conditions for preparing phenyl silicone oil, the organic film layer on the surface of the magnetic core material will not be destroyed, thereby avoiding contact between the magnetic core material and the reaction system.

[0087] The purpose of S230 is to load the magnetic particles onto a porous carrier. It is understood that porous inorganic materials such as porous ceramics, attapulgite, montmorillonite, hydroxyapatite, halloysite, and zeolite can all serve as solid catalyst supports. The magnetic particles can be loaded onto the porous carrier by mechanically mixing the magnetic particles with the porous carrier, granulating and forming the particles, and then sintering them. Alternatively, the magnetic particles can be deposited or filled into the pores of the porous carrier in a liquid phase through ultrasound, stirring, wet chemistry, and other methods.

[0088] In some embodiments of the present invention, S230 specifically includes:

[0089] S231. Mix magnetic particles, ethyl orthosilicate, ethanol, and water in a mass ratio of magnetic particles: ethyl orthosilicate: ethanol: water = (10-15): (30-50): (30-50): 100 to obtain a silicon source suspension.

[0090] S232, by adding sulfuric acid aqueous solution to the silicon source suspension and stirring, adjusting the pH value of the silicon source suspension to 4 to 5, and continuing to stir for 2.5 hours to 3 hours to obtain a silica sol containing magnetic particles;

[0091] S233, soaking the silica sol in anhydrous ethanol and aging it for 20 to 24 hours to obtain a silica gel containing magnetic particles;

[0092] S234. Using carbon dioxide as a medium, supercritically drying the silica gel at a temperature of 31° C. to 33° C. and a pressure of 7.3 MPa to 7.5 MPa to obtain a porous carrier.

[0093] In the above steps, the purpose of S231 is to uniformly disperse the magnetic particles in the organosilicon source solution, obtaining a suspended magnetic particle-silicon source suspension. Using sulfuric acid as a catalyst, a sol-gel method can be used to obtain a silica gel mixed with magnetic particles. Supercritical drying can then yield a porous silica structure. Thus, the above steps can produce a porous silica carrier uniformly loaded with magnetic particles.

[0094] In some embodiments of the present invention, S240 specifically includes:

[0095] S241. Dissolve ammonium dihydrogen phosphate in water at a mass ratio of ammonium dihydrogen phosphate: porous carrier: water = (25-30): (30-35): 100, add the porous carrier, and disperse uniformly by ultrasonication to obtain a catalyst suspension;

[0096] S242, evaporating the catalyst suspension to dryness, washing and drying the solid matter to obtain a solid catalyst.

[0097] In the above steps, ammonium dihydrogen phosphate is used as a catalyst, which is loaded on a porous silica carrier containing magnetic particles as a catalyst for driving the catalytic reaction in the preparation process of phenyl silicone oil.

[0098] Example 1

[0099] In this example, a series of solid catalyst samples were prepared. The raw material ratios were shown in Table 1. The preparation process was as follows:

[0100] S1. KH550 aminopropyltriethoxysilane, xanthan gum, anhydrous ethanol, and deionized water were mixed in a beaker, and ferric nitrate was gradually added while magnetically stirring at 300 rpm / min until the pH reached 5 to obtain an iron salt solution.

[0101] S2. Mix 1,4-diaminobenzene and anhydrous ethanol in a beaker, add sodium hydroxide and deionized water, and mix again to obtain an alkaline solution;

[0102] S3, adding alkaline solution dropwise to the iron salt solution and continuously stirring with magnetic stirring at a speed of 180 rpm / min until the pH value is 9, and after the addition is completed, the iron salt solution is continuously stirred with magnetic stirring at a temperature of 90° C. and evaporated to dryness in a water bath to obtain iron sol;

[0103] S4, feeding the iron sol into a reactor, and performing a hydrothermal treatment for 2.5 hours under a pressure of 3.8 MPa and a temperature of 180° C. After the hydrothermal treatment, separating and filtering the solids, washing them once with water, and drying them with hot air at 110° C. to obtain a magnetic core material;

[0104] S5. Mix 1,4-benzenedicarboxaldehyde, azo(2-amidinopropane) dihydrochloride, methacryloyloxyethyltrimethylammonium chloride, acrylamide, and deionized water in a beaker, heat to 45° C., add ammonium persulfate and a magnetic core material, keep warm, and homogenize by ultrasonication at a power of 400 W for 15 minutes to obtain a first mixture;

[0105] S6. Heating the first mixture to 60° C. and irradiating the first mixture with ultraviolet light for 2 hours using an ultraviolet light source with a wavelength of 254 nm and a power of 600 W while simultaneously stirring and keeping the mixture warm;

[0106] S7, separating and filtering the solids, washing with acetone twice, washing with water twice, and drying with hot air at 110° C. to obtain magnetic particles;

[0107] S8. Mix the magnetic particles, tetraethyl orthosilicate, anhydrous ethanol, and deionized water in a beaker to obtain a silicon source suspension;

[0108] S9, by adding 12% sulfuric acid aqueous solution to the silicon source suspension and stirring, the pH value of the silicon source suspension is adjusted to 4, and the magnetic stirring is continued at a speed of 200 rpm / min for 2.5 hours to obtain a silica sol containing magnetic particles;

[0109] S10, soaking the silica sol in anhydrous ethanol and aging it for 24 hours to obtain a silica gel containing magnetic particles;

[0110] S11, using carbon dioxide as a medium, supercritical drying the silica gel at a temperature of 32° C. and a pressure of 7.4 MPa to obtain a porous carrier;

[0111] S12, dissolving ammonium dihydrogen phosphate in deionized water, adding a porous carrier, and ultrasonically treating at a power of 400 W for 30 minutes to obtain a catalyst suspension;

[0112] S13, evaporating the catalyst suspension to dryness, washing the solid twice with water and drying it with hot air at 110° C. to obtain a solid catalyst.

[0113] Table 1

[0114]

[0115] Comparative Example 1

[0116] In this comparative example, solid catalyst sample 5 was prepared. The raw material ratio is shown in Table 2, and the preparation process is as follows:

[0117] S1. KH550 aminopropyltriethoxysilane, xanthan gum, anhydrous ethanol, and deionized water were mixed in a beaker, and ferric nitrate was gradually added while magnetically stirring at 300 rpm / min until the pH reached 5 to obtain an iron salt solution.

[0118] S2. Mix sodium hydroxide and deionized water to prepare an 8 wt % alkaline solution;

[0119] S3, adding alkaline solution dropwise to the iron salt solution and continuously stirring with magnetic stirring at a speed of 180 rpm / min until the pH value is 9, and after the addition is completed, the iron salt solution is continuously stirred with magnetic stirring at a temperature of 90° C. and evaporated to dryness in a water bath to obtain iron sol;

[0120] S4, feeding the iron sol into a reactor, and performing a hydrothermal treatment for 2.5 hours under a pressure of 3.8 MPa and a temperature of 180° C. After the hydrothermal treatment, separating and filtering the solids, washing them once with water, and drying them with hot air at 110° C. to obtain a magnetic core material;

[0121] S5. Mix azo(2-amidinopropane) dihydrochloride, methacryloyloxyethyltrimethylammonium chloride, acrylamide, and deionized water in a beaker, heat to 45° C., add ammonium persulfate and a magnetic core material, keep warm, and homogenize using ultrasound at a power of 400 W for 15 minutes to obtain a first mixture;

[0122] S6. Heat the first mixture to 60° C., continue magnetic stirring at 400 rpm / min, and keep warm for 2 h;

[0123] S7 to S13 are the same as those in the first embodiment.

[0124] Table 2

[0125]

[0126] Comparative Example 2

[0127] In this comparative example, solid catalyst sample 6 was prepared. Its raw material ratio was the same as that of sample 1 in Example 1. Its preparation process was as follows:

[0128] S1 to S5 are the same as in Example 1;

[0129] S6. Heat the first mixture to 60° C., continue magnetic stirring at 400 rpm / min, and keep warm for 2 h;

[0130] S7 to S13 are the same as those in the first embodiment.

[0131] Example 2

[0132] In this embodiment, a series of phenyl silicone oil samples were prepared. The raw material ratios are shown in Table 3, and the preparation process is as follows:

[0133] S1. Add dehydrated trimethyltriphenylcyclotrisiloxane and solid catalyst to the first reaction device, heat to 55° C. and stir evenly;

[0134] S2, adding 50% of the total amount of diphenyl double end cap, heating to 75 ° C and stirring for 2.5 hours to perform a prepolymerization reaction to obtain a prepolymer;

[0135] S3. Under nitrogen protection, the prepolymer and solid catalyst were transferred to the second reaction device, the remaining 50% of the diphenyl double-end was added, the temperature was raised to 100° C., and the mixture was stirred and reacted for 3 hours to allow the prepolymer to undergo a ring-opening copolymerization reaction;

[0136] S4. After the ring-opening copolymerization reaction is completed, the pH value is adjusted to 7, and the solid catalyst is recovered to obtain a copolymer;

[0137] S5, allowing the copolymer to stand for 3 hours and separate into layers;

[0138] S6, distilling the copolymer under reduced pressure at 205° C. under a vacuum condition of −0.08 MPa to remove low-boiling-point substances, thereby obtaining a special phenyl silicone oil;

[0139] The performance test parameters of the phenyl silicone oil sample prepared in this example are shown in Table 3.

[0140] Table 3

[0141]

[0142] Accelerated testing

[0143] In order to measure the recycling performance of the catalyst, the present invention further implements an accelerated test, and the test method of the accelerated test is as follows:

[0144] S1, according to the mass ratio of trimethyltriphenylcyclotrisiloxane: diphenyl double head: solid catalyst = 100:5:3, respectively, using solid catalyst samples 1 to 6 as solid catalysts, and using the steps of Example 2 to prepare phenyl silicone oil;

[0145] S2. After each reaction, the solid catalyst is recovered by magnetic separation, and the same solid catalyst sample is used to repeat the above reaction step S1 20 times;

[0146] S3, for the last reaction in the cyclic execution step of above-mentioned S2, the phenyl silicone oil yield of this reaction is tested, and the test results are shown in Table 4.

[0147] Table 4

[0148]

[0149] Although the present invention is disclosed as above, the present invention is not limited thereto. Any person skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention should be based on the scope defined by the claims.

Claims

1. A method for preparing special phenyl silicone oil for cosmetics, characterized in that: The preparation method comprises: S110, performing a prepolymerization reaction using raw materials including trimethyltriphenylcyclotrisiloxane, diphenyl double end cap, and a solid catalyst to obtain a prepolymer; S120, adding the diphenyl double end to the prepolymer again to carry out a ring-opening copolymerization reaction to obtain a copolymer; S130, distilling the copolymer under reduced pressure to remove low-boiling-point substances to obtain the special phenyl silicone oil; Wherein, the solid catalyst is prepared by the following steps: S210, preparing a magnetic core material containing anionic polymer; S220, coating the surface of the magnetic core material with an organic substance containing a cationic polymer to obtain magnetic particles; by coating the surface of the magnetic core material with an organic film layer, the magnetic core material is prevented from contacting the reaction system; and by electrostatic adsorption, the film layer containing the cationic polymer is evenly and densely coated on the surface of the magnetic core material containing the anionic polymer; S230, preparing a porous silica carrier using a raw material including the magnetic particles; S240, loading ammonium dihydrogen phosphate on the porous silica support to obtain the acidic solid catalyst; S210 specifically includes: S211, uniformly mixing the aminopropyltriethoxysilane, the xanthan gum, the ethanol, and the water in a mass ratio of aminopropyltriethoxysilane:xanthan gum:ethanol:water = (1-2):(2-4):(5-10):100, gradually adding ferric nitrate and stirring until the pH reaches 5, to obtain an iron salt solution; S212, mixing the 1,4-diaminobenzene in the ethanol in a mass ratio of 1,4-diaminobenzene: sodium hydroxide: ethanol: water = (2-4): (8-10): (10-20): 100, adding the sodium hydroxide and the water and mixing again to obtain an alkaline solution; S213, adding the alkaline solution dropwise to the iron salt solution and continuously stirring until the pH value reaches 9, and after the addition is complete, stirring the iron salt solution at a temperature of 85° C. to 95° C. and evaporating it in a water bath to obtain an iron sol; S214, feeding the iron sol into a reactor, and performing a hydrothermal treatment for 2.5 hours to 3 hours under a pressure of 3 MPa to 5 MPa and a temperature of 180° C. to 190° C. After the hydrothermal treatment, separating and filtering the solids, washing, and drying to obtain the magnetic core material; S220 specifically includes: S221. Evenly mix the 1,4-benzenedicaldehyde, the azo(2-amidinopropane) dihydrochloride, the methacryloyloxyethyltrimethylammonium chloride, the acrylamide, and water in a mass ratio of ammonium sulfate:1,4-benzenedicaldehyde:azo(2-amidinopropane) dihydrochloride:methacryloyloxyethyltrimethylammonium chloride:acrylamide:magnetic core material:water=(0.2-0.3):(0.4-1.2):(1-2):(6-8):(6-8):(20-25):100, heat to 45° C. to 50° C., add the ammonium sulfate and the magnetic core material, maintain the temperature, and evenly mix again to obtain a first mixture; S222, heating the first mixture to 55° C. to 60° C., and irradiating the first mixture with ultraviolet light for 1.5 to 2 hours using an ultraviolet light source with a wavelength of 254 to 365 nm and a power of 600 to 800 W while stirring and keeping the mixture warm; S223, after the heating treatment and the ultraviolet irradiation treatment are completed, the solid matter is separated and filtered, washed, and dried to obtain the magnetic particles.

2. The preparation method according to claim 1, characterized in that Calculated by mass ratio, trimethyltriphenylcyclotrisiloxane: diphenyl double head: solid catalyst = (80-100): (2-6): (1-3).

3. The preparation method according to claim 1, characterized in that S110 specifically includes: S111, adding the dehydrated trimethyltriphenylcyclotrisiloxane and the solid catalyst to the first reaction device, heating to 50° C. to 60° C. and stirring evenly; S112, adding the diphenyl double head in an amount of 40% to 60% of the total addition amount, raising the temperature to 70° C. to 75° C. and stirring the mixture for 2 h to 3 h to carry out the prepolymerization reaction and obtain the prepolymer.

4. The preparation method according to claim 1, characterized in that S120 specifically includes: S121. Under the protection of an inert gas, the prepolymer and the solid catalyst are transferred to a second reaction apparatus, the remaining diphenyl double end cap is added, the temperature is raised to 100° C. to 105° C., and the mixture is stirred and reacted for 3 to 4 hours to allow the prepolymer to undergo the ring-opening copolymerization reaction; S122. After the ring-opening copolymerization reaction is completed, the pH value is adjusted to neutral, and the solid catalyst is recovered to obtain the copolymer.

5. The preparation method according to claim 1, characterized in that S130 specifically includes: S131, allowing the copolymer to stand and separate; S132, distilling the copolymer under reduced pressure at 200° C. to 210° C. under a vacuum condition of -0.08 to -0.05 MPa to remove low-boiling point substances, thereby obtaining the special phenyl silicone oil.

6. The preparation method according to claim 1, characterized in that S230 specifically includes: S231, uniformly mixing the magnetic particles, the ethyl orthosilicate, the ethanol, and the water in a mass ratio of magnetic particles: ethyl orthosilicate: ethanol: water = (10-15): (30-50): (30-50): 100 to obtain a silicon source suspension; S232, by adding sulfuric acid aqueous solution to the silicon source suspension and stirring, adjusting the pH value of the silicon source suspension to 4 to 5, and continuing stirring for 2.5 hours to 3 hours to obtain a silica sol containing the magnetic particles; S233, soaking the silica sol in anhydrous ethanol and aging it for 20 to 24 hours to obtain a silica gel containing the magnetic particles; S234. Using carbon dioxide as a medium, supercritically drying the silica gel at a temperature of 31° C. to 33° C. and a pressure of 7.3 MPa to 7.5 MPa to obtain the porous carrier.

7. The preparation method according to claim 1, characterized in that S240 specifically includes: S241, dissolving the ammonium dihydrogen phosphate in the water at a mass ratio of ammonium dihydrogen phosphate: porous carrier: water = (25-30): (30-35): 100, adding the porous carrier, and uniformly dispersing by ultrasonication to obtain a catalyst suspension; S242, evaporating the catalyst suspension to dryness, washing and drying the solid matter to obtain the solid catalyst.

8. A special phenyl silicone oil for cosmetics, characterized in that: The special phenyl silicone oil is obtained by the preparation method according to any one of claims 1 to 7.

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