Preparation method of bis-ethyl hexyloxyphenol methoxyphenyl triazine

Abstract

The embodiment of the invention provides a preparation method of bis-ethylhexyloxyphenol methoxyphenyl triazine, and the preparation method comprises the following steps: taking 2, 4-dichloro-6-(4-methoxyphenyl) triazine and resorcinol mono-isooctane ether as raw materials, taking a synergistic activated resin as a catalyst, and reacting at the temperature of 80-90 DEG C to obtain the bis-ethylhexyloxyphenol methoxyphenyl triazine. The preparation method comprises the following steps: synthesizing bis-ethyl hexyloxyphenol methoxyphenyl triazine through a direct alkylation method; wherein the synergistic activated resin is acidic resin loaded with metal ions. According to the preparation method provided by the embodiment of the invention, at least the catalyst can be recycled and reused, a large amount of aluminum trichloride wastewater existing in a traditional synthesis method is avoided, and the preparation method is easily applied to actual industrial production.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis technology, specifically relating to a method for preparing bis-ethylhexyloxyphenol methoxyphenyl triazine. Background Technology

[0002] Bis-ethylhexyloxyphenol methoxyphenyl triazine (UV627) is a highly efficient and broad-spectrum ultraviolet absorber with strong absorption in both the UVA (320-400nm) and UVB (290-320nm) regions, showing promising application prospects in fields such as polymer aging resistance.

[0003] In the traditional synthesis method (US5955060A), 2,4-dichloro-6-(4-methoxyphenyl)triazine and resorcinol are used as raw materials. The product is obtained through alkylation reaction with aluminum trichloride catalyst and then through etherification reaction with haloisooctane. In this process, aluminum trichloride has poor solubility and is difficult to recover and reuse. The multi-substituted impurities generated are not easy to remove. A large amount of wastewater is generated after water washing, resulting in high cost of waste treatment.

[0004] Although CN115073388A proposes using supercritical CO2 as a reaction solvent, which has good solubility for the reactants, solves the problem of heterogeneous reaction, and avoids the need to use a large amount of water to wash aluminum trichloride, making aluminum trichloride easy to separate from the system, supercritical CO2 is difficult to apply in industrial production. Summary of the Invention

[0005] To address the aforementioned problems in the prior art, embodiments of this application propose a method for preparing bis-ethylhexyloxyphenol methoxyphenyl triazine. This method allows for catalyst recycling, avoids the large amounts of aluminum trichloride wastewater present in traditional synthesis methods, and is easily applicable to actual industrial production. The preparation method of this application exhibits high selectivity and high yield, and solves the problem of difficult removal of multi-substituted impurities.

[0006] According to one aspect of this application, a method for preparing bis-ethylhexyloxyphenol methoxyphenyl triazine is provided. The method includes using 2,4-dichloro-6-(4-methoxyphenyl)triazine and resorcinol monoisooctyl ether as raw materials and a co-activating resin as a catalyst to synthesize bis-ethylhexyloxyphenol methoxyphenyl triazine via direct alkylation. The co-activating resin is an acidic resin loaded with metal ions.

[0007] In some embodiments, 2,4-dichloro-6-(4-methoxyphenyl)triazine, resorcinol monoisooctyl ether, synergistic activating resin and a first solvent are mixed evenly and subjected to a Friedel-Crafts alkylation reaction. The synergistic activating resin is recovered by filtration, and the filtered solution is distilled, crystallized and dried to obtain bis-ethylhexyloxyphenol methoxyphenyltriazine.

[0008] In some embodiments, the acidic resin is one of sulfonic acid resin, phosphoric acid resin, carboxylic acid resin, and phenolic hydroxyl resin; the metal ion is Al. 3+ Fe 3+ Zn 2+ Cu 2+ Mg 2+ One or more of them.

[0009] In some embodiments, the synergistic activating resin is a sulfonic acid resin loaded with aluminum ions.

[0010] In some embodiments, the acid strength pKa value of the synergistically activated resin at 25°C is 1-2.

[0011] In some embodiments, the molar ratio of 2,4-dichloro-6-(4-methoxyphenyl)triazine to resorcinol monoisooctyl ether is 1:2.0-2.15.

[0012] In some embodiments, the mass ratio of the synergistic activating resin to resorcinol monoisooctyl ether is 0.1-1.5:1.

[0013] In some embodiments, the preparation method of bis-ethylhexyloxyphenol methoxyphenyl triazine includes one or more of the following features:

[0014] 1) The reaction temperature for Friedel-Crafts alkylation is 0-40℃;

[0015] 2) The reaction time for Friedel-Crafts alkylation is 6-10 hours;

[0016] 3) The first solvent is one or more of aromatic hydrocarbons, haloaromatic hydrocarbons, haloalkanes, and aromatic nitro compounds.

[0017] 4) The solvent used for crystallization is a second solvent, which is an alcohol or aromatic hydrocarbon solvent.

[0018] In some embodiments, the filtered synergistically activated resin is soaked in saturated brine to allow the resin to fully swell, and then dynamically regenerated with hydrogen chloride solution.

[0019] In some embodiments, dynamic regeneration is performed using a hydrogen chloride solution with a flow rate of 3-5 m / h and a mass percentage concentration of 5-10%.

[0020] Compared with the prior art, the technical solutions conceived in this application have the following advantages and effects:

[0021] Compared to existing synthesis methods that generate large amounts of aluminum-containing wastewater, have difficulty in recycling catalysts, and produce low product purity, this application uses a synergistic activated resin as a catalyst, which is easy to filter, recycle, and reuse. This eliminates the extensive water washing process in traditional synthesis methods, avoids the generation of aluminum-containing wastewater, and meets green environmental protection requirements. It also exhibits good catalytic selectivity and a product purity of up to 99.9%. Detailed Implementation

[0022] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention. It should be understood that the technical features involved in the various embodiments of this application described below can be combined with each other as long as they do not conflict with each other.

[0023] The conventional method for synthesizing UV-627 uses a strong Lewis acid (aluminum trichloride) as a catalyst. Its core function is to activate the electron-deficient triazine ring of 2,4-dichloro-6-(4-methoxyphenyl)triazine. After the chlorine atom is coordinated and activated by the strong Lewis acid, a Friedel-Crafts alkylation reaction occurs. Bronsted acids can catalyze conventional condensation reactions, but they exhibit low selectivity for the reaction in this application and do not provide satisfactory catalytic performance. Furthermore, existing Bronsted acid catalysts do not involve the specific reactant combination of an electron-deficient triazine ring and a sterically hindered phenol. Those skilled in the art generally believe that Bronsted acids have weaker catalytic activity for Friedel-Crafts alkylation reactions than Lewis acids and cannot activate the chlorine atom of the electron-deficient triazine ring, thus preventing the reaction from starting.

[0024] Furthermore, the resorcinol monoisooctyl ether raw material contains two phenolic hydroxyl units, one of which is attached to a sterically hindered isooctyl group, while the other is unsubstituted. Under conventional Lewis acid catalysis, polysubstituted side reactions are prone to occur, such as the reaction of both phenolic hydroxyl carbons with triazine, or the isooctyl group migrating before reacting. If a general acidic resin is used instead, those skilled in the art may worry that the lack of steric selectivity at the resin's acidic sites could exacerbate polysubstituted side reactions.

[0025] This application uses a synergistically activated resin as a catalyst, which utilizes the synergistic activation of Bronsted and Lewis acids to overcome the shortcomings of insufficient activity. For example, sulfonic acid groups (-SO3H) provide Bronsted acid sites; supported Al 3+As a Lewis acid activation site, it coordinates and activates the chlorine atom of the triazine ring. The synergistic effect of these two active sites overcomes the limitation that Bronsted acids alone cannot activate electron-deficient rings, achieving the required reactivity. The acidic resin is a solid particle; its surface acidic sites are encapsulated by the resin framework, forming a steric hindrance sieve. The highly sterically hindered isooctyl group of resorcinol monoisooctyl ether is blocked by the resin framework, allowing only the unsubstituted phenolic hydroxyl terminus to approach the triazine ring and react. This sterically suppresses multi-substitution side reactions, effectively reducing impurity generation.

[0026] This application provides a method for preparing bis-ethylhexyloxyphenol methoxyphenyl triazine. The method involves using 2,4-dichloro-6-(4-methoxyphenyl)triazine and resorcinol monoisooctyl ether as raw materials, and a co-activating resin as a catalyst, to synthesize bis-ethylhexyloxyphenol methoxyphenyl triazine via direct alkylation. The co-activating resin is an acidic resin loaded with metal ions. This method offers a novel approach to synthesizing bis-ethylhexyloxyphenol methoxyphenyl triazine with mild reaction conditions, high selectivity, and recyclable catalyst. The catalyst used in this method—the co-activating resin—is easy to filter and recycle, eliminating the extensive water washing process in traditional synthesis methods and avoiding the generation of aluminum-containing wastewater, thus meeting green environmental protection requirements. The co-activating resin in this application exhibits good catalytic selectivity, and the product purity can reach 99.9%.

[0027] In some embodiments, the acidic resin may be one of sulfonic acid resin, phosphoric acid resin, carboxylic acid resin, or phenolic hydroxyl resin, and the supported metal ions may be Al. 3+ Fe 3+ Zn 2+ Cu 2+ Mg 2+ One or more of the following. In a preferred embodiment, the synergistic activating resin is a sulfonic acid resin loaded with aluminum ions. In some embodiments, the acid strength pKa value of the synergistic activating resin at 25°C is 1-2.

[0028] In some embodiments, the molar ratio of 2,4-dichloro-6-(4-methoxyphenyl)triazine to resorcinol monoisooctyl ether is 1:2.0-2.15, for example, 1:2.05. Traditional Friedel-Crafts reactions often use an excess ratio of 1:2.2-2.5 to ensure complete reaction of the expensive raw material. However, due to the good selectivity of the synergistic activated resin, only a small excess is required in this application. When the molar amount of resorcinol monoisooctyl ether is 2.0-2.15 times the molar amount of 2,4-dichloro-6-(4-methoxyphenyl)triazine, an excess of 0.05-0.15 times the resorcinol derivative can ensure complete reaction of 2,4-dichloro-6-(4-methoxyphenyl)triazine, resulting in a conversion rate of >99% for the raw material 2,4-dichloro-6-(4-methoxyphenyl)triazine. This avoids monosubstituted impurities that are difficult to remove by crystallization. When the amount of resorcinol monoisooctyl ether is less than 2.0 times the amount of 2,4-dichloro-6-(4-methoxyphenyl)triazine, the conversion rate of 2,4-dichloro-6-(4-methoxyphenyl)triazine decreases, the amount of monosubstituted impurities increases, and the purity decreases. When the amount of resorcinol monoisooctyl ether is greater than 2.15 times the amount of 2,4-dichloro-6-(4-methoxyphenyl)triazine, the resorcinol derivative is excessive and difficult to remove completely during crystallization, resulting in a decrease in product purity.

[0029] In some embodiments, the mass ratio of the synergistic activating resin to resorcinol monoisooctyl ether is 0.1-1.5:1, for example, 0.6:1. When the mass ratio is 0.1-1.5, the amount of synergistic activating resin can cover the activation requirements of all raw material molecules, ensuring the completion of the reaction. When the mass ratio exceeds 1.5, there is an excess of active sites, but the raw material concentration is fixed, and the reaction rate does not increase significantly (the reaction time changes from 6 hours to 5.9 hours). On the contrary, the excessive solid resin leads to an increase in system viscosity, uneven stirring, local overheating and side reactions, and increased filtration and recovery time. When the mass ratio is less than 0.1, there are insufficient active sites, the reaction rate is extremely slow, only 50% conversion is completed in 10 hours, there is a large amount of 2,4-dichloro-6-(4-methoxyphenyl)triazine residue, an increase in monosubstituted impurities, and a low yield (<60%).

[0030] In some embodiments, 2,4-dichloro-6-(4-methoxyphenyl)triazine, resorcinol monoisooctyl ether, synergistic activating resin and a first solvent are mixed evenly and subjected to a Friedel-Crafts alkylation reaction. The synergistic activating resin is recovered by filtration, and the filtered solution is distilled, crystallized and dried to obtain bis-ethylhexyloxyphenol methoxyphenyltriazine.

[0031] In some embodiments, the first solvent may be one or more of aromatic hydrocarbons, halogenated aromatic hydrocarbons, halogenated alkanes, and aromatic nitro compounds. For example, the first solvent may be one or more of toluene, chlorobenzene, dichloromethane, and nitrobenzene.

[0032] In some embodiments, the solvent used for crystallization is a second solvent, which is an alcohol or aromatic hydrocarbon solvent. For example, the second solvent may be methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, toluene, m-xylene, p-xylene, ethylbenzene, cumene, tert-butylbenzene, etc.

[0033] It should be understood that the first solvent and the second solvent can also be any other suitable solvent.

[0034] In some embodiments, the Friedel-Crafts alkylation reaction is carried out at a temperature of 0-40°C, for example, 30°C. Traditional aluminum trichloride catalysis requires activation at 50-80°C, while this application, due to the synergistic active sites of the synergistic activating resin, allows for reaction at a milder temperature. A reaction temperature of 0-40°C suppresses side reactions and ensures the reaction rate. The Friedel-Crafts reaction is exothermic; temperatures above 40°C cause alkyl migration of the isooctyl group in resorcinol monoisooctyl ether, leading to increased impurities and decreased purity; temperatures below 0°C decrease the reaction rate, resulting in a significant reduction in yield after 10 hours.

[0035] In some embodiments, the Friedel-Crafts alkylation reaction takes 6-10 hours. A reaction time of 6 hours ensures the reaction endpoint. Verification by examples shows that with a reaction time of 6 hours, the triazine conversion is >99%, monosubstituted impurities are <0.1%, and the yield is >90%. An upper limit of 10 hours avoids product degradation. Prolonged exposure (>10 hours) under acidic conditions may cause the triazine ring of the product to decompose, or the phenolic hydroxyl group to be substituted by the solvent, resulting in decreased purity. If the reaction time is less than 6 hours, the reaction does not reach the endpoint, resulting in a large amount of residual triazine and a low yield. If the reaction time is greater than 10 hours (e.g., 12 hours), decomposition impurities increase, as does phenoxy impurities, and the purity decreases from 90.4% (10 hours) to below 66.7% (12 hours).

[0036] In some embodiments, the recycled synergistic activated resin can be obtained by soaking the filtered synergistic activated resin in saturated brine to allow the resin to fully swell, and then dynamically regenerating it with hydrogen chloride solution. Preferably, the filtered synergistic activated resin is soaked in saturated brine (for 18-20 hours) to allow the resin to fully swell, and then dynamically regenerated using a hydrogen chloride solution with a flow rate of 3-5 m / h and a mass percentage concentration of 5-10%, wherein the contact time can be 30-60 minutes.

[0037] The present application will be described in more detail below through examples and comparative examples.

[0038] Example 1

[0039] Under normal pressure, in a clean reactor, 511 g of 2,4-dichloro-6-(4-methoxyphenyl)triazine, 888 g of resorcinol monoisooctyl ether, 205 g of supported aluminum sulfonic acid resin, and 3322 ml of chlorobenzene were mixed and stirred. The mixture was heated to 30°C and maintained at 30-40°C. After reacting for 6 hours, the resin was filtered and regenerated. The chlorobenzene was distilled off by steam distillation, and 1900 g of ethanol was added. After crystallization and drying, 1129.9 g of bis-ethylhexyloxyphenol methoxyphenyl triazine was obtained, with a yield of 90.1% and a purity of 99.9%.

[0040] Example 2

[0041] Under normal pressure, in a clean reactor, 511 g of 2,4-dichloro-6-(4-methoxyphenyl)triazine, 888 g of resorcinol monoisooctyl ether, 205 g of supported aluminum phosphate resin, and 3322 ml of chlorobenzene were mixed and stirred. The mixture was heated to 30°C and maintained at 30-40°C. After reacting for 6 hours, the resin was filtered and regenerated. The chlorobenzene was distilled off by steam distillation, and 1900 g of ethanol was added. After crystallization and drying, 1126.1 g of bis-ethylhexyloxyphenol methoxyphenyl triazine was obtained, with a yield of 89.8% and a purity of 99.9%.

[0042] Example 3

[0043] Under normal pressure, in a clean reactor, 511 g of 2,4-dichloro-6-(4-methoxyphenyl)triazine, 954.6 g of resorcinol monoisooctyl ether, 219.6 g of supported aluminum sulfonic acid resin, and 3322 ml of chlorobenzene were mixed and stirred. The mixture was heated to 30°C and maintained at 30-40°C. After reacting for 6 hours, the resin was filtered and regenerated. The chlorobenzene was distilled off by steam distillation, and 1900 g of ethanol was added. After crystallization and drying, 1131.1 g of bis-ethylhexyloxyphenol methoxyphenyl triazine was obtained, with a yield of 90.2% and a purity of 99.9%.

[0044] Example 4

[0045] Under normal pressure, in a clean reactor, 511 g of 2,4-dichloro-6-(4-methoxyphenyl)triazine, 888 g of resorcinol monoisooctyl ether, 88.8 g of supported aluminum sulfonic acid resin, and 3322 ml of chlorobenzene were mixed and stirred. The mixture was heated to 30°C and maintained at 30-40°C. After reacting for 6 hours, the resin was filtered and regenerated. The chlorobenzene was distilled off with steam, and 1900 g of ethanol was added. After crystallization and drying, 1048.3 g of bis-ethylhexyloxyphenol methoxyphenyl triazine was obtained, with a yield of 83.6% and a purity of 90.8%.

[0046] Example 5

[0047] Under normal pressure, in a clean reactor, 511 g of 2,4-dichloro-6-(4-methoxyphenyl)triazine, 888 g of resorcinol monoisooctyl ether, 1332 g of supported aluminum sulfonic acid resin, and 3322 ml of chlorobenzene were mixed and stirred. The mixture was heated to 30°C and maintained at 30-40°C. After reacting for 6 hours, the resin was filtered and regenerated. The chlorobenzene was distilled off by steam distillation. 1900 g of ethanol was added, and the mixture was crystallized and dried to obtain 1112.3 g of bis-ethylhexyloxyphenol methoxyphenyl triazine, with a yield of 88.7% and a purity of 91.4%.

[0048] Example 6

[0049] Under normal pressure, in a clean reactor, 511 g of 2,4-dichloro-6-(4-methoxyphenyl)triazine, 888 g of resorcinol monoisooctyl ether, 205 g of supported aluminum sulfonic acid resin, and 3322 ml of chlorobenzene were mixed and stirred. The mixture was cooled to 0°C and maintained at 0-10°C. After reacting for 6 hours, the resin was filtered and regenerated. The chlorobenzene was distilled off by steam distillation, and 1900 g of ethanol was added. After crystallization and drying, 843.9 g of bis-ethylhexyloxyphenol methoxyphenyl triazine was obtained, with a yield of 67.3% and a purity of 83.6%.

[0050] Example 7

[0051] Under normal pressure, in a clean reactor, 511 g of 2,4-dichloro-6-(4-methoxyphenyl)triazine, 888 g of resorcinol monoisooctyl ether, 205 g of supported aluminum sulfonic acid resin, and 3322 ml of chlorobenzene were mixed and stirred. The mixture was heated to 40°C and maintained at 30-40°C. After reacting for 6 hours, the resin was filtered and regenerated. The chlorobenzene was distilled off by steam distillation. 1900 g of ethanol was added, and the mixture was crystallized and dried to obtain 1121.1 g of bis-ethylhexyloxyphenol methoxyphenyl triazine, with a yield of 89.4% and a purity of 92.2%.

[0052] Example 8

[0053] Under normal pressure, in a clean reactor, 511 g of 2,4-dichloro-6-(4-methoxyphenyl)triazine, 888 g of resorcinol monoisooctyl ether, 205 g of supported aluminum sulfonic acid resin, and 3322 ml of chlorobenzene were mixed and stirred. The mixture was heated to 30°C and maintained at 30-40°C. After reacting for 10 hours, the resin was filtered and regenerated. The chlorobenzene was distilled off by steam distillation, and 1900 g of ethanol was added. After crystallization and drying, 984.4 g of bis-ethylhexyloxyphenol methoxyphenyl triazine was obtained, with a yield of 78.5% and a purity of 90.4%.

[0054] Example 9

[0055] Under normal pressure, in a clean reactor, 511 g of 2,4-dichloro-6-(4-methoxyphenyl)triazine and 888 g of resorcinol monoisooctyl ether, along with 205 g of Fe, were... 3+The carboxylic acid type resin was mixed with 3322 ml of chlorobenzene and stirred. The temperature was raised to 30°C and maintained at 30-40°C. After reacting for 6 hours, the resin was filtered and regenerated. Chlorobenzene was distilled off by steam distillation. 1900 g of ethanol was added, and the mixture was crystallized and dried to obtain 1074.7 g of bis-ethylhexyloxyphenol methoxyphenyl triazine, with a yield of 85.7% and a purity of 97.9%.

[0056] Example 10

[0057] Under normal pressure, in a clean reactor, 511 g of 2,4-dichloro-6-(4-methoxyphenyl)triazine, 888 g of resorcinol monoisooctyl ether, and 205 g of Zn were loaded. 2+ The phenolic hydroxyl resin was mixed with 3322 ml of chlorobenzene and stirred. The temperature was raised to 30°C and maintained at 30-40°C. After reacting for 6 hours, the resin was filtered and regenerated. The chlorobenzene was distilled off with steam. 1900 g of ethanol was added, and the mixture was crystallized and dried to obtain 1048.3 g of bis-ethylhexyloxyphenol methoxyphenyl triazine, with a yield of 83.6% and a purity of 86.4%.

[0058] Comparative Example 1

[0059] Under normal pressure, in a clean reactor, 511 g of 2,4-dichloro-6-(4-methoxyphenyl)triazine, 799.2 g of resorcinol monoisooctyl ether, 183.8 g of supported aluminum sulfonic acid resin, and 3322 ml of chlorobenzene were mixed and stirred. The mixture was heated to 30°C and maintained at 30-40°C. After reacting for 6 hours, the resin was filtered and regenerated. The chlorobenzene was distilled off by steam distillation. 1900 g of ethanol was added, and the mixture was crystallized and dried to obtain 856.5 g of bis-ethylhexyloxyphenol methoxyphenyl triazine, with a yield of 68.3% and a purity of 76.2%.

[0060] Comparative Example 2

[0061] Under normal pressure, in a clean reactor, 511 g of 2,4-dichloro-6-(4-methoxyphenyl)triazine, 976.8 g of resorcinol monoisooctyl ether, 224.7 g of supported aluminum sulfonic acid resin, and 3322 ml of chlorobenzene were mixed and stirred. The mixture was heated to 30°C and maintained at 30-40°C. After reacting for 6 hours, the resin was filtered and regenerated. The chlorobenzene was distilled off by steam distillation, and 1900 g of ethanol was added. After crystallization and drying, 1073.4 g of bis-ethylhexyloxyphenol methoxyphenyl triazine was obtained, with a yield of 85.6% and a purity of 87.4%.

[0062] Comparative Example 3

[0063] Under normal pressure, in a clean reactor, 511 g of 2,4-dichloro-6-(4-methoxyphenyl)triazine, 888 g of resorcinol monoisooctyl ether, 44.4 g of supported aluminum sulfonic acid resin, and 3322 ml of chlorobenzene were mixed and stirred. The mixture was heated to 30°C and maintained at 30-40°C. After reacting for 6 hours, the resin was filtered and regenerated. The chlorobenzene was distilled off by steam distillation, and 1900 g of ethanol was added. After crystallization and drying, 734.8 g of bis-ethylhexyloxyphenol methoxyphenyl triazine was obtained, with a yield of 58.6% and a purity of 68.2%.

[0064] Comparative Example 4

[0065] Under normal pressure, in a clean reactor, 511 g of 2,4-dichloro-6-(4-methoxyphenyl)triazine, 888 g of resorcinol monoisooctyl ether, 1776 g of supported aluminum sulfonic acid resin, and 3322 ml of chlorobenzene were mixed and stirred. The mixture was heated to 30°C and maintained at 30-40°C. After reacting for 6 hours, the resin was filtered and regenerated. The chlorobenzene was distilled off by steam distillation, and 1900 g of ethanol was added. After crystallization and drying, 976.9 g of bis-ethylhexyloxyphenol methoxyphenyl triazine was obtained, with a yield of 77.9% and a purity of 83.4%.

[0066] Comparative Example 5

[0067] Under normal pressure, in a clean reactor, 511 g of 2,4-dichloro-6-(4-methoxyphenyl)triazine, 888 g of resorcinol monoisooctyl ether, 205 g of supported aluminum sulfonic acid resin, and 3322 ml of chlorobenzene were mixed and stirred. The mixture was cooled to -10°C and maintained at -5 to -10°C. After reacting for 6 hours, the resin was filtered and regenerated. The chlorobenzene was distilled off by steam distillation, and 1900 g of ethanol was added. The mixture was then crystallized and dried to obtain 588.1 g of bis-ethylhexyloxyphenol methoxyphenyl triazine, with a yield of 46.9% and a purity of 55.4%.

[0068] Comparative Example 6

[0069] Under normal pressure, in a clean reactor, 511 g of 2,4-dichloro-6-(4-methoxyphenyl)triazine, 888 g of resorcinol monoisooctyl ether, 205 g of supported aluminum sulfonic acid resin, and 3322 ml of chlorobenzene were mixed and stirred. The mixture was heated to 50°C and maintained at 50-60°C. After reacting for 6 hours, the resin was filtered and regenerated. The chlorobenzene was distilled off by steam distillation, and 1900 g of ethanol was added. After crystallization and drying, 869.0 g of bis-ethylhexyloxyphenol methoxyphenyl triazine was obtained, with a yield of 69.3% and a purity of 82.2%.

[0070] Comparative Example 7

[0071] Under normal pressure, in a clean reactor, 511 g of 2,4-dichloro-6-(4-methoxyphenyl)triazine, 888 g of resorcinol monoisooctyl ether, 205 g of supported aluminum sulfonic acid resin, and 3322 ml of chlorobenzene were mixed and stirred. The mixture was heated to 30°C and maintained at 30-40°C. After reacting for 4 hours, the resin was filtered and regenerated. The chlorobenzene was distilled off by steam distillation. 1900 g of ethanol was added, and the mixture was crystallized and dried to obtain 847.7 g of bis-ethylhexyloxyphenol methoxyphenyl triazine, with a yield of 67.6% and a purity of 79.2%.

[0072] Comparative Example 8

[0073] Under normal pressure, in a clean reactor, 511 g of 2,4-dichloro-6-(4-methoxyphenyl)triazine, 888 g of resorcinol monoisooctyl ether, 205 g of supported aluminum sulfonic acid resin, and 3322 ml of chlorobenzene were mixed and stirred. The mixture was heated to 30°C and maintained at 30-40°C. After reacting for 12 hours, the resin was filtered and regenerated. The chlorobenzene was distilled off by steam distillation, and 1900 g of ethanol was added. After crystallization and drying, 865.3 g of bis-ethylhexyloxyphenol methoxyphenyl triazine was obtained, with a yield of 69.0% and a purity of 66.7%.

[0074] Comparative Example 9

[0075] Under normal pressure, in a clean reactor, 511 g of 2,4-dichloro-6-(4-methoxyphenyl)triazine, 888 g of resorcinol monoisooctyl ether, 205 g of sulfonic acid resin, and 3322 ml of chlorobenzene were mixed and stirred. The mixture was heated to 30°C and maintained at 30-40°C. After reacting for 6 hours, the resin was filtered and regenerated. The chlorobenzene was distilled off by steam distillation. 1900 g of ethanol was added, and the mixture was crystallized and dried to obtain 16 g of bis-ethylhexyloxyphenol methoxyphenyl triazine, with a yield of 1.3% and a purity of 10.2%.

[0076] Comparative Example 10

[0077] Under normal pressure, in a clean reactor, 511 g of 2,4-dichloro-6-(4-methoxyphenyl)triazine, 888 g of resorcinol monoisooctyl ether, 205 g of phosphate resin, and 3322 ml of chlorobenzene were mixed and stirred. The mixture was heated to 30°C and maintained at 30-40°C. After reacting for 6 hours, the resin was filtered and regenerated. The chlorobenzene was distilled off by steam distillation. 1900 g of ethanol was added, and the mixture was crystallized and dried to obtain 14 g of bis-ethylhexyloxyphenol methoxyphenyl triazine, with a yield of 1.1% and a purity of 9.5%.

[0078] This application uses a synergistically activated resin as a catalyst and 2,4-dichloro-6-(4-methoxyphenyl)triazine and resorcinol monoisooctyl ether as raw materials to synthesize bis-ethylhexyloxyphenol methoxyphenyltriazine via direct alkylation. The reaction can be carried out at a lower temperature under mild conditions, without the need for supercritical CO2 or other environmental conditions. The reaction has high selectivity, high yield, and high purity. The catalyst can be reused after regeneration, which reduces production costs.

[0079] The above description is merely a preferred embodiment of this application and is not intended to limit this application. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this application should be included within the protection scope of this application.

Claims

1. A method for preparing bis-ethylhexyloxyphenol methoxyphenyl triazine, characterized in that, The bis-ethylhexyloxyphenol methoxyphenyl triazine was synthesized by direct alkylation using 2,4-dichloro-6-(4-methoxyphenyl)triazine and resorcinol monoisooctyl ether as raw materials and synergistic activated resin as catalyst. The synergistic activating resin is an acidic resin loaded with metal ions.

2. The preparation method according to claim 1, characterized in that, The 2,4-dichloro-6-(4-methoxyphenyl)triazine, the resorcinol monoisooctyl ether, the synergistic activating resin, and the first solvent were mixed evenly and subjected to a Friedel-Crafts alkylation reaction. The synergistic activating resin was recovered by filtration, and the filtered solution was distilled, crystallized, and dried to obtain the bis-ethylhexyloxyphenol methoxyphenyltriazine.

3. The preparation method according to claim 1, characterized in that, The acidic resin is one of sulfonic acid resin, phosphoric acid resin, carboxylic acid resin, and phenolic hydroxyl resin; the metal ion is Al. 3+ Fe 3+ Zn 2+ Cu 2+ Mg 2+ One or more of them.

4. The preparation method according to claim 3, characterized in that, The synergistic activating resin is a sulfonic acid resin loaded with aluminum ions.

5. The preparation method according to claim 3, characterized in that, The acid strength pKa value of the synergistically activated resin at 25°C is 1-2.

6. The preparation method according to claim 1, characterized in that, The molar ratio of the 2,4-dichloro-6-(4-methoxyphenyl)triazine to the resorcinol monoisooctyl ether is 1:2.0-2.

15.

7. The preparation method according to claim 1, characterized in that, The mass ratio of the synergistic activating resin to the resorcinol monoisooctyl ether is 0.1-1.5:

1.

8. The preparation method according to claim 2, characterized in that, Includes one or more of the following characteristics: 1) The reaction temperature of the Friedel-Crafts alkylation reaction is 0-40℃; 2) The reaction time for the Friedel-Crafts alkylation reaction is 6-10 hours; 3) The first solvent is one or more of aromatic hydrocarbons, haloaromatic hydrocarbons, haloalkanes, and aromatic nitro compounds; 4) The solvent used for crystallization is a second solvent, which is an alcohol or aromatic hydrocarbon solvent.

9. The preparation method according to claim 2, characterized in that, The filtered synergistic activated resin was soaked in saturated saline solution to allow the resin to fully swell, and then dynamically regenerated with hydrogen chloride solution.

10. The preparation method according to claim 9, characterized in that, The dynamic regeneration is performed using a hydrogen chloride solution with a flow rate of 3-5 m / h and a mass percentage concentration of 5-10%.