A hydrophilically modified silicone wax and methods of making and using the same

Abstract

The application discloses a kind of hydrophilic modified silicone waxes and its preparation method and application.The hydrophilic modified silicone waxes has the structure shown in formula (1).The silicone wax of the application introduces hydroxyl-containing sulfonate structure side chain and polyether side chain on polysiloxane main chain, which improves the interfacial compatibility of silicone wax and water and further enhances the self-emulsifying ability of silicone wax, avoids the damage of excessive hydrophilicity to long-chain alkyl crystalline region, realizes the good balance of hydrophilicity and crystallinity, can obtain good water dispersibility while retaining the wax-like touch and structural strength of silicone wax, and is suitable for various daily-use products, can form a stable dispersion system in water under the condition of reducing additional emulsifier, and also considers the high storage stability and excellent use skin feel of product.

Description

Technical Field

[0001] This invention belongs to the field of organosilicon materials technology, specifically relating to a hydrophilic modified organosilicon wax, its preparation method, and its application. Background Technology

[0002] Organosilicon waxes are a class of waxy organosilicon materials obtained through long-chain alkyl modification. They are solid or semi-solid at room temperature, combining the smooth, slippery properties of silicone with the structural contribution capabilities of waxes. They are widely used in daily chemical products such as creams, lotions, and sunscreens. In practical applications, organosilicon waxes are often used in the form of aqueous emulsions or dispersions to facilitate compounding with other water-soluble ingredients. However, traditional organosilicon waxes are inherently hydrophobic and difficult to disperse directly in water, usually requiring the addition of emulsifiers and high shear forces to form a stable aqueous system. This not only increases the complexity and cost of formulations, but the choice of emulsifier can also adversely affect the sensory properties of the final product (such as stickiness and residue) or skin compatibility.

[0003] To improve the water dispersibility of silicone waxes, current technologies typically introduce hydrophilic segments into the polysiloxane molecular chain to reduce the interfacial tension between the silicone wax and water, making it easier to disperse in water and thus reducing reliance on external emulsifiers. However, the introduction of conventional hydrophilic segments usually disrupts the crystallinity of long-chain alkyl groups, leading to weakened crystallinity of the silicone wax. This makes it difficult for silicone waxes to provide sufficient cohesive structure and high-temperature stability in daily chemical compositions, resulting in problems such as water separation, layering, or softening of the paste during storage. Some studies have attempted to restore the structural support function of long-chain alkyl groups by increasing their carbon chain length or degree of substitution. However, this significantly affects the dispersibility of silicone waxes in aqueous matrices, reduces product spreadability, causes a greasy and dragging feel on the skin, and may even cause the precipitation of microcrystalline particles, resulting in a grainy and gritty feeling during application, severely impairing the skin experience. This contradiction makes achieving a silicone wax that balances excellent water dispersibility, high storage stability, and excellent skin feel technically challenging.

[0004] Therefore, developing a hydrophilic silicone wax that can achieve a better balance of overall performance will give it greater market competitiveness in the daily chemical products sector. Summary of the Invention

[0005] To overcome the shortcomings of the existing technology, the present invention aims to provide a hydrophilic modified silicone wax with excellent self-emulsifying properties, suitable for various daily chemical products, and capable of achieving high storage stability and excellent skin feel of the product while reducing the amount of added emulsifier.

[0006] The objective of this invention is achieved through the following technical solution: In a first aspect, the present invention provides a hydrophilic modified organosilicon wax having the structure shown in formula (1): Equation (1); Wherein, R1 is selected from alkylene groups having 2 to 10 carbon atoms; M represents an ether bond, ester bond, or single bond; X represents Na, Mg, or K; R2 is a hydrogen atom, an acetyl group, or an alkyl group having 1 to 4 carbon atoms; R3 is selected from alkyl groups having 18 to 30 carbon atoms; R4 and R5 are each independently selected from alkyl groups having 1 to 18 carbon atoms or unsaturated hydrocarbon groups. m and n are each independent integers from 0 to 15, and 0 < m + n < 30; a is an integer from 2 to 20 (for example, it can be any value among 2, 4, 6, 8, 10, 12, 14, 16, 18, 20 or a range between the two). b is an integer from 2 to 40 (for example, it can be any value among 2, 5, 8, 10, 12, 15, 18, 20, 22, 25, 28, 30, 32, 35, 38, 40 or a range between the two). c is an integer from 5 to 50 (for example, it can be any value among 5, 10, 15, 20, 25, 30, 35, 40, 45, 50 or a range between the two). d is an integer from 10 to 65 (for example, it can be any value among 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65 or a range between the two).

[0007] Preferably, R1 is selected from a straight-chain alkylene group having 3 to 6 carbon atoms; M represents an ether bond; and X represents Na.

[0008] Preferably, m and n are each an independent integer from 0 to 12 (for example, any value among 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 or a range between the two), and 5≤m+n≤24.

[0009] Preferably, the hydrophilic modified silicone wax of the present invention has a melting point of 30~55℃. The melting point is determined with reference to standard GB / T2539-2023.

[0010] Furthermore, the raw materials for preparing the hydrophilic modified silicone wax include: (a) Hydrogen-containing polysiloxanes; (b) Alkenyl epoxy compounds; (c) Allyl polyether; (d) α-olefins; (e) Platinum catalyst; (f) Bisulfite.

[0011] The hydrogen-containing polysiloxane has a siloxane backbone and silane-hydrogen bonds as shown in formula (1), providing sites for hydrosilylation reactions. Preferably, the number-average molecular weight of the hydrogen-containing polysiloxane is 1000~20000 g / mol, and the hydrogen content is 0.1%~1.6%. More preferably, the number-average molecular weight of the hydrogen-containing polysiloxane is 3000~15000 g / mol. The number-average molecular weight is determined according to standard GB / T 27843-2011.

[0012] The alkenyl epoxy compound is a compound whose molecular structure contains both an alkenyl group and a terminal epoxy group. Its alkenyl group can undergo a hydrosilylation reaction with the silane-hydrogen bond of a hydrogen-containing polysiloxane, introducing an epoxy-containing side chain into the siloxane backbone and providing an active site for subsequent ring-opening sulfonation reactions. Preferably, the alkenyl epoxy compound is selected from any one of allyl glycidyl ether, 2-methylallyl glycidyl ether, vinyl glycidyl ether, 1,2-epoxy-5-hexene, 1,2-epoxy-7-octene, 1,2-epoxy-9-decene, glycidyl methacrylate, and glycidyl acrylate.

[0013] The allyl polyether undergoes a hydrosilylation reaction with the alkenyl group and the hydrogen siloxane via a silane-hydrogen bond, introducing polyether side chains into the siloxane backbone. Preferably, the allyl polyether is selected from any one of allyl polyoxyethylene ether, allyl polyoxypropylene ether, and allyl polyoxyethylene-polyoxypropylene copolyether. Further, the number average molecular weight of the allyl polyether is preferably 100-1800 g / mol (e.g., any value from 100, 300, 500, 700, 900, 1100, 1300, 1500, 1800 or a range between the two), more preferably 200-1400 g / mol.

[0014] The α-olefin undergoes a hydrosilylation reaction with the alkenyl group and the hydrogen siloxane via a silane-hydrogen bond, introducing a long-chain alkyl side chain into the siloxane backbone. Further, the α-olefin is preferably at least one of straight-chain α-olefins having 18 to 30 carbon atoms; more preferably at least one of straight-chain α-olefins having 22 to 28 carbon atoms.

[0015] This invention introduces sulfonate groups by reacting a bisulfite salt with an epoxy group through a ring-opening sulfonation reaction. The bisulfite salt is selected from any one of sodium bisulfite, magnesium bisulfite, and potassium bisulfite.

[0016] Preferably, the platinum catalyst can be a conventional platinum-based catalyst such as a Karstedt catalyst, a Speier catalyst, or a MOF-modified Karstedt catalyst.

[0017] Furthermore, the molar ratio of the hydrogen-containing polysiloxane, alkenyl epoxy compound, allyl polyether, α-olefin, and platinum catalyst is 1:(2~20):(2~40):(5~50):(10) -7 ~10 -4 The preferred ratio is 1:(4~16):(5~20):(8~30):(10). -7 ~10 -4 ).

[0018] Furthermore, the molar ratio of the bisulfite to the alkenyl epoxy compound is 1:(0.8~1.0).

[0019] Furthermore, depending on the actual application requirements, a small amount of auxiliary components such as antioxidants, anti-yellowing agents, and dispersants can be added. The amount added is 0.01% to 0.5% of the total mass of the core components, preferably 0.05% to 0.3%, to further improve the product's resistance to yellowing and storage stability without affecting the product's core performance and reactivity.

[0020] Secondly, the present invention provides a method for preparing the aforementioned hydrophilic modified organosilicon wax, comprising the following steps: S1. Under inert gas protection, hydrogen-containing polysiloxane, alkenyl epoxy compound, allyl polyether, α-olefin and platinum catalyst are mixed and subjected to hydrosilylation reaction at 70~130℃ for 2~10 h to obtain epoxy-polyether-long-chain alkyl modified polysiloxane. S2. The product obtained in step S1 and the bisulfite are added to a mixture of propylene glycol methyl ether and water, and the ring-opening sulfonation reaction is carried out at 60~110℃ for 3~24h. After the reaction is completed, the mixture is filtered while hot, and the filtrate is distilled under reduced pressure to prepare the hydrophilic modified organosilicon wax.

[0021] Furthermore, the mass ratio of propylene glycol methyl ether to water is (25-35):1.

[0022] Furthermore, the amount of propylene glycol methyl ether and water used is 20%-50% of the total mass of the reactants.

[0023] Thirdly, this invention provides the application of the aforementioned hydrophilic modified silicone wax in cosmetics. These cosmetics include, for example, skincare products, makeup products, and hair care products.

[0024] Fourthly, the present invention provides a cosmetic composition comprising the hydrophilic modified silicone wax as described in the first aspect.

[0025] Compared with the prior art, the present invention has the following beneficial effects: The organosilicone wax of this invention, by rationally introducing hydroxysulfonate-containing side chains and polyether side chains onto the polysiloxane backbone, synergistically improves the interfacial compatibility between silicone wax and water and further enhances the self-emulsifying ability of silicone wax. It also avoids the damage to the long-chain alkyl crystalline regions caused by excessive hydrophilicity, achieving a good balance between hydrophilicity and crystallinity. This allows for good water dispersibility while retaining the waxy feel and structural strength of silicone wax. The hydrophilically modified organosilicone wax of this invention exhibits excellent self-emulsifying properties, forming a stable dispersion system in water with reduced external emulsifiers. It also ensures high storage stability and excellent skin feel, making it a promising product for the daily chemical industry. Attached Figure Description

[0026] Figure 1 The infrared spectrum of hydrophilic modified organosilicon wax AH1 in Example 1; Figure 2 The infrared spectrum of hydrophilic modified organosilicon wax AH2 in Example 2; Figure 3 The infrared spectrum of hydrophilic modified organosilicon wax AH3 in Example 3; Figure 4 The infrared spectrum of hydrophilic modified organosilicon wax AH4 in Example 4; Figure 5 The infrared spectrum of hydrophilic modified organosilicon wax AH5 in Example 5; Figure 6 Images of the cream prepared using the hydrophilic modified silicone wax AH1 from Example 1 after a storage stability test; Figure 7 Images of the cream prepared using the hydrophilic modified silicone wax AH2 from Example 2 after storage stability testing; Figure 8 Images of the cream prepared using the hydrophilic modified silicone wax AH3 of Example 3 after storage stability testing; Figure 9 Images of the cream prepared using the hydrophilic modified silicone wax AH4 from Example 4 after storage stability testing; Figure 10 Images of the cream prepared using the hydrophilic modified silicone wax AH5 from Example 5 after storage stability testing; Figure 11 Images of the cream prepared using hydrophilic modified silicone wax DH1 (Comparative Example 1) after storage stability testing. Figure 12 Images of the cream prepared using the hydrophilic modified silicone wax DH2 from Comparative Example 2 after storage stability testing; Figure 13Images of the cream prepared using hydrophilic modified silicone wax DH3 (Comparative Example 3) after storage stability testing. Detailed Implementation

[0027] The following embodiments are provided to better understand the present invention and are not limited to the preferred embodiments described. They do not constitute a limitation on the content and scope of protection of the present invention. Any product that is the same as or similar to the present invention, derived by any person under the guidance of the present invention or by combining the features of the present invention with other prior art, falls within the protection scope of the present invention.

[0028] For experiments not specifically described in the examples, the procedures or conditions should be followed according to the conventional experimental procedures described in the literature in this field. Reagents or instruments whose manufacturers are not specified are all commercially available conventional reagent products.

[0029] Unless otherwise specified, room temperature or normal temperature in the embodiments of the present invention refers to 25±1℃. Example 1

[0030] This embodiment provides a hydrophilic modified organosilicon wax, the raw materials for which are prepared as follows: (a) Hydrogen-containing polysiloxane: number average molecular weight approximately 4300 g / mol, hydrogen content 0.46%; (b) Allyl glycidyl ether; (c) Allyl polyoxyethylene ether: CH2=CHCH2O(CH2CH2O)5H; (d) 1-Ecicoside; (e) Karstedt catalyst; (f) Sodium bisulfite; The molar ratio of hydrogen-containing polysiloxane, allyl glycidyl ether, allyl polyoxyethylene ether, 1-eicosadiene, and Karstedt catalyst is 1:4:6:10:10. -6 ; The molar ratio of sodium bisulfite to allyl glycidyl ether is 1:0.8.

[0031] The preparation method is as follows: S1. Under nitrogen protection, hydrogen-containing polysiloxane was added to the reactor, heated to 70°C, and a mixture of allyl glycidyl ether, allyl polyoxyethylene ether, and 1-docosahexaene was slowly added dropwise. At the same time, Karstedt catalyst was added and mixed. The temperature was raised to 80°C and the reaction was kept at a constant temperature for 6 h to obtain epoxy-polyether-long-chain alkyl modified polysiloxane A1. S2. Add sodium bisulfite to the reactor and add 30% of the total material mass of propylene glycol methyl ether-water mixed solvent (the mass ratio of propylene glycol methyl ether to water is 30:1). Heat to 60℃ and react at a constant temperature for 12 h. After the reaction is completed, filter while hot to remove a small amount of impurities. Remove the solvent from the filtrate by vacuum distillation to obtain hydrophilic modified organosilicon wax AH1 with a melting point of 42℃.

[0032] The structure of the hydrophilic modified organosilicon wax AH1 prepared in this embodiment is as follows: .

[0033] The infrared spectrum of the hydrophilic modified organosilicon wax AH1 prepared in this embodiment is as follows: Figure 1 As shown. Example 2

[0034] This embodiment provides a hydrophilic modified organosilicon wax, the raw materials for which are prepared as follows: (a) Hydrogen-containing polysiloxane: number average molecular weight approximately 6700 g / mol, hydrogen content 0.53%; (b) Allyl glycidyl ether; (c) Allyl polyoxyethylene-polyoxypropylene block copolyether: CH2=CHCH2O(CH2CH2O)5(CH(CH3)CH2O)2CH3; (d) 1-Hexadecene; (e) Karstedt catalyst; (f) Sodium bisulfite; The molar ratio of hydrogen-containing polysiloxane, allyl glycidyl ether, allyl polyoxyethylene ether, 1-hexadecene, and Karstedt catalyst is 1:8:8:20:5*10. -5 ; The molar ratio of sodium bisulfite to allyl glycidyl ether is 1:0.8.

[0035] The preparation method is as follows: S1. Under nitrogen protection, hydrogen-containing polysiloxane was added to the reactor, heated to 70°C, and a mixture of allyl glycidyl ether, allyl polyoxyethylene-polyoxypropylene block copolymer ether, and 1-hexadecene was slowly added dropwise. At the same time, Karstedt catalyst was added and mixed. The temperature was raised to 110°C and the reaction was kept at a constant temperature for 10 h to obtain epoxy-polyether-long-chain alkyl modified polysiloxane A2. S2. Add sodium bisulfite to the reactor and add 40% of the total material mass of propylene glycol methyl ether-water mixed solvent (the mass ratio of propylene glycol methyl ether to water is 30:1). Heat to 80℃ and react at a constant temperature for 24 h. After the reaction is completed, filter while hot to remove a small amount of impurities. Remove the solvent from the filtrate by vacuum distillation to obtain hydrophilic modified organosilicon wax AH2 with a melting point of 54℃.

[0036] The structure of the hydrophilic modified organosilicon wax AH2 prepared in this embodiment is as follows: .

[0037] The infrared spectrum of the hydrophilic modified organosilicon wax AH2 prepared in this embodiment is as follows: Figure 2 As shown. Example 3

[0038] This embodiment provides a hydrophilic modified organosilicon wax, the raw materials for which are prepared as follows: (a) Hydrogen-containing polysiloxane: number average molecular weight approximately 4100 g / mol, hydrogen content 0.42%; (b) Allyl glycidyl ether; (c) Allyl polyoxyethylene-polyoxypropylene random copolymer: CH2=CHCH2O(CH2CH2O)5(CH(CH3)CH2O)2CH3; (d) 1-Ecicoside; (e) Karstedt catalyst; (f) Sodium bisulfite; The molar ratio of hydrogen-containing polysiloxane, allyl glycidyl ether, allyl polyoxyethylene ether, 1-eicosadiene, and Karstedt catalyst is 1:5:5:8:10. -7 ; The molar ratio of sodium bisulfite to allyl glycidyl ether is 1:0.8.

[0039] The preparation method is as follows: S1. Under nitrogen protection, hydrogen-containing polysiloxane was added to the reactor, heated to 75°C, and a mixture of allyl glycidyl ether, allyl polyoxyethylene-polyoxypropylene random copolymer ether, and 1-eicosadiene was slowly added dropwise. At the same time, Karstedt catalyst was added and mixed. The temperature was raised to 80°C and the reaction was kept at a constant temperature for 9 h to obtain epoxy-polyether-long-chain alkyl modified polysiloxane A3. S2. Add sodium bisulfite to the reactor and add 30% of the total material mass of propylene glycol methyl ether-water mixed solvent (the mass ratio of propylene glycol methyl ether to water is 30:1). Heat to 60℃ and react at a constant temperature for 14 h. After the reaction is completed, filter while hot to remove a small amount of impurities. Remove the solvent from the filtrate by vacuum distillation to obtain hydrophilic modified organosilicon wax AH3 with a melting point of 38℃.

[0040] The structure of the hydrophilic modified organosilicon wax AH3 prepared in this embodiment is as follows: .

[0041] The infrared spectrum of the hydrophilic modified organosilicon wax AH3 prepared in this embodiment is as follows: Figure 3 As shown. Example 4

[0042] This embodiment provides a hydrophilic modified silicone wax, which differs from Example 1 only in that the alkenyl epoxy compound used in the preparation raw material is glycidyl methacrylate, and all other aspects are the same as in Example 1; the hydrophilic modified silicone wax AH4 is obtained with a melting point of 44°C.

[0043] The structure of the hydrophilic modified organosilicon wax AH4 prepared in this embodiment is as follows: .

[0044] The infrared spectrum of the hydrophilic modified organosilicon wax AH4 prepared in this embodiment is as follows: Figure 4 As shown. Example 5

[0045] This embodiment provides a hydrophilic modified silicone wax, which differs from Example 1 only in that the alkenyl epoxy compound used in the preparation raw material is 1,2-epoxy-5-hexene, and all other aspects are the same as in Example 1; the hydrophilic modified silicone wax AH5 is obtained with a melting point of 38°C.

[0046] The structure of the hydrophilic modified organosilicon wax AH5 prepared in this embodiment is as follows: .

[0047] The infrared spectrum of the hydrophilic modified organosilicon wax AH5 prepared in this embodiment is as follows: Figure 5 As shown.

[0048] Comparative Example 1 This comparative example provides a hydrophilic modified organosilicon wax, the raw materials for which are prepared as follows: (a) Hydrogen-containing polysiloxane: number average molecular weight approximately 4300 g / mol, hydrogen content 0.46%; (b) Allyl glycidyl ether; (c) 1-Ecicoside; (d) Karstedt catalyst; (e) Sodium bisulfite; The molar ratio of hydrogen-containing polysiloxane, allyl glycidyl ether, 1-eicosadiene, and Karstedt catalyst is 1:10:10:10. -6 ; The molar ratio of sodium bisulfite to allyl glycidyl ether is 1:0.8.

[0049] The preparation method is as follows: S1. Under nitrogen protection, hydrogen-containing polysiloxane is added to the reactor, the temperature is raised to 70°C, and a mixture of allyl glycidyl ether and 1-docosahexaene is slowly added dropwise. At the same time, Karstedt catalyst is added and mixed. The temperature is raised to 80°C and the reaction is kept at a constant temperature for 6 hours to obtain epoxy-long-chain alkyl modified polysiloxane. S2. Add sodium bisulfite to the reactor and add 30% of the total material mass of propylene glycol methyl ether-water mixed solvent (the mass ratio of propylene glycol methyl ether to water is 30:1). Heat to 60℃ and react at a constant temperature for 12 h. After the reaction is completed, filter while hot to remove a small amount of impurities. Remove the solvent from the filtrate by vacuum distillation to obtain hydrophilic modified organosilicon wax DH1.

[0050] The structure of the hydrophilic modified organosilicon wax DH1 prepared in this comparative example is as follows: .

[0051] Comparative Example 2 This comparative example provides a hydrophilic modified organosilicon wax, the raw materials for which are prepared as follows: (a) Hydrogen-containing polysiloxane: number average molecular weight approximately 4300 g / mol, hydrogen content 0.46%; (b) Allyl polyoxyethylene ether: CH2=CHCH2O(CH2CH2O)5H; (c) 1-Ecicoside; (d) Karstedt catalyst; The molar ratio of hydrogen-containing polysiloxane, allyl polyoxyethylene ether, 1-eicosadiene, and Karstedt catalyst is 1:10:10:10. -6 ; The preparation method is as follows: Under nitrogen protection, hydrogen-containing polysiloxane was added to the reactor and heated to 70°C. A mixture of allyl polyoxyethylene ether and 1-eicosadiene was slowly added dropwise, and Karstedt catalyst was added and mixed. The temperature was raised to 80°C and the reaction was kept constant for 6 hours. After the reaction was completed, the temperature was lowered to room temperature and filtered to remove a small amount of impurities, yielding hydrophilic modified organosilicon wax DH2.

[0052] The structure of the hydrophilic modified organosilicon wax DH2 prepared in this comparative example is as follows: .

[0053] Comparative Example 3 This comparative example provides a hydrophilic modified organosilicon wax, the raw materials for which are prepared as follows: (a) Hydrogen-containing polysiloxane: number average molecular weight approximately 4300 g / mol, hydrogen content 0.46%; (b) Allyl-terminated epoxy polyether: CH2=CHCH2O(CH2CH2O)5CH2(CHCH2)O; (c) 1-Ecicoside; (d) Karstedt catalyst; (e) Sodium bisulfite; The molar ratio of hydrogen-containing polysiloxane, allyl-terminated epoxy polyether, 1-eicosadiene, and Karstedt catalyst is 1:10:10:10. -6 ; The molar ratio of sodium bisulfite to allyl-terminated epoxy polyether is 1:0.8.

[0054] The preparation method is as follows: S1. Under nitrogen protection, hydrogen-containing polysiloxane is added to the reactor, the temperature is raised to 70°C, and a mixture of allyl-terminated epoxy polyether and 1-eicosadiene is slowly added dropwise. At the same time, Karstedt catalyst is added and mixed. The temperature is raised to 80°C and the reaction is kept at a constant temperature for 6 hours to obtain polyether epoxy-long-chain alkyl modified polysiloxane. S2. Add sodium bisulfite to the reactor and add 30% of the total material mass of propylene glycol methyl ether-water mixed solvent (the mass ratio of propylene glycol methyl ether to water is 30:1). Heat to 60℃ and react at a constant temperature for 12 h. After the reaction is completed, filter while hot to remove a small amount of impurities. Remove the solvent from the filtrate by vacuum distillation to obtain hydrophilic modified organosilicon wax DH3.

[0055] The structure of the hydrophilic modified organosilicon wax DH3 prepared in this comparative example is as follows: .

[0056] Relevant performance testing methods: 1. Evaluation of self-emulsifying properties Hydrophilic modified silicone wax was mixed with deionized water at a mass ratio of 1:9, heated to 80°C and stirred until completely melted. The mixture was then homogenized at 3000 rpm for 3 min, cooled to room temperature, and allowed to stand for 24 h. The appearance of the emulsion was then observed. The self-emulsifying performance was evaluated according to the following grades: Grade 5: A homogeneous, stable milky white or translucent emulsion, without stratification, precipitation, or separation; Grade 4: Homogeneous emulsion with a very small amount of oil droplets or slight stratification on the surface, which can be restored after shaking. Level 3: There is obvious stratification or sedimentation, but it can become temporarily homogenized after shaking; Level 2: Severe stratification, unable to be restored to uniformity through oscillation; Level 1: Complete demulsification, oil and water separation.

[0057] 2. The hydrophilic modified silicone waxes from the examples and comparative examples were used to prepare creams, and the cream formulations are as follows (by weight): Oil phase: 3.0 parts stearic acid, 2.0 parts cetyl alcohol, 3.5 parts hydrophilic modified silicone wax, 5.0 parts isohexadecane, 4.0 parts caprylic / capric triglyceride, 0.1 parts vitamin E; Aqueous phase: 8.0 parts glycerin, 1.0 part panthenol, 0.1 parts sodium hyaluronate, 0.05 parts disodium EDTA, 71.75 parts deionized water; Emulsifier and neutralizer: 2.0 parts cetearyl alcohol polyether-21, 0.5 parts triethanolamine; Preservative: 0.8 parts phenoxyethanol.

[0058] Preparation steps: S1. Accurately weigh all raw materials according to the formula and classify them into groups. Mix stearic acid, cetyl alcohol, hydrophilic modified silicone wax, isohexadecane, caprylic / capric triglyceride, vitamin E, cetearyl alcohol polyether-21, and other oil phase materials evenly. Heat the mixture in a water bath to 80°C and stir at a constant temperature until the silicone wax and various oils are completely melted, resulting in a clear and transparent homogeneous oil phase system. Simultaneously, mix deionized water, glycerin, panthenol, sodium hyaluronate, disodium EDTA, and other aqueous phase materials, and heat to 80°C. Continue stirring until all powder materials are completely dissolved and the aqueous phase system is clear and free of impurities. Maintain the temperature of both the oil and water phases at 80°C. Under low-speed stirring, slowly add the molten oil phase to the aqueous phase. After the addition is complete, homogenize at 8000 r / min for 3 min, then adjust the speed to 300 r / min and stir at a constant temperature for 10 min. Finally, slowly add triethanolamine and stir evenly. Adjust the pH of the system to 5.5~6.5.

[0059] S2. After the cream base is prepared, maintain low-speed stirring and allow it to cool naturally. When the system temperature drops to 45℃, add the preservative phenoxyethanol and continue stirring for 3-5 minutes to ensure uniform dispersion of the preservative. Continue stirring at low speed and cooling to room temperature until the paste viscosity is stable and the texture is uniform. Then, fill the cream into clean, sealed containers and let it stand at room temperature for 24 hours to defoam and completely eliminate micro-bubbles in the system, finally obtaining the finished cream for subsequent performance tests.

[0060] (1) Storage stability test The prepared cream sample was sealed and placed in a constant temperature oven at 45±2℃ for 8 weeks. The sample was removed weekly to observe its condition and record any signs of water separation, layering, or softening of the cream.

[0061] (2) Film-forming and moisturizing properties test Twenty healthy adult subjects were selected. A test area (3 cm × 3 cm) was marked on the inner forearm. After sitting quietly for 30 minutes in a constant temperature and humidity environment (22±2℃, 50±5%RH), the baseline TEWL value was measured using a transdermal water loss meter (average of three consecutive measurements). Subsequently, 5 mg of the test cream sample was applied to the test area, and the TEWL value was measured again at 1 h, 2 h, and 4 h after application (again, average of three consecutive measurements). The TEWL reduction rate after 4 h was calculated as follows: Reduction rate (%) = (baseline value - measured value) / baseline value × 100%. A higher TEWL reduction rate indicates better film-forming moisturizing properties.

[0062] (3) Use of skin feel evaluation Twenty healthy adult subjects were selected. A test area (5 cm × 5 cm) was marked on the inner forearm. After sitting quietly for 30 minutes in a constant temperature and humidity environment (22±2℃, 50±5%RH), 30 mg of the test cream sample was placed in the test area and spread evenly over the entire test area using the index finger in a circular motion. A 5-point scoring system (1 point is the worst, 5 points is the best) was used, and the subjects independently completed the immediate evaluation of the following three indicators (within 10 seconds after application): Spreadability: 1 point (difficult to spread, noticeable dragging sensation), 5 points (extremely easy to spread, silky smooth).

[0063] Refreshing feeling: 1 point (very sticky, with a noticeable oily film), 5 points (completely non-sticky, refreshing and comfortable).

[0064] Fineness: 1 point (there is a noticeable grainy feel when applying), 5 points (the texture is delicate and smooth when applying, without any roughness).

[0065] Calculate the average score (accurate to 0.1 points) of 20 subjects for each indicator.

[0066] The test results are shown in Table 1.

[0067] Table 1. Performance test results of hydrophilic modified silicone waxes in the examples and comparative examples.

[0068] The results above show that the organosilicon wax of the present invention introduces both hydroxysulfonate-containing side chains and polyether side chains on the polysiloxane backbone. Its amphiphilic molecular structure can not only enhance the interfacial compatibility of the oil and water phases and effectively improve the stability of the emulsion system, but also form a continuous, dense, long-lasting water-locking protective film on the skin surface, significantly improving moisturizing ability; at the same time, it optimizes the application feel, taking into account the multiple advantages of smooth spread, refreshing and non-sticky, and delicate cream.

[0069] Application Example 1 This application example provides a hair conditioner serum with the following formula (by weight): 30 parts of cyclopentamethoxysiloxane, 45 parts of isohexadecane, 5 parts of the silicone wax from Example 1, 2 parts of panthenol, 0.8 parts of vitamin E, 3 parts of plant squalane, 0.2 parts of fragrance, 2.2 parts of phenoxyethanol, 0.8 parts of ethylhexylglycerin, 0.7 parts of 1,2-hexanediol, and 0.3 parts of p-hydroxyacetophenone.

[0070] Preparation steps: All oil-phase raw materials are added to the reaction vessel, heated to 70℃ and stirred at low speed until the silicone wax is completely melted and homogenized. After cooling to 40℃, fragrance and preservatives are added and stirred evenly. The mixture is then bottled at room temperature to prepare the leave-in repair hair essence. The system is homogeneous and stable with good storage stability. When used, it spreads smoothly and evenly without clumping or pilling. At the same time, it can form a thin and breathable protective film on the hair surface, effectively reducing the hair's friction coefficient, inhibiting static electricity, improving frizz and dryness, and giving the hair a refreshing and fluffy texture.

[0071] Application Example 2 This application example provides a scrub with the following formula (by weight): 42 parts deionized water, 10 parts glycerin, 4 parts silicone wax from Example 1, 6 parts cetyl alcohol, 3 parts stearic acid, 18 parts walnut seed exfoliating particles, 2 parts cocoamide DEA, 0.3 parts citric acid, and 1.7 parts phenoxyethanol.

[0072] Preparation steps: S1. Add all oil phase materials to a water bath reactor equipped with a stirrer, stir at 250 r / min, heat the water bath to 80℃ and maintain the temperature for 8 min, until the silicone wax, cetyl alcohol, and stearic acid are completely melted, and the system is transparent without wax particles or solid lumps. In a separate container, add deionized water, glycerin, and cocoamide (DEA), and simultaneously heat in a water bath to 80℃, stir at 200 r / min for 5 min, until the surfactant and humectant are completely dissolved, and the aqueous phase is clear without flocculent matter.

[0073] S2. Maintaining a stable oil-water phase temperature of 80℃, the hot water phase is uniformly poured into the molten oil phase while stirring at a low speed of 300 r / min. After the addition is complete, homogenize at a high speed of 8000 r / min for 3 min to form a uniform and delicate cream base. Then, turn off the homogenizer and maintain a low speed of 250 r / min for natural cooling. When the system temperature drops to 45℃, add walnut seed exfoliating particles, phenoxyethanol, and citric acid in sequence, and continue stirring for 5 min to ensure that the exfoliating particles are uniformly suspended and the preservatives and pH adjusters are completely dispersed. Finally, continue stirring at a low speed and cool to room temperature of 25℃. Discharge the material into a sealed container and let it stand at room temperature for 24 h to defoam, obtaining the finished body scrub. The system is homogeneous and stable with good storage stability. When used, it applies smoothly without any obstruction, and the particles have a soft touch. It is also easy to clean with warm water, leaving no slippery or sticky residue.

Claims

1. A hydrophilic modified organosilicon wax, characterized in that, It has the structure shown in equation (1): Equation (1); Wherein, R1 is selected from alkylene groups having 2 to 10 carbon atoms; M represents an ether bond, ester bond, or single bond; X represents Na, Mg, or K; R2 is a hydrogen atom, an acetyl group, or an alkyl group having 1 to 4 carbon atoms; R3 is selected from alkyl groups having 18 to 30 carbon atoms; R4 and R5 are each independently selected from alkyl groups having 1 to 18 carbon atoms or unsaturated hydrocarbon groups. m and n are each independent integers from 0 to 15, and 0 < m + n < 30; a is an integer from 2 to 20; b is an integer from 2 to 40; c is an integer from 5 to 50; d is an integer from 10 to 65. The melting point of the hydrophilic modified silicone wax is 30~55℃.

2. The hydrophilic modified organosilicon wax according to claim 1, characterized in that, R1 is selected from straight-chain alkylene groups with 3 to 6 carbon atoms; M represents an ether bond; X represents Na.

3. The hydrophilic modified organosilicon wax according to claim 1, characterized in that, The raw materials for preparing the hydrophilic modified silicone wax include: (a) Hydrogen-containing polysiloxanes; (b) Alkenyl epoxy compounds; (c) Allyl polyether; (d) α-olefins; (e) Platinum catalyst; (f) Bisulfite.

4. The hydrophilic modified organosilicon wax according to claim 3, characterized in that, The hydrogen-containing polysiloxane has a number average molecular weight of 1000~20000 g / mol and a hydrogen content of 0.1%~1.6%.

5. The hydrophilic modified organosilicon wax according to claim 3, characterized in that, The alkenyl epoxy compound is selected from any one of allyl glycidyl ether, 2-methyl allyl glycidyl ether, vinyl glycidyl ether, 1,2-epoxy-5-hexene, 1,2-epoxy-7-octene, 1,2-epoxy-9-decene, glycidyl methacrylate, and glycidyl acrylate; the allyl polyether is selected from any one of allyl polyoxyethylene ether, allyl polyoxypropylene ether, and allyl polyoxyethylene-polyoxypropylene copolyether; the number average molecular weight of the allyl polyether is 100~1800 g / mol; the α-olefin is selected from at least one of straight-chain α-olefins with 18~30 carbon atoms; the bisulfite is selected from any one of sodium bisulfite, magnesium bisulfite, and potassium bisulfite.

6. The hydrophilic modified organosilicon wax according to claim 3, characterized in that, The molar ratio of the hydrogen-containing polysiloxane, alkenyl epoxy compound, allyl polyether, α-olefin, and platinum catalyst is 1:(2~20):(2~40):(5~50):(10) -7 ~10 -4 ); The molar ratio of the bisulfite to the alkenyl epoxy compound is 1:(0.8~1.0).

7. The method for preparing hydrophilic modified organosilicon wax according to any one of claims 1 to 6, characterized in that, Includes the following steps: S1. Under inert gas protection, hydrogen-containing polysiloxane, alkenyl epoxy compound, allyl polyether, α-olefin and platinum catalyst are mixed and subjected to hydrosilylation reaction at 70~130℃ for 2~10 h to obtain epoxy-polyether-long-chain alkyl modified polysiloxane. S2. The product obtained in step S1 and the bisulfite are added to a mixture of propylene glycol methyl ether and water, and the ring-opening sulfonation reaction is carried out at 60~110℃ for 3~24h. After the reaction is completed, the mixture is filtered while hot, and the filtrate is distilled under reduced pressure to prepare the hydrophilic modified organosilicon wax.

8. The application of the hydrophilic modified silicone wax according to any one of claims 1 to 6 in cosmetics.

9. A cosmetic composition, characterized in that, Includes the hydrophilic modified organosilicon wax according to any one of claims 1 to 6.

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