Preparation method and application of ethylhexyl triazone

Abstract

The application belongs to the technical field of fine chemical industry, and specifically discloses a preparation method and application of ethylhexyl triazone. The preparation method of ethylhexyl triazone comprises the following steps: condensation reaction, pretreatment, dehydration and filtration, filtrate purification, reduction reaction, post-treatment, filtration, coupling, secondary pretreatment, desolventization, and crystal form treatment, so that ethylhexyl triazone is obtained. The method is accurate in operation, and each step is accurate and explicit, so that the obtained ethylhexyl triazone product is of regular crystal form, high purity, light color, and good stability.

Description

Technical Field

[0001] This application relates to the technical field of fine chemicals, and in particular to a method for preparing and using ethylhexyltriazine ketone. Background Technology

[0002] Ultraviolet (UV) radiation is one of the main environmental factors causing sunburn, photoaging, and skin cancer. UV absorbers used in sunscreens are the core ingredients for protecting against this damage. There are many types of UV absorbers, and they are widely used; however, in actual sunscreen products, the protective effects of different absorbers vary considerably.

[0003] Ethylhexyltriazine is a highly effective oil-soluble ultraviolet absorber, often marketed as UVT-150 or Uvinul T 150. Its molecular structure consists of a central triazine ring conjugated with three 2-ethylhexyl-4-aminobenzoate chromophores. It strongly absorbs UVB rays and also provides some UVA protection. Due to its good photostability, water resistance, and skin affinity, it is widely used in high-end sunscreens and skincare products.

[0004] Industrially, a two-step synthesis method is mainly used. Starting with p-nitrobenzoic acid, the target molecule is constructed through a path of esterification followed by hydrogenation. In the esterification reaction, p-nitrobenzoic acid reacts with isooctanol to form the corresponding ester. In the hydrogenation and coupling reaction, the ester generated in the previous step is hydrogenated in the presence of a catalyst to generate an intermediate product, which is then coupled with a triazine derivative to obtain the final product.

[0005] This method has the advantages of controllable raw material and process costs, high production feasibility, and low environmental impact, but it has the disadvantage of low purity of the extracted product. Summary of the Invention

[0006] To improve the quality stability and safety of ethylhexyltriazine ketone products, this application provides a method for preparing ethylhexyltriazine ketone.

[0007] This application provides a method for preparing ethylhexyltriazine ketone, using the following technical solution: A method for preparing ethylhexyltriazine ketone includes the following steps: (1) Condensation reaction: p-nitrobenzoic acid, isooctyl alcohol and the catalyst p-toluenesulfonic acid are mixed and heated to 145-155℃. The water generated in the reaction is separated. The reaction is continued until no more water is generated. The reaction ends and a condensation reaction solution is obtained. (2) Pretreatment: Wash the condensation reaction solution with water to obtain the washed condensation reaction solution; (3) Dehydration and filtration: The washed condensation reaction solution was added to toluene and refluxed at 120-130℃ to remove water and dehydrate, and the filtrate was obtained. (4) Purification of filtrate: The filtrate was subjected to vacuum distillation, and the fraction from 175-184℃ was collected to obtain isooctyl p-nitrobenzoate; (5) Reduction reaction: Add isooctyl p-nitrobenzoate to ethanol, add concentrated hydrochloric acid and iron powder, and reflux at 70-80℃ for 10h; (6) Post-treatment: Cool the reaction solution to 25-30℃, add sodium hydroxide, adjust pH to 9-10, filter to remove solid insoluble matter and iron powder, heat to 60-70℃, concentrate under reduced pressure, add water to the concentrate, precipitate solid, and stir thoroughly. (7) Filtration: Filtration yields isooctyl para-aminobenzoate, which is dried at 80-90℃; (8) Coupling: Mix isooctyl p-aminobenzoate, cyanuric chloride and toluene, heat to 110-120℃ and reflux until no more gas is produced, the reaction is complete and the liquid is obtained; (9) Secondary pretreatment: Add sodium carbonate aqueous solution to the feed solution, neutralize to pH 6-7 of the reaction solution, and react to obtain a mixed solution. Wash with water to obtain a pretreated mixed solution. (10) Desolventizing: The pretreated mixture is heated to 110-120℃ to remove toluene, and then condensed to obtain the mixture; (11) Crystal form treatment: The hot dissolution and cold precipitation method is used to carry out secondary recrystallization to obtain filter cake and filtrate. After the filtrate is desolventized, ethanol is recovered to obtain filter residue. After the filter cake is dried, ethylhexyltriazine ketone is obtained.

[0008] By employing the above technical solution, p-nitrobenzoic acid and isooctyl alcohol undergo an esterification condensation reaction under the catalysis of p-toluenesulfonic acid to generate isooctyl p-nitrobenzoate, with water as a byproduct. A high temperature of 145-155℃ promotes the forward reaction, and the generated water is continuously removed through separation, bringing the reaction closer to completion.

[0009] The system is washed with water to remove p-toluenesulfonate, preventing acidic impurities from affecting subsequent reduction and coupling reactions and improving product purity and yield. Toluene is added for azeotropic dehydration at 120-130℃ to completely remove residual water from the system; high-purity isooctyl p-nitrobenzoate is obtained by vacuum distillation, removing light components, high-boiling impurities, and unreacted raw materials. In an iron powder-hydrochloric acid reduction system, the nitro group of isooctyl p-nitrobenzoate is reduced to an amino group, generating isooctyl p-aminobenzoate.

[0010] Hydrochloric acid was neutralized with NaOH, causing the iron salt to precipitate as ferric hydroxide. The precipitate was then removed by pressure filtration to remove iron sludge and insoluble matter. Water was added to precipitate the product from the alcohol-water system. Filtration yielded solid isooctyl p-aminobenzoate, which was dried to remove residual solvent and water, providing a high-purity intermediate for the next coupling step. Isooctyl p-aminobenzoate was then condensed with cyanuric chloride in toluene at high temperature to generate the ethylhexyl triazine ketone core structure.

[0011] Sodium carbonate neutralization and water washing remove water-soluble salts and polar impurities, improving product purity and stability. High-temperature removal of toluene solvent yields crude ethylhexyltriazine ketone. Hot dissolution followed by cold rehydration and secondary recrystallization further removes organic impurities, isomers, and residual solvent, resulting in a finished ethylhexyltriazine ketone product with regular crystal structure, high purity, light color, and good stability.

[0012] Preferably, in step (2), the wastewater after water washing is evaporated and salted out, and in step (6), the wastewater after water washing is evaporated and salted out.

[0013] By adopting the above technical solution, the role of step (2) evaporation and salting out of the washing wastewater is to evaporate, concentrate, and salt out the washing wastewater, recover water-soluble sulfonate by-products, reduce the direct discharge of high-salt wastewater, and improve the cleanliness and economy of the process.

[0014] The role of step (6) in the evaporation and salting out of the water washing wastewater is to enrich and precipitate inorganic iron and sodium salts, reduce the COD and salt content of the wastewater, recover usable fractions, and meet the environmental protection compliance requirements of industrialization.

[0015] Preferably, in step (3), the dehydrated liquid contains a small amount of insoluble solid salts and is then filtered.

[0016] By adopting the above technical solution, inorganic salts, mechanical impurities and other insoluble solids precipitated during the dehydration process are removed by filtration, which prevents impurities from entering the subsequent vacuum distillation process and prevents problems such as coking, boiling, and pipeline blockage during distillation. At the same time, the purity of the distillate is improved, ensuring the purity and quality of the obtained isooctyl p-nitrobenzoate intermediate, and providing a stable foundation for the subsequent reduction reaction and the quality of the final product.

[0017] Preferably, in step (5), the gas produced is hydrogen chloride gas, which is then absorbed by three stages of water to prepare hydrochloric acid as a byproduct.

[0018] By adopting the above technical solution, hydrogen chloride gas is generated in the reduction reaction when iron powder reacts with concentrated hydrochloric acid and in the nitro reduction process. Hydrogen chloride gas is highly corrosive and irritating. Direct emission will pollute the environment, corrode equipment and endanger the health of operators. The three-stage water absorption can achieve efficient capture of hydrogen chloride gas, avoid the discharge of waste gas and meet the environmental protection compliance requirements of industrial production.

[0019] Secondly, this application also provides a sunscreen composition comprising the following ingredients: ethylhexyl triazine ketone, diethylamino hydroxybenzoyl hexyl benzoate, bis-ethylhexyloxyphenol methoxyphenyl triazine, PEG-10 polydimethylsiloxane, oat extract, glycerin, pentanediol, 1,3-propanediol, diisopropyl sebacate, cyclopentamethoxysiloxane, cetyl PEG / PPG-10 / 1 polydimethylsiloxane, phenoxyethanol, nano titanium dioxide, tocopherol, and deionized water.

[0020] By employing the above technical solutions, ethylhexyl triazine absorbs UVB rays, exhibiting high sun protection strength and good photostability, significantly improving SPF values, and is water and sweat resistant. Diethylamino hydroxybenzoyl hexyl benzoate has strong absorption capacity for UVA rays, improving PA values ​​and preventing photoaging, dark spots, and deep skin damage. Bis-ethylhexyloxyphenol methoxyphenyl triazine absorbs both UVA and UVB rays simultaneously, possesses excellent photostability, and synergistically enhances with other sunscreen agents, improving overall SPF and durability.

[0021] PEG-10 polydimethylsiloxane disperses sunscreen powder nano-TiO2, preventing agglomeration and pilling, and improving sunscreen evenness. Cetyl PEG / PPG-10 / 1 polydimethylsiloxane stabilizes the emulsion system, forming a thin protective film, improving spreadability, and reducing white cast and stickiness. Diisopropyl sebacic acid dissolves chemical sunscreen agents, reducing greasiness and improving skin feel. Cyclopentasiloxane spreads and evaporates quickly to form a film, providing a silky feel, reducing stickiness, and helping sunscreen agents form a uniform film.

[0022] Glycerin absorbs and locks in moisture, relieving dryness and tightness in sunscreen products and improving skin comfort. Pentylene glycol assists in moisturizing, while also improving preservative efficiency and formula solubility. 1,3-Propane glycol enhances the refreshing, non-sticky feel and helps dissolve active ingredients and sunscreen agents. Oat extract soothes inflammation, repairs the skin barrier, reduces UV irritation and redness, and lowers the potential irritation of the sunscreen formula. Phenoxyethanol inhibits bacteria and fungi, ensuring product shelf life and safety. Tocopherol scavenge free radicals, protects against photo-oxidative damage, and stabilizes oils and sunscreen agents in the formula, extending shelf life.

[0023] The overall formula works synergistically to create a stable, gentle, and highly tolerable silicone-in-water sunscreen system, achieving broad-spectrum and highly effective sun protection, a lightweight feel, soothing and moisturizing, and antioxidant properties all in one. It is suitable for daily high-SPF sun protection and outdoor sun protection, balancing efficacy and user comfort.

[0024] Preferably, the mass ratio of ethylhexyl triazine ketone, diethylamino hydroxybenzoyl hexyl benzoate, and bis-ethylhexyloxyphenol methoxyphenyl triazine is 1:1-1.5:0.5-2.5.

[0025] By employing the above technical solution, ethylhexyl triazine ketone provides strong UVB absorption, responsible for preventing sunburn, redness, and pain, and improving SPF. Diethylamino hydroxybenzoyl hexyl benzoate provides strong UVA absorption, responsible for preventing photoaging, dark spots, and deep damage, and improving PA. Bis-ethylhexyloxyphenol methoxyphenyl triazine provides broad-spectrum UVA+UVB dual absorption, filling the gap in the middle bands and forming a continuous and complete protective spectrum. After the three are combined, the bands that cannot be covered by a single component are complemented by each other, achieving truly high-efficiency protection across the entire spectrum.

[0026] When combined, these three ingredients mutually inhibit photodegradation, preventing the rapid failure of individual sunscreen agents under sunlight. This significantly improves the longevity, water resistance, and sweat resistance of sunscreens, making long-term outdoor protection more reliable. The protective effect of the combined ingredients is far superior to that of a single ingredient in the same total amount, achieving high SPF and high PA with a lower total addition amount, reducing the burden on the formulation and lowering the risk of irritation. The three ingredients have complementary solubility in oil and siloxane systems, making it easier to form a uniform and transparent oil phase after combination. This reduces the likelihood of sunscreen crystallization, precipitation, whitening, pilling, and other problems, resulting in a more uniform and continuous film formation.

[0027] Preferably, the oat extract is composed of montmorillonite, rosemary extract, and modified montmorillonite.

[0028] By employing the above-mentioned technical solutions, oat extract possesses soothing and anti-inflammatory properties, repairs the skin barrier, alleviates redness, burning, and stinging caused by UV radiation, reduces the irritation of sunscreen systems on the skin, moisturizes and locks in moisture, and improves the dryness and tightness issues associated with sunscreen products. Modified montmorillonite has excellent adsorption and suspension stability, adsorbing excess oil and sweat from the skin surface, enhancing the oil control, anti-stickiness, and anti-sweat effects of sunscreen products, improving the application feel, reducing pilling and whitening, and helping to form a uniform and continuous sunscreen film, thereby improving the water resistance and durability of the sunscreen film.

[0029] Rosemary extract, a natural antioxidant, anti-inflammatory, and antibacterial active ingredient, eliminates free radicals induced by UV radiation, inhibits oil oxidation, delays formula rancidity, improves product stability, and synergistically soothes inflammation, reduces photodamage and formula irritation, and assists in anti-photoaging. The combination of these three ingredients soothes and repairs synergistically, reducing irritation to the sunscreen system and resolving issues such as oiliness, breakouts, and shine in sunscreen products. It also improves powder dispersibility, reduces titanium dioxide whitening and pilling, resulting in a lighter and smoother overall feel. The synergistic system stability ensures more even and long-lasting sun protection. Combined with the antioxidant properties of rosemary extract, it delays oil phase deterioration, ensuring a long-lasting, even, and intact sunscreen film, improving sun protection durability, water resistance, and sweat resistance.

[0030] Preferably, the modified montmorillonite is composed of montmorillonite, polydimethylsiloxane / vinyl polydimethylsiloxane cross-linked polymer, and polyglycerol-2 diisostearate.

[0031] By employing the above technical solutions, montmorillonite exhibits adsorption and suspension properties, enabling it to absorb oils and sweat, stabilize the powder, and improve skin feel. However, its poor lipophilicity makes it prone to aggregation and stratification when directly added to sunscreen systems. The polydimethylsiloxane / vinyl polydimethylsiloxane crosspolymer acts as a thickener, thixotropic agent, and skin-softening agent, enhancing the silky feel of the formula, reducing stickiness, and simultaneously helping montmorillonite disperse in the oil phase and preventing sedimentation. Polyglycerol-2-diisostearate provides surface organic modification and wetting coating to montmorillonite, improving its compatibility and dispersibility in oil and siloxane systems.

[0032] The synergistic effect of these three components in preparing modified montmorillonite: Polyglycerol-2 diisostearate coats the surface of montmorillonite, reducing its surface polarity. Combined with the steric hindrance of the silicone elastomer, this transforms montmorillonite from a hydrophilic-oleophobic material to an oleophilic-hydrophobic material, allowing it to disperse uniformly in the sunscreen oil and silicone oil phases, preventing agglomeration, sedimentation, and pilling. Together, they form a three-dimensional stable network, effectively suspending nano-titanium dioxide and sunscreen microcrystals, reducing stratification, oil separation, and powder sedimentation, and improving product storage stability. It can form a continuous, dense, and water-resistant protective film on the skin surface, enhancing the integrity of the sunscreen film and improving its water, sweat, and abrasion resistance.

[0033] This modified montmorillonite is organically hydrophobically modified by compounding montmorillonite, polydimethylsiloxane / vinyl polydimethylsiloxane crosspolymer, and polyglycerol-2 diisostearate. This significantly improves its dispersibility and compatibility stability in the sunscreen oil phase system. At the same time, it synergistically imparts excellent suspension stability, smooth skin feel, oil control matte finish, and water-resistant film-forming effect to the formula, thereby enhancing the overall user experience and long-lasting efficacy of the sunscreen composition.

[0034] Preferably, the nano-titanium dioxide is pretreated as follows: Polyvinylpyrrolidone / hexadecane copolymer is dispersed in isododecane, stirred at 40-50℃ for 30-35 min, then sprayed onto the surface of nano-titanium dioxide, and spray-dried to obtain pretreated nano-titanium dioxide.

[0035] By employing the above technical solution, polyvinylpyrrolidone / hexadecane copolymer is used to modify the surface of nano-titanium dioxide by increasing its oleophilicity, reducing the surface energy of the powder, preventing particle agglomeration, and improving its dispersion stability in silicone oil and synthetic ester systems. After surface coating treatment, the nano-titanium dioxide exhibits reduced photocatalytic activity, improved dispersibility, and reduced whitening and pilling.

[0036] Polyvinylpyrrolidone / hexadecane copolymer is first fully dissolved and dispersed in isododecane, then uniformly coated onto the surface of TiO2 particles via spraying. The coating layer is continuous, thin, and uniform, avoiding localized excessive thickness or uneven coating. It does not settle or agglomerate during long-term storage and does not pill upon application. The polymer coating layer prevents TiO2 from directly contacting the skin, inhibiting its photocatalytic activity under UV excitation, reducing free radical generation, lowering irritation, and improving formula safety. After coating, TiO2 binds more tightly to film-forming agents and oils in the formula, forming a more continuous and dense film that is water-resistant, sweat-resistant, and abrasion-resistant, resulting in a longer-lasting sun protection effect.

[0037] Polyvinylpyrrolidone / hexadecane copolymer was dissolved in isododecane, stirred evenly, and then sprayed onto the surface of nano-titanium dioxide. After spray drying, a surface-modified powder was obtained. This treatment achieves uniform oleophilic coating of nano-titanium dioxide, significantly improving its dispersion stability in sunscreen systems, reducing agglomeration, whitening, and pilling. Simultaneously, it reduces photocatalytic activity, enhances the mildness of the formulation, and improves the water resistance and uniformity of the sunscreen film, resulting in a sunscreen composition that combines high-efficiency protection with excellent skin feel.

[0038] In summary, this application has the following beneficial effects: 1. In this application, hot melting and cold recrystallization are used to further remove organic impurities, isomers and residual solvents, so as to obtain ethylhexyltriazine ketone product with regular crystal form, high purity, light color and good stability.

[0039] 2. In this application, in the iron powder-hydrochloric acid reduction system, the nitro group of p-nitrobenzoate isooctyl ester is reduced to an amino group, generating p-aminobenzoate isooctyl ester.

[0040] 3. In this application, NaOH is added to neutralize hydrochloric acid, converting iron salt into ferric hydroxide precipitate, iron mud and insoluble matter are removed by pressure filtration, and water is added to precipitate the product from the alcohol-water system. Detailed Implementation

[0041] The present application will be further described in detail below with reference to the embodiments.

[0042] The raw materials used in the examples and comparative examples are all commercially available.

[0043] Example 1 A method for preparing ethylhexyltriazine ketone includes the following steps: (1) Condensation reaction: 1 eq p-nitrobenzoic acid (HPLC: 98.5%), 4 eq isooctyl alcohol (HPLC: 99.0%) and 0.03 eq catalyst p-toluenesulfonic acid are mixed and heated to 150°C. The water generated in the reaction is separated and the reaction is continued until no more water is generated. The reaction ends and the condensation reaction solution is obtained. (2) Pretreatment: Wash the condensation reaction solution with water to obtain the washed condensation reaction solution; (3) Dehydration and filtration: Add 0.5 times the mass of toluene to the washed condensation reaction solution and reflux at 125°C to remove water and dehydrate, and obtain filtrate; (4) Purification of filtrate: The filtrate was subjected to vacuum distillation (580 Pa), and the fraction at 180 °C was collected to obtain isooctyl p-nitrobenzoate; (5) Reduction reaction: The obtained product, p-nitrobenzoate isooctyl ester, was added to 5 times the mass of ethanol, 4%mol concentrated hydrochloric acid and 6eq iron powder were added, and the mixture was heated to 75℃ and refluxed for 10h. (6) Post-treatment: Cool the reaction solution to 28°C, add 5% sodium hydroxide, adjust pH=9, filter to remove solid insoluble matter and iron powder, heat to 65°C, concentrate to 4 times the amount of ethanol under reduced pressure of -0.09Mpa, add 4 times the amount of water to the concentrate, precipitate solid, and stir thoroughly for 1h. (7) Filtration: The filtered product isooctyl para-aminobenzoate was dried at 85°C for 3 hours. (8) Coupling: Mix 3.05 eq of isooctyl p-aminobenzoate, 1 eq of cyanuric chloride, and 5 times the mass of isooctyl p-aminobenzoate with toluene, heat to 115°C and reflux for about 6 hours until no more gas is produced, the reaction is complete, and the liquid is obtained. (9) Secondary pretreatment: Add 10% sodium carbonate aqueous solution to the feed solution, neutralize to pH 6 of the reaction solution, and react to obtain a mixed solution. Wash with water to obtain a pretreated mixed solution. (10) Desolventizing: The pretreated mixture is heated to 115°C to remove toluene, and then condensed to obtain a mixture; (11) Crystal form treatment: The hot dissolution and cold precipitation method is used, with 2.5 times ethanol as the crystallization solvent, and secondary recrystallization is carried out to obtain filter cake and filtrate. After desolvation of the filtrate, ethanol is recovered to obtain filter residue. After drying, the filter cake is used to obtain ethylhexyltriazine ketone.

[0044] Hot melting and cold precipitation: Stir at 78℃ for 30 minutes, control the temperature at 70℃, filter while hot to remove impurities, slowly cool down at 12℃ / h, final temperature 3℃, and keep warm for 2 hours.

[0045] In step (2), the wastewater after water washing is evaporated and salted out. In step (6), the wastewater after water washing is evaporated and salted out.

[0046] In step (3), the dehydrated liquid contains a small amount of insoluble solid salts, which are then filtered.

[0047] In step (5), the gas produced is hydrogen chloride gas. The hydrogen chloride gas is absorbed by three stages of water to prepare hydrochloric acid as a byproduct.

[0048] Example 2: A method for preparing ethylhexyl triazine ketone, which differs from Example 1 in that it includes the following steps: (1) Condensation reaction: 1.2 eq p-nitrobenzoic acid (HPLC: 98.5%), 4.3 eq isooctyl alcohol (HPLC: 99.0%) and 0.035 eq catalyst p-toluenesulfonic acid are mixed and heated to 155°C. The water generated in the reaction is separated. The reaction is continued until no more water is generated. The reaction ends and the condensation reaction solution is obtained. (2) Pretreatment: Wash the condensation reaction solution with water to obtain the washed condensation reaction solution; (3) Dehydration and filtration: Add 0.6 times the mass of toluene to the washed condensation reaction solution and reflux at 120°C to remove water and dehydrate, and obtain filtrate; (4) Purification of filtrate: The filtrate was subjected to vacuum distillation (590 Pa), and the fraction at 175 °C was collected to obtain isooctyl p-nitrobenzoate; (5) Reduction reaction: The obtained product, p-nitrobenzoate isooctyl ester, was added to 5 times the mass of ethanol, 4%mol concentrated hydrochloric acid and 6eq iron powder were added, and the mixture was heated to 80℃ and refluxed for 10h. (6) Post-treatment: Cool the reaction solution to 25°C, add 5% sodium hydroxide by mass, adjust pH=10, filter to remove solid insoluble matter and iron powder, heat to 60°C, concentrate to 4 times the amount of ethanol under reduced pressure of -0.09Mpa, add 4 times the amount of water by mass to the concentrate, precipitate solid, and stir thoroughly for 1h. (7) Filtration: The filtered product isooctyl para-aminobenzoate was dried at 80°C for 3 hours. (8) Coupling: Mix 3.05 eq of isooctyl p-aminobenzoate, 1 eq of cyanuric chloride, and 5 times the mass of isooctyl p-aminobenzoate with toluene, heat to 110°C and reflux for about 6 hours until no more gas is produced, the reaction is complete, and the liquid is obtained. (9) Secondary pretreatment: Add 10% sodium carbonate aqueous solution to the feed solution, neutralize to pH 6 of the reaction solution, and react to obtain a mixed solution. Wash with water to obtain a pretreated mixed solution. (10) Desolventizing: The pretreated mixture is heated to 110°C to remove toluene, and then condensed to obtain a mixture; (11) Crystal form treatment: The hot dissolution and cold precipitation method is used, with 2.5 times ethanol as the crystallization solvent, and secondary recrystallization is carried out to obtain filter cake and filtrate. After desolvation of the filtrate, ethanol is recovered to obtain filter residue. After drying, the filter cake is used to obtain ethylhexyltriazine ketone.

[0049] Hot melting and cold precipitation: Stir at 75℃ for 30 minutes, control the temperature at 65℃, filter while hot to remove impurities, slowly cool down at 10℃ / h, final temperature 0℃, and keep warm for 2 hours.

[0050] Example 3: A method for preparing ethylhexyltriazine ketone, which differs from Example 1 in that it includes the following steps: (1) Condensation reaction: 1.1 eq p-nitrobenzoic acid (HPLC: 98.5%), 4.2 eq isooctyl alcohol (HPLC: 99.0%) and 0.032 eq catalyst p-toluenesulfonic acid are mixed and heated to 145°C. The water generated in the reaction is separated. The reaction is continued until no more water is generated. The reaction ends and a condensation reaction solution is obtained. (2) Pretreatment: Wash the condensation reaction solution with water to obtain the washed condensation reaction solution; (3) Dehydration and filtration: Add 0.5 times the mass of toluene to the washed condensation reaction solution and reflux at 130°C to remove water and dehydrate, and obtain filtrate; (4) Purification of filtrate: The filtrate was subjected to vacuum distillation (570 Pa), and the fraction at 184 °C was collected to obtain isooctyl p-nitrobenzoate; (5) Reduction reaction: The obtained product, p-nitrobenzoate isooctyl ester, was added to 5 times the mass of ethanol, 4%mol concentrated hydrochloric acid and 6eq iron powder were added, and the mixture was heated to 70℃ and refluxed for 10h. (6) Post-treatment: Cool the reaction solution to 30°C, add 5% sodium hydroxide by mass, adjust pH=9, filter to remove solid insoluble matter and iron powder, heat to 70°C, concentrate to 4 times the amount of ethanol under reduced pressure of -0.09Mpa, add 4 times the amount of water by mass to the concentrate, precipitate solid, and stir thoroughly for 1h. (7) Filtration: The filtered product isooctyl para-aminobenzoate was dried at 90°C for 3 hours. (8) Coupling: Mix 3.05 eq of isooctyl p-aminobenzoate, 1 eq of cyanuric chloride, and 5 times the mass of isooctyl p-aminobenzoate with toluene, heat to 120°C and reflux for about 6 hours until no more gas is produced, the reaction is complete, and the liquid is obtained. (9) Secondary pretreatment: Add 10% sodium carbonate aqueous solution to the feed solution, neutralize to pH=7 of the reaction solution, and react to obtain a mixed solution. Wash with water to obtain a pretreated mixed solution. (10) Desolventizing: The pretreated mixture is heated to 120°C to remove toluene, and then condensed to obtain a mixture; (11) Crystal form treatment: The hot dissolution and cold precipitation method is used, with 2.5 times ethanol as the crystallization solvent, and secondary recrystallization is carried out to obtain filter cake and filtrate. After desolvation of the filtrate, ethanol is recovered to obtain filter residue. After drying, the filter cake is used to obtain ethylhexyltriazine ketone.

[0051] Hot melting and cold precipitation: Stir at 80℃ for 30 minutes, control the temperature at 70℃, filter while hot to remove impurities, slowly cool down at 15℃ / h, final temperature 5℃, and keep warm for 2 hours.

[0052] Comparative Example 1 A method for preparing an ethylhexyltriazine ketone product, using Example 1 from patent CN 116178291 A.

[0053] Application Example 1 A sunscreen composition comprising the following ingredients: 1 kg of ethylhexyl triazine obtained by the method of Example 1, 1 kg of diethylamino hydroxybenzoyl hexyl benzoate, bis-ethylhexyloxyphenol methoxyphenyl triazine, 4 kg of PEG-10 polydimethylsiloxane, 0.7 kg of oat extract, 3 kg of glycerin, 2 kg of pentanediol, 1 kg of 1,3-propanediol, 5 kg of diisopropyl sebacate, 7 kg of cyclopentamethoxysiloxane, 4 kg of cetyl PEG / PPG-10 / 1 polydimethylsiloxane, 0.5 kg of phenoxyethanol, 3 kg of nano titanium dioxide, 0.1 kg of tocopherol, and deionized water to 100%.

[0054] A method for preparing a sunscreen composition includes the following: Oil phase: Ethylhexyl triazine ketone, diethylamino hydroxybenzoyl hexyl benzoate, bis-ethylhexyloxyphenol methoxyphenyl triazine, cyclopentamethoxysilane, nano titanium dioxide, diisopropyl sebacate, PEG-10 polydimethylsiloxane, cetyl PEG / PPG-10 / 1 polydimethylsiloxane, and tocopherol are mixed and heated to 60°C to dissolve evenly; Aqueous phase: Deionized water, glycerol, pentanediol, and 1,3-propanediol are mixed and stirred until homogeneous to obtain a homogeneous aqueous solution; Emulsification: The oil phase is slowly added to the aqueous phase while stirring, and homogenized (12000 rpm, 8 min) to obtain a uniform and fine emulsion. Cool to 30°C, then add phenoxyethanol and oat extract. Stir well to obtain the final product.

[0055] The mass ratio of ethylhexyl triazine ketone, diethylamino hydroxybenzoyl hexyl benzoate, and bis-ethylhexyloxyphenol methoxyphenyl triazine is 1:1:2.5.

[0056] The oat extract is composed of montmorillonite, rosemary extract, and modified montmorillonite in a mass ratio of 1:0.3:0.5.

[0057] Preparation of oat extract: 1 kg of oats was ground into powder and then dispersed in 10 L of water. 0.2% of the oat mass of amylase was added, and the mixture was enzymatically hydrolyzed at 45 °C for 2 h. The enzyme was then inactivated at 90 °C. The mixture was filtered, and then rosemary extract and modified montmorillonite were added. The mixture was stirred for 3 h and then freeze-dried to obtain oat extract.

[0058] The modified montmorillonite is composed of montmorillonite in a mass ratio of 1:0.4:0.2, polydimethylsiloxane / vinyl polydimethylsiloxane cross-linked polymer, and polyglycerol-2 diisostearate.

[0059] Preparation of modified montmorillonite: 0.6 kg of montmorillonite was dispersed in 5 L of 0.6% sodium hydroxide solution, soaked for 2 h, washed with water, dried, calcined at 400 °C for 3 h, and ground to obtain pretreated montmorillonite. The pretreated montmorillonite, polydimethylsiloxane / vinyl polydimethylsiloxane crosspolymer, and polyglycerol-2 diisostearate were mixed evenly and dried to obtain modified montmorillonite.

[0060] The pretreatment of nano-titanium dioxide is as follows: 1 kg of polyvinylpyrrolidone / hexadecane copolymer is dispersed in 10 L of isododecane, stirred at 45 °C for 35 min, and then sprayed onto the surface of nano-titanium dioxide and spray dried (inlet air temperature 120 °C, outlet air temperature 60 °C, atomization pressure 0.2 MPa, feed rate 10 mL / min) to obtain pretreated nano-titanium dioxide.

[0061] Nano-titanium dioxide was purchased from Hangzhou Jiuli Biomaterials Co., Ltd.

[0062] Application Example 2 A sunscreen composition, differing from Application Example 1, comprises the following ingredients: 3 kg of ethylhexyl triazine obtained by the method of Example 1, ethylamino hydroxybenzoyl hexyl benzoate, bis-ethylhexyloxyphenol methoxyphenyl triazine, 5 kg of PEG-10 polydimethylsiloxane, 0.8 kg of oat extract, 5 kg of glycerin, 1 kg of pentanediol, 2 kg of 1,3-propanediol, 7 kg of diisopropyl sebacate, 9 kg of cyclopentamethoxysiloxane, 3 kg of cetyl PEG / PPG-10 / 1 polydimethylsiloxane, 1 kg of phenoxyethanol, 2 kg of nano titanium dioxide, 0.2 kg of tocopherol, and deionized water to bring the total to 100%.

[0063] The mass ratio of ethylhexyl triazine ketone, diethylamino hydroxybenzoyl hexyl benzoate, and bis-ethylhexyloxyphenol methoxyphenyl triazine is 1:1.5:0.5.

[0064] Application Example 3 A sunscreen composition differs from Application Example 1 in that the mass ratio of ethylhexyl triazine ketone, diethylamino hydroxybenzoyl hexyl benzoate, and bis-ethylhexyloxyphenol methoxyphenyl triazine is 1:3.5:0.1.

[0065] Application Example 4 A sunscreen composition, which differs from Application Example 1 in that the oat extract does not contain rosemary extract.

[0066] Application Example 5 A sunscreen composition, which differs from Application Example 1 in that the oat extract does not contain modified montmorillonite.

[0067] Application Example 6 A sunscreen composition, differing from Application Example 1, in that the modified montmorillonite does not contain polydimethylsiloxane / vinyl polydimethylsiloxane cross-linked polymer.

[0068] Application Example 7 A sunscreen composition, which differs from Application Example 1 in that the modified montmorillonite does not contain polyglycerol-2 diisostearate.

[0069] Application Example 8 A sunscreen composition differs from Application Example 1 in that the nano-titanium dioxide pretreatment does not include polyvinylpyrrolidone / hexadecane copolymer.

[0070] Application Comparative Example 1 A sunscreen composition, which differs from Application Example 1 in that it does not contain diethylaminohydroxybenzoylhexylbenzoate.

[0071] Application Comparative Example 2 A sunscreen composition, differing from Application Example 1, in that it does not contain bis-ethylhexyloxyphenol methoxyphenyl triazine.

[0072] Application Comparative Example 3 A sunscreen composition, which differs from Application Example 1 in that it does not contain nano-titanium dioxide.

[0073] Performance testing The preparation methods of ethylhexyl triazine ketone obtained in Examples 1-3 and Comparative Example 1 were subjected to performance testing. 1. The purity and yield of the ethylhexyltriazine prepared in the examples and comparative examples were determined. Purity was tested by high performance liquid chromatography (HPLC), according to the national standard GB / T 35953-2018 (Determination of Ultraviolet Absorbers in Cosmetics by High Performance Liquid Chromatography). The yield was calculated using the formula: Yield (%) = (Actual yield of the target product / Theoretical yield of the target product) × 100%.

[0074] 2. The sun protection factor (SPF) of the sun protection compositions used in the application examples and comparative examples was tested: The SPF of the sun protection compositions used in the examples and comparative examples was tested according to the method for determining the sun protection factor of sun protection products (standard PROTOCOL#700) issued by the U.S. Food and Drug Administration (FDA).

[0075] Stability test: The conditions for heat resistance stability were: temperature 45℃ for 1 month. The test results are shown in Table 1 and Table 2.

[0076] Table 1 Test data for the examples and comparative examples

[0077] Table 2 Test data for application examples and comparative examples

[0078] As can be seen from Table 1, the ethylhexyl triazine ketones prepared according to the preparation method of ethylhexyl triazine ketone in Examples 1-3 of this application have good purity and yield. Among them, the purity of Example 1 is 99.96% and the yield is 95.65%. It is evident that the ethylhexyl triazine ketone product prepared according to the preparation method of ethylhexyl triazine ketone in this application has regular crystal form, high purity, light color, and good stability.

[0079] The sunscreen compositions in Application Examples 1-2 exhibit good stability and sun protection efficacy. As shown in Table 2, Application Example 1 has a sun protection factor (SPF) of 63, good heat resistance, and a stable and homogeneous emulsion. This indicates that the overall formulation works synergistically to construct a stable, gentle, and highly tolerable silicone-in-water sunscreen system, achieving broad-spectrum and highly effective sun protection, a lightweight feel, soothing and moisturizing properties, and antioxidant effects, making it suitable for daily high-SPF sun protection and outdoor sun protection.

[0080] The sunscreen composition of Application Example 3 was modified by changing the mass ratio of ethylhexyl triazine ketone, diethylamino hydroxybenzoyl hexyl benzoate, and bis-ethylhexyloxyphenol methoxyphenyl triazine. As can be seen from Table 2, the sun protection factor (SPF) of Application Example 3 decreased, indicating that the three components have complementary solubilities in the oil and siloxane system. After compounding, it is easier to form a uniform and transparent oil phase, and it is less likely to cause problems such as sunscreen crystallization, precipitation, whitening, and pilling. The film formation is more uniform and continuous.

[0081] In the sunscreen compositions of Application Examples 4-5, rosemary extract and modified montmorillonite were not added to the oat extract, respectively. Table 2 shows that the sun protection factor (SPF) of Application Examples 4-5 decreased, heat stability was reduced, and slight emulsion stratification occurred. This indicates that rosemary extract, a natural antioxidant, anti-inflammatory, and antibacterial active ingredient, scavenges UV-induced free radicals, inhibits oil oxidation, delays formulation rancidity, and improves product stability. Modified montmorillonite possesses excellent adsorption and suspension stability, adsorbing excess oil and sweat from the skin surface, enhancing the sunscreen's oil control, anti-stickiness, and anti-sweat effects, improving the application feel, and increasing the sunscreen film's water resistance and durability.

[0082] In the sunscreen compositions of Application Examples 6-7, the modified montmorillonite was neither composed of polydimethylsiloxane / vinyl polydimethylsiloxane crosspolymer nor polyglycerol-2-diisostearate. Table 2 shows that the sun protection factor (SPF) of Application Examples 6-7 decreased, along with heat stability and varying degrees of emulsion stratification. This indicates that the polydimethylsiloxane / vinyl polydimethylsiloxane crosspolymer acts as a thickener, thixotropic agent, and skin-softening agent, improving the silky feel of the formulation, reducing stickiness, and simultaneously helping to disperse montmorillonite in the oil phase and preventing sedimentation. Polyglycerol-2-diisostearate provides surface organic modification and wetting coating to the montmorillonite, improving its compatibility and dispersibility in oil and siloxane systems.

[0083] In Application Example 8, no polyvinylpyrrolidone / hexadecane copolymer was added during the pretreatment of nano-titanium dioxide. Table 2 shows that the SPF of Application Example 8 decreased, along with reduced heat resistance and varying degrees of emulsion stratification. This indicates that the polyvinylpyrrolidone / hexadecane copolymer modifies the surface of nano-titanium dioxide, reducing the powder's surface energy, preventing particle agglomeration, and improving dispersion stability in silicone oil and synthetic ester systems.

[0084] The sunscreen compositions of Comparative Examples 1-2 were used without diethylaminohydroxybenzoylhexylbenzoate and bis-ethylhexyloxyphenol methoxyphenyl triazine, respectively. Table 2 shows that the sun protection factor (SPF) decreased with Comparative Examples 1-2. This indicates that diethylaminohydroxybenzoylhexylbenzoate has strong absorption capacity for long-wave ultraviolet radiation, increasing the PA value and preventing photoaging, dark spots, and deep skin damage; bis-ethylhexyloxyphenol methoxyphenyl triazine absorbs both UVA and UVB, exhibits excellent photostability, and synergistically enhances the overall sun protection factor and durability with other sunscreen agents.

[0085] Comparative Example 3 sunscreen compositions were applied without the addition of nano-titanium dioxide. Table 2 shows that Comparative Example 3 exhibited a decreased SPF, reduced heat stability, and moderate emulsion stratification. This indicates that nano-titanium dioxide effectively absorbs and scatters ultraviolet radiation, protecting the skin from sunburn, photoaging, and DNA damage, and possesses stable chemical properties.

[0086] This specific embodiment is merely an explanation of this application and is not intended to limit it. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they fall within the scope of the claims of this application.

Claims

1. A method for preparing ethylhexyltriazine ketone, characterized in that, Includes the following steps: (1) Condensation reaction: p-nitrobenzoic acid, isooctyl alcohol and the catalyst p-toluenesulfonic acid are mixed and heated to 145-155℃. The water generated in the reaction is separated. The reaction is continued until no more water is generated. The reaction ends and a condensation reaction solution is obtained. (2) Pretreatment: Wash the condensation reaction solution with water to obtain the washed condensation reaction solution; (3) Dehydration and filtration: The washed condensation reaction solution was added to toluene and refluxed at 120-130℃ to remove water and dehydrate, and the filtrate was obtained. (4) Purification of filtrate: The filtrate was subjected to vacuum distillation, and the fraction from 175-184℃ was collected to obtain isooctyl p-nitrobenzoate; (5) Reduction reaction: Add isooctyl p-nitrobenzoate to ethanol, add concentrated hydrochloric acid and iron powder, and reflux at 70-80℃ for 10h; (6) Post-treatment: Cool the reaction solution to 25-30℃, add sodium hydroxide, adjust pH to 9-10, filter to remove solid insoluble matter and iron powder, heat to 60-70℃, concentrate under reduced pressure, add water to the concentrate, precipitate solid, and stir thoroughly. (7) Filtration: Filtration yields isooctyl para-aminobenzoate, which is dried at 80-90℃; (8) Coupling: Mix isooctyl p-aminobenzoate, cyanuric chloride and toluene, heat to 110-120℃ and reflux until no more gas is produced, the reaction is complete and the liquid is obtained; (9) Secondary pretreatment: Add sodium carbonate aqueous solution to the feed solution, neutralize to pH 6-7 of the reaction solution, and wash with water to obtain a pretreated mixture; (10) Desolventizing: The pretreated mixture is heated to 110-120℃ to remove toluene, and then condensed to obtain a mixture; (11) Crystal form treatment: The hot dissolution and cold precipitation method is used to carry out secondary recrystallization to obtain filter cake and filtrate. After the filtrate is desolventized, ethanol is recovered to obtain filter residue. After the filter cake is dried, ethylhexyltriazine ketone is obtained.

2. The method for preparing ethylhexyl triazine ketone according to claim 1, characterized in that, In step (2), the wastewater after water washing is evaporated and salted out. In step (6), the wastewater after water washing is evaporated and salted out.

3. The method for preparing ethylhexyltriazine ketone according to claim 1, characterized in that, In step (3), the dehydrated liquid contains a small amount of insoluble solid salts, which are then filtered.

4. The method for preparing ethylhexyl triazine ketone according to claim 1, characterized in that, In step (5), the gas produced is hydrogen chloride gas. The hydrogen chloride gas is absorbed by three stages of water to prepare hydrochloric acid as a byproduct.

5. A sunscreen composition, characterized in that, The product comprises the following raw materials: ethylhexyl triazine ketone, diethylamino hydroxybenzoyl hexyl benzoate, bis-ethylhexyloxyphenol methoxyphenyl triazine, PEG-10 polydimethylsiloxane, oat extract, glycerin, pentanediol, 1,3-propanediol, diisopropyl sebacate, cyclopentamethoxysiloxane, cetyl PEG / PPG-10 / 1 polydimethylsiloxane, phenoxyethanol, nano titanium dioxide, tocopherol, and deionized water.

6. The sunscreen composition according to claim 5, characterized in that, The mass ratio of ethylhexyl triazine ketone, diethylamino hydroxybenzoyl hexyl benzoate, and bis-ethylhexyloxyphenol methoxyphenyl triazine is 1:1-1.5:0.5-2.

5.

7. The sunscreen composition according to claim 5, characterized in that, The oat extract is composed of montmorillonite, rosemary extract, and modified montmorillonite.

8. A sunscreen composition according to claim 7, characterized in that, The modified montmorillonite is composed of montmorillonite, polydimethylsiloxane / vinyl polydimethylsiloxane cross-linked polymer, and polyglycerol-2 diisostearate.

9. A sunscreen composition according to claim 5, characterized in that, The pretreatment of the nano-titanium dioxide is as follows: polyvinylpyrrolidone / hexadecane copolymer is dispersed in isododecane, stirred at 40-50℃ for 30-35 min, then sprayed onto the surface of nano-titanium dioxide, and spray-dried to obtain pretreated nano-titanium dioxide.

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