Purification method of 2-(2, 4-dihydroxyphenyl)-4, 6-bis (2, 4-dimethylphenyl)-S-triazine
By using mixture of water, ethyl acetate, and hydrochloric acid to remove miscellaneous and crystalline, 2- (2,4-dihydroxylphenyl) -4,6-2 (2,4-dihydonhel)- The problem of different discoloration and impurities in the intermediate body of the S-triazine has achieved high purity and high-quality intermediate preparation.
Patent Information
- Application Number
- CN202310882058.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2023-07-18
- Publication Date
- 2025-01-21
AI Technical Summary
In the prior art, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-S-triazine intermediates are prone to discoloration and have many impurities, which affects subsequent reaction products. quality.
Water, ethyl acetate and hydrochloride were used to remove miscellaneous solutions, and then crystals were performed. By controlling the crystallization temperature and the selection of solvents, the intermediate removal was removed.
Effectively improves the purity of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-S-triazine to more than 99.5%, reducing the need for subsequent products influence and improve the color purity of the product.
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Abstract
Description
Technical Field
[0001] The invention relates to the technical field of ultraviolet absorbers, and in particular to a method for purifying 2-(2,4-dihydroxyphenyl)-4,6-di(2,4-dimethylphenyl)-S-triazine. Background Art
[0002] A triazine ultraviolet absorber, whose chemical name is 2,4-bis(2,4-xylyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, is a high-efficiency anti-aging additive with excellent performance and is widely used in polymers such as PE, PET, and PA.
[0003] 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-S-triazine is an important intermediate for preparing the above-mentioned triazine ultraviolet absorbers, which is usually synthesized using cyanuric chloride, meta-xylene, and resorcinol as raw materials. However, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-S-triazine prepared by existing synthesis methods will produce undesirable discoloration and impurities, resulting in the product color appearing gray-black. 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-S-triazine has many discolorations and impurities, which will continue to be introduced into the 2,4-bis(2,4-xylyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine product prepared by subsequent reactions, affecting the product quality of triazine ultraviolet absorbers. Therefore, it is necessary to purify 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-S-triazine. Summary of the invention
[0004] The invention provides a purification method for 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-S-triazine, which is used to solve the defects of discoloration and a large number of impurities of the intermediate in the prior art, achieve impurity removal and decolorization of the intermediate, and reduce the influence on the subsequent preparation of 2,4-bis(2,4-xylyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine products.
[0005] The present invention provides a method for purifying 2-(2,4-dihydroxyphenyl)-4,6-di(2,4-dimethylphenyl)-S-triazine, comprising:
[0006] The reaction liquid containing 2-(2,4-dihydroxyphenyl)-4,6-di(2,4-dimethylphenyl)-S-triazine is decontaminated with a mixed solution of water, ethyl acetate and hydrochloric acid to remove the solvent and water-soluble impurities to obtain a solid base material; the solid base material is crystallized, and the crystallization solvent is xylene, toluene, n-heptane or cyclohexane.
[0007] The invention adopts impurity removal and crystallization under specific conditions, which can better remove impurities and make the purity of the obtained 2-(2,4-dihydroxyphenyl)-4,6-di(2,4-dimethylphenyl)-S-triazine reach more than 99.5%.
[0008] According to the preparation method provided by the present invention, the crystallization step comprises: mixing the solid base material with a crystallization solvent, stirring at a temperature below 140°C for 1-2 hours to dissolve, then cooling to 5-15°C to crystallize, and after the crystallization is completed, filtering the filter cake to obtain a wet crude product.
[0009] The amount of the crystallization solvent used is based on the amount that can completely dissolve the solid base material, but it should not be too much, otherwise it will affect the yield.
[0010] In addition, the crystallization temperature needs to be controlled at 5-15°C, which is conducive to the precipitation of the crystallized product and improves the yield of the crystallized product.
[0011] Furthermore, the preparation method provided by the present invention also includes: mixing the wet crude product with a mixed solution of a recrystallization solvent and an adsorbent material, stirring at a temperature of 1-2 hours, filtering the filtrate, cooling the filtrate to -10 to 10°C for recrystallization, and after the crystallization is completed, filtering the filter cake to obtain a yellow wet fine product with a purity greater than or equal to 99.5%.
[0012] The invention can further purify the wet crude product and further decolorize the product, so as to change the gray wet crude product into a yellow wet fine product, which is beneficial to improving the quality of 2,4-bis(2,4-xylyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine.
[0013] Wherein, the re-crystallization solvent is ethyl acetate, methanol, ethanol or methyl isobutyl ketone. Preferably, the re-crystallization solvent is ethyl acetate, and the temperature of heat preservation and stirring is 70-90° C., more preferably 75-80° C. The amount of the re-crystallization solvent is based on the total dissolution of the wet crude product.
[0014] The adsorption material is activated carbon, diatomaceous earth, primary silica gel or activated white clay.
[0015] Preferably, the adsorption material is activated carbon with a particle size of 100-200 mesh, which is 5%-10% of the crude wet mass quality.
[0016] Furthermore, after obtaining the wet fine product, it is dried at 100-150° C. to obtain the 2-(2,4-dihydroxyphenyl)-4,6-di(2,4-dimethylphenyl)-S-triazine fine product.
[0017] In some specific embodiments of the present invention, the step of obtaining a solid base material comprises:
[0018] Using cyanuric chloride and m-xylene as raw materials, adding a reaction solvent to react under the catalytic action of aluminum chloride to generate an intermediate, and the intermediate reacts with resorcinol to generate 2-(2,4-dihydroxyphenyl)-4,6-di(2,4-dimethylphenyl)-S-triazine;
[0019] The reaction solution containing 2-(2,4-dihydroxyphenyl)-4,6-di(2,4-dimethylphenyl)-S-triazine is extracted with a mixed solution of water, ethyl acetate and hydrochloric acid at an extraction temperature of 70-90° C., the aqueous phase is removed, the organic phase is retained and desolventized under reduced pressure to obtain the solid base material.
[0020] The reaction process is specifically divided into the following two steps:
[0021]
[0022] (1) Add appropriate amounts of cyanuric chloride, o-dichlorobenzene and aluminum chloride to a reaction container to prepare a mixed solution, wherein o-dichlorobenzene is a solvent and aluminum chloride is a catalyst, heat and stir the mixed solution, and continue to keep the temperature and stir until the internal temperature is heated to 80-100° C. to fully dissolve the cyanuric chloride; take a certain amount of m-xylene, slowly drop it into the mixed solution, and keep the temperature to react until the reaction is complete; then slowly cool the reaction solution to 30-40° C., drop a certain amount of m-xylene again, and continue to keep the temperature to react until the reaction is complete after the drop is complete, thereby obtaining a first reaction solution.
[0023] In the above scheme, the solvent o-dichlorobenzene can also be selected from solvents such as DMF, PEG-400, toluene, xylene, chlorobenzene, dichloroethane, etc. that can dissolve cyanuric chloride.
[0024] (2) After the first step of the reaction is completed, the first reaction liquid is cooled to 10-20°C. Too high a temperature will cause a large number of bubbles to form in the reaction liquid. Take an appropriate amount of resorcinol and add it to the first reaction liquid to react for about 1 hour; then slowly heat it to 75-85°C and react for about 2 hours to obtain a second reaction liquid. The second reaction liquid is the target reaction liquid containing 2-(2,4-dihydroxyphenyl)-4,6-di(2,4-dimethylphenyl)-S-triazine.
[0025] The reaction solution containing 2-(2,4-dihydroxyphenyl)-4,6-di(2,4-dimethylphenyl)-S-triazine is a mixture. The research of the present invention finds that for the reaction solution containing 2-(2,4-dihydroxyphenyl)-4,6-di(2,4-dimethylphenyl)-S-triazine, a mixed solution of water, ethyl acetate and hydrochloric acid is used to extract the target compound, the extraction temperature is 70-90°C, and the impurity removal effect is good.
[0026] Further, the amount of water used is calculated to be 100g / 0.1mol-150g / 0.1mol cyanuric chloride relative to the molar amount of cyanuric chloride;
[0027] The amount of ethyl acetate used is calculated to be 80 g / 0.1 mol-150 g / 0.1 mol cyanuric chloride relative to the molar amount of cyanuric chloride;
[0028] The hydrochloric acid is concentrated hydrochloric acid, and its usage is calculated as 2g / 0.1mol-8g / 0.1mol cyanuric chloride relative to the molar amount of cyanuric chloride.
[0029] In a preferred embodiment of the present invention, the extraction solution consists of 150 g of water, 100 g of ethyl acetate and 5 g of concentrated hydrochloric acid relative to 0.1 mol of cyanuric chloride.
[0030] Furthermore, the extraction step includes: fully stirring at a temperature of 70-90°C, standing for stratification, separating the aqueous phase and the organic phase, and washing the organic phase twice at a temperature of 70-90°C.
[0031] Furthermore, the step of desolventizing under reduced pressure includes: desolventizing the organic phase under reduced pressure, controlling the vacuum degree to be greater than or equal to 0.090 MPa, and gradually raising the distillation temperature to above 150° C. until there is no obvious fraction to obtain a solid bottom material. The desolventizing under reduced pressure can remove residual o-dichlorobenzene and improve the yield of the intermediate.
[0032] The present invention also provides a triazine ultraviolet absorber product, which is prepared by reacting 1-chlorooctane and 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-S-triazine obtained by any of the above purification methods as raw materials. Using the 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-S-triazine purified by the present invention as a raw material, a 2,4-bis(2,4-xylyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine product with excellent product color and quality can be prepared.
[0033] The invention provides a purification method for 2-(2,4-dihydroxyphenyl)-4,6-di(2,4-dimethylphenyl)-S-triazine. By adopting impurity removal and crystallization under specific conditions, impurity removal and decolorization can be better performed, so that the color of the obtained 2-(2,4-dihydroxyphenyl)-4,6-di(2,4-dimethylphenyl)-S-triazine is pure, and the purity can reach more than 99.5%. High-quality conditions are provided for the subsequent preparation of high-quality 2,4-bis(2,4-xylyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, and the purification method is simple and easy to industrialize. BRIEF DESCRIPTION OF THE DRAWINGS
[0034] Figure 1 This is a physical picture of the 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-S-triazine product in Example 1;
[0035] Figure 2 The HPLC chromatogram of the 2-(2,4-dihydroxyphenyl)-4,6-di(2,4-dimethylphenyl)-S-triazine product in Example 1;
[0036] Figure 3 This is a physical picture of the 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-S-triazine product in Example 2;
[0037] Figure 4 The HPLC chromatogram of the 2-(2,4-dihydroxyphenyl)-4,6-di(2,4-dimethylphenyl)-S-triazine product in Example 2;
[0038] Figure 5 This is a physical picture of the 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-S-triazine product in Examples 1 to 8;
[0039] Figure 6 This is a physical picture of the 2-(2,4-dihydroxyphenyl)-4,6-di(2,4-dimethylphenyl)-S-triazine product in Comparative Examples 1 to 3. DETAILED DESCRIPTION
[0040] In order to make the purpose, technical solution and advantages of the present invention clearer, the technical solution of the present invention will be described clearly and completely below. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
[0041] Unless otherwise specified, the technical means used in the embodiments of the present invention are conventional means well known to those skilled in the art. Unless otherwise specified, the materials and reagents used in the embodiments of the present invention can be obtained through regular commercial channels.
[0042] Example 1
[0043] This embodiment provides a method for purifying 2-(2,4-dihydroxyphenyl)-4,6-di(2,4-dimethylphenyl)-S-triazine, and the steps are as follows:
[0044] Add 32.67 g (0.245 mol) of aluminum chloride, 18.45 g (0.10 mol) of cyanuric chloride and 60.00 g of o-dichlorobenzene into a reaction container, mix, heat and stir, and wait until the internal temperature is heated to 84°C-86°C. Continue to keep warm and stir, take 9.76 g (0.092 mol) of m-xylene, slowly add dropwise, control the reaction time to 4 hours, then slowly cool the reaction solution to 34°C-36°C, continue to add dropwise 14.12 g (0.133 mol) of m-xylene, continue to keep warm and react after the addition is complete, control the second addition reaction time to 4 hours, and obtain the first reaction solution.
[0045] After the first step of the reaction was completed, the temperature was lowered to 13°C-17°C, 9.91 g (0.09 mol) of resorcinol was added to the first reaction solution, and the mixture was kept warm for 1 hour. The temperature was then slowly raised to 75°C-80°C, and the mixture was kept warm for 2 hours to obtain a second reaction solution.
[0046] 150.00 g of water, 100.00 g of ethyl acetate and 5 g of concentrated hydrochloric acid are stirred at room temperature to obtain a mixed solution, and the above-mentioned second reaction liquid is slowly added to the mixed solution. After the addition is completed, stirring is continued at 70-80°C for sufficient time, and the mixture is allowed to stand for stratification to separate the aqueous phase and the organic phase. 60 g of water is added to the organic phase, and the mixture is kept warm and stirred at 80°C-90°C, and the mixture is allowed to stand for stratification to separate the aqueous phase and the organic phase.
[0047] The organic phase was decompressed and desolventized, and the vacuum degree was controlled to be greater than or equal to 0.090Mpa. The distillation temperature was gradually increased to 150°C until there was no obvious fraction. 150g of xylene was added to the distillation bottom residue, and the mixture was stirred for 1h. Then the reaction solution was cooled to 5°C. After crystallization was completed, the filter cake, i.e., the wet crude product, was obtained by suction filtration.
[0048] The obtained wet crude product was added to a mixture of 1.50g activated carbon and 155.0g ethyl acetate, stirred at 75-80℃ for 1h, filtered, cooled to 0℃ for crystallization, and after the crystallization was completed, a yellow filter cake was obtained by suction filtration, i.e., the wet fine product. The obtained wet fine product was placed in a 100℃ forced air oven for drying to obtain 27.32g of 2-(2,4-dihydroxyphenyl)-4,6-di(2,4-dimethylphenyl)-S-triazine product, with a yield of 68.73% based on cyanuric chloride and a purity of 99.9%.
[0049] The physical picture and purity chromatogram of the 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-S-triazine product obtained in this example are shown in Figure 1 and Figure 2 shown.
[0050] Example 2
[0051] This embodiment provides a method for purifying 2-(2,4-dihydroxyphenyl)-4,6-di(2,4-dimethylphenyl)-S-triazine, and the steps are as follows:
[0052] Add 32.67 g (0.245 mol) of aluminum chloride, 18.45 g (0.10 mol) of cyanuric chloride and 60.00 g of o-dichlorobenzene into a reaction container, mix, heat and stir, and wait until the internal temperature is heated to 84°C-86°C. Continue to keep warm and stir, take 9.76 g (0.092 mol) of m-xylene, slowly add dropwise, control the reaction time to 4 hours, then slowly cool the reaction solution to 34°C-36°C, continue to add dropwise 14.12 g (0.133 mol) of m-xylene, continue to keep warm and react after the addition is complete, control the second addition reaction time to 4 hours, and obtain the first reaction solution.
[0053] After the first step of the reaction was completed, the temperature was lowered to 13°C-17°C, 9.91 g (0.09 mol) of resorcinol was added to the first reaction solution, and the mixture was kept warm for 1 hour. The temperature was then slowly raised to 75°C-80°C, and the mixture was kept warm for 2 hours to obtain a second reaction solution.
[0054] 150.00 g of water, 100.00 g of ethyl acetate and 5 g of concentrated hydrochloric acid are stirred at room temperature to obtain a mixed solution, and the above-mentioned second reaction liquid is slowly added to the mixed solution. After the addition is completed, stirring is continued at 70-80°C for sufficient stirring, and the mixture is allowed to stand for stratification to separate the aqueous phase and the organic phase. 60 g of water is added to the organic phase, and after stirring at 70°C-80°C, the mixture is allowed to stand for stratification to separate the aqueous phase and the organic phase.
[0055] The organic phase was decompressed and desolventized, and the vacuum degree was controlled to be greater than or equal to 0.090Mpa. The distillation temperature was gradually increased to 150°C until there was no obvious fraction. 150g of toluene was added to the distillation bottom residue, and the mixture was stirred for 1h. Then the reaction solution was cooled to 10°C. After crystallization was completed, the filter cake was obtained by suction filtration, i.e., the wet crude product.
[0056] The obtained wet crude product was added to a mixture of 1.50g activated carbon and 155.0g ethyl acetate, stirred at 75-80℃ for 1h, filtered, cooled to 10℃ for crystallization, and after the crystallization was completed, a yellow filter cake was obtained by suction filtration, i.e., the wet fine product. The obtained wet fine product was placed in a 100℃ forced air oven for drying to obtain 26.33g of 2-(2,4-dihydroxyphenyl)-4,6-di(2,4-dimethylphenyl)-S-triazine, with a yield of 66.24% based on cyanuric chloride and a purity of 99.56%.
[0057] The physical picture and purity chromatogram of the 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-S-triazine product obtained in this example are shown in Figure 3 and Figure 4 shown.
[0058] Example 3
[0059] This embodiment provides a method for purifying 2-(2,4-dihydroxyphenyl)-4,6-di(2,4-dimethylphenyl)-S-triazine, and the steps are as follows:
[0060] Add 32.67 g (0.245 mol) of aluminum chloride, 18.45 g (0.10 mol) of cyanuric chloride and 60.00 g of o-dichlorobenzene into a reaction container, mix, heat and stir, and wait until the internal temperature is heated to 84°C-86°C. Continue to keep warm and stir, take 9.76 g (0.092 mol) of m-xylene, slowly add dropwise, control the reaction time to 4 hours, then slowly cool the reaction solution to 34°C-36°C, continue to add dropwise 14.12 g (0.133 mol) of m-xylene, continue to keep warm and react after the addition is complete, control the second addition reaction time to 4 hours, and obtain the first reaction solution.
[0061] After the first step of the reaction was completed, the temperature was lowered to 13°C-17°C, 9.91 g (0.09 mol) of resorcinol was added to the first reaction solution, and the mixture was kept warm for 1 hour. The temperature was then slowly raised to 75°C-80°C, and the mixture was kept warm for 2 hours to obtain a second reaction solution.
[0062] 150.00 g of water, 100.00 g of ethyl acetate and 5 g of concentrated hydrochloric acid are stirred at room temperature to obtain a mixed solution, and the above-mentioned second reaction liquid is slowly added to the mixed solution. After the addition is completed, stirring is continued at 70-80°C for sufficient stirring, and the mixture is allowed to stand for stratification to separate the aqueous phase and the organic phase. 60 g of water is added to the organic phase, and after stirring at 70°C-80°C, the mixture is allowed to stand for stratification to separate the aqueous phase and the organic phase.
[0063] The organic phase was decompressed and desolventized, and the vacuum degree was controlled to be greater than or equal to 0.090Mpa. The distillation temperature was gradually increased to 150°C until there was no obvious fraction. 150g of n-heptane was added to the distillation bottom residue, and the mixture was stirred for 1h. Then the reaction solution was cooled to 10°C. After crystallization was completed, the filter cake was obtained by suction filtration, i.e., the wet crude product.
[0064] The obtained wet crude product was added to a mixture of 1.50g activated carbon and 155.0g ethyl acetate, stirred at 75-80℃ for 1h, filtered, cooled to -10℃ for crystallization, and after the crystallization was completed, a yellow filter cake was obtained by suction filtration, i.e., the wet fine product. The obtained wet fine product was placed in a 100℃ forced air oven for drying to obtain 25.91g of 2-(2,4-dihydroxyphenyl)-4,6-di(2,4-dimethylphenyl)-S-triazine, with a yield of 65.19% based on cyanuric chloride and a purity of 99.61%.
[0065] Example 4
[0066] This embodiment provides a method for purifying 2-(2,4-dihydroxyphenyl)-4,6-di(2,4-dimethylphenyl)-S-triazine, and the steps are as follows:
[0067] Add 32.67 g (0.245 mol) of aluminum chloride, 18.45 g (0.10 mol) of cyanuric chloride and 60.00 g of o-dichlorobenzene into a reaction container, mix, heat and stir, and wait until the internal temperature is heated to 84°C-86°C. Continue to keep warm and stir, take 9.76 g (0.092 mol) of m-xylene, slowly add dropwise, control the reaction time to 4 hours, then slowly cool the reaction solution to 34°C-36°C, continue to add dropwise 14.12 g (0.133 mol) of m-xylene, continue to keep warm and react after the addition is complete, control the second addition reaction time to 4 hours, and obtain the first reaction solution.
[0068] After the first step of the reaction was completed, the temperature was lowered to 13°C-17°C, 9.91 g (0.09 mol) of resorcinol was added to the first reaction solution, and the mixture was kept warm for 1 hour. The temperature was then slowly raised to 75°C-80°C, and the mixture was kept warm for 2 hours to obtain a second reaction solution.
[0069] 150.00 g of water, 100.00 g of ethyl acetate and 5 g of concentrated hydrochloric acid are stirred at room temperature to obtain a mixed solution, and the above-mentioned second reaction liquid is slowly added to the mixed solution. After the addition is completed, stirring is continued at 70-80°C for sufficient stirring, and the mixture is allowed to stand for stratification to separate the aqueous phase and the organic phase. 60 g of water is added to the organic phase, and after stirring at 70°C-80°C, the mixture is allowed to stand for stratification to separate the aqueous phase and the organic phase.
[0070] The organic phase was decompressed and desolventized, and the vacuum degree was controlled to be greater than or equal to 0.090Mpa. The distillation temperature was gradually increased to 150°C until there was no obvious fraction. 150g of cyclohexane was added to the distillation bottom residue, and the mixture was stirred for 1h. Then the reaction solution was cooled to 10°C. After crystallization was completed, the filter cake was obtained by suction filtration, i.e., the wet crude product.
[0071] The obtained wet crude product was added to a mixture of 1.50g activated carbon and 155.0g ethyl acetate, stirred at 75-80℃ for 1h, filtered, cooled to -5℃ for crystallization, and after the crystallization was completed, a yellow filter cake was obtained by suction filtration, i.e., the wet fine product. The obtained wet fine product was placed in a 100℃ forced air oven for drying to obtain 25.73g of 2-(2,4-dihydroxyphenyl)-4,6-di(2,4-dimethylphenyl)-S-triazine, with a yield of 64.73% based on cyanuric chloride and a purity of 99.62%.
[0072] Example 5
[0073] This embodiment provides a method for purifying 2-(2,4-dihydroxyphenyl)-4,6-di(2,4-dimethylphenyl)-S-triazine, and the steps are as follows:
[0074] Add 32.67 g (0.245 mol) of aluminum chloride, 18.45 g (0.10 mol) of cyanuric chloride and 60.00 g of o-dichlorobenzene into a reaction container, mix, heat and stir, and wait until the internal temperature is heated to 84°C-86°C. Continue to keep warm and stir, take 9.76 g (0.092 mol) of m-xylene, slowly add dropwise, control the reaction time to 4 hours, then slowly cool the reaction solution to 34°C-36°C, continue to add dropwise 14.12 g (0.133 mol) of m-xylene, continue to keep warm and react after the addition is complete, control the second addition reaction time to 4 hours, and obtain the first reaction solution.
[0075] After the first step of the reaction was completed, the temperature was lowered to 13°C-17°C, 9.91 g (0.09 mol) of resorcinol was added to the first reaction solution, and the mixture was kept warm for 1 hour. The temperature was then slowly raised to 75°C-80°C, and the mixture was kept warm for 2 hours to obtain a second reaction solution.
[0076] 150.00 g of water, 100.00 g of ethyl acetate and 5 g of concentrated hydrochloric acid are stirred at room temperature to obtain a mixed solution, and the above-mentioned second reaction liquid is slowly added to the mixed solution. After the addition is completed, stirring is continued at 70-80°C for sufficient stirring, and the mixture is allowed to stand for stratification to separate the aqueous phase and the organic phase. 60 g of water is added to the organic phase, and after stirring at 70°C-80°C, the mixture is allowed to stand for stratification to separate the aqueous phase and the organic phase.
[0077] The organic phase was decompressed and desolventized, and the vacuum degree was controlled to be greater than or equal to 0.090Mpa. The distillation temperature was gradually increased to 150°C until there was no obvious fraction. 150g of xylene was added to the distillation bottom residue, and the mixture was stirred for 1h. Then the reaction solution was cooled to 15°C. After crystallization was completed, the filter cake was obtained by suction filtration, i.e., the wet crude product.
[0078] The obtained wet crude product was added to a mixture of 1.50 g diatomaceous earth and 155.0 g methanol, stirred at 75-80°C for 1 hour, filtered, cooled to 5°C for crystallization, and after the crystallization was completed, a brown filter cake was obtained by suction filtration, i.e., a wet fine product. The obtained wet fine product was placed in a 100°C blast oven for drying to obtain 26.42 g of 2-(2,4-dihydroxyphenyl)-4,6-di(2,4-dimethylphenyl)-S-triazine, with a yield of 66.47% based on cyanuric chloride and a purity of 99.51%.
[0079] Example 6
[0080] This embodiment provides a method for purifying 2-(2,4-dihydroxyphenyl)-4,6-di(2,4-dimethylphenyl)-S-triazine, wherein the step of obtaining the second reaction solution is the same as that of Example 1, and the subsequent steps are as follows:
[0081] 150.00 g of water, 100.00 g of ethyl acetate and 5 g of concentrated hydrochloric acid are stirred at room temperature to obtain a mixed solution, and the above-mentioned second reaction liquid is slowly added to the mixed solution. After the addition is completed, stirring is continued at 70-80°C for sufficient stirring, and the mixture is allowed to stand for stratification to separate the aqueous phase and the organic phase. 60 g of water is added to the organic phase, and after stirring at 70°C-80°C, the mixture is allowed to stand for stratification to separate the aqueous phase and the organic phase.
[0082] The organic phase was decompressed and desolventized, and the vacuum degree was controlled to be greater than or equal to 0.090Mpa. The distillation temperature was gradually increased to 150°C until there was no obvious fraction. 150g of xylene was added to the distillation bottom residue, and the mixture was stirred for 1h. Then the reaction solution was cooled to 10°C. After crystallization was completed, the filter cake was obtained by suction filtration, i.e., the wet crude product.
[0083] The obtained wet crude product was added to a mixture of 1.50g primary silica gel and 155.0g ethanol, stirred at 75-80℃ for 1h, filtered, cooled to 10℃ for crystallization, and after the crystallization was completed, a brown filter cake was obtained by suction filtration, i.e., the wet fine product. The obtained wet fine product was placed in a 100℃ forced air oven for drying to obtain 25.97g of 2-(2,4-dihydroxyphenyl)-4,6-di(2,4-dimethylphenyl)-S-triazine, with a yield of 65.34% based on cyanuric chloride and a purity of 99.52%.
[0084] Example 7
[0085] This embodiment provides a method for purifying 2-(2,4-dihydroxyphenyl)-4,6-di(2,4-dimethylphenyl)-S-triazine, and the steps are as follows:
[0086] Add 32.67 g (0.245 mol) of aluminum chloride, 18.45 g (0.10 mol) of cyanuric chloride and 60.00 g of o-dichlorobenzene into a reaction container, mix, heat and stir, and wait until the internal temperature is heated to 84°C-86°C. Continue to keep warm and stir, take 9.76 g (0.092 mol) of m-xylene, slowly add dropwise, control the reaction time to 4 hours, then slowly cool the reaction solution to 34°C-36°C, continue to add dropwise 14.12 g (0.133 mol) of m-xylene, continue to keep warm and react after the addition is complete, control the second addition reaction time to 4 hours, and obtain the first reaction solution.
[0087] After the first step of the reaction was completed, the temperature was lowered to 13°C-17°C, 9.91 g (0.09 mol) of resorcinol was added to the first reaction solution, and the mixture was kept warm for 1 hour. The temperature was then slowly raised to 75°C-80°C, and the mixture was kept warm for 2 hours to obtain a second reaction solution.
[0088] 150.00 g of water, 100.00 g of ethyl acetate and 5 g of concentrated hydrochloric acid are stirred at room temperature to obtain a mixed solution, and the above-mentioned second reaction liquid is slowly added to the mixed solution. After the addition is completed, stirring is continued at 70-80°C for sufficient stirring, and the mixture is allowed to stand for stratification to separate the aqueous phase and the organic phase. 60 g of water is added to the organic phase, and after stirring at 70°C-80°C, the mixture is allowed to stand for stratification to separate the aqueous phase and the organic phase.
[0089] The organic phase was decompressed and desolventized, and the vacuum degree was controlled to be greater than or equal to 0.090Mpa. The distillation temperature was gradually increased to 150°C until there was no obvious fraction. 150g of xylene was added to the distillation bottom residue, and the mixture was stirred for 1h. Then the reaction solution was cooled to 5°C. After crystallization was completed, the filter cake, i.e., the wet crude product, was obtained by suction filtration.
[0090] The obtained wet crude product was added to a mixture of 1.50g activated clay and 155.0g methyl isobutyl ketone, stirred at 75-80°C for 1h, filtered, cooled to 0°C for crystallization, and after the crystallization was completed, a brown filter cake was obtained by suction filtration, i.e., a wet fine product. The obtained wet fine product was placed in a 100°C blast oven for drying to obtain 25.40g of 2-(2,4-dihydroxyphenyl)-4,6-di(2,4-dimethylphenyl)-S-triazine, with a yield of 63.91% based on cyanuric chloride and a purity of 99.53%.
[0091] Example 8
[0092] This embodiment provides a method for purifying 2-(2,4-dihydroxyphenyl)-4,6-di(2,4-dimethylphenyl)-S-triazine, wherein the step of obtaining the second reaction solution is the same as that of Example 1, and the subsequent steps are as follows:
[0093] 150.00 g of water, 100.00 g of ethyl acetate and 5 g of concentrated hydrochloric acid are stirred at room temperature to obtain a mixed solution, and the above-mentioned second reaction liquid is slowly added to the mixed solution. After the addition is completed, stirring is continued at 80-90°C for sufficient stirring, and the mixture is allowed to stand for stratification to separate the aqueous phase and the organic phase. 60 g of water is added to the organic phase, and the mixture is kept warm and stirred at 70°C-80°C, and the mixture is allowed to stand for stratification to separate the aqueous phase and the organic phase.
[0094] The organic phase was decompressed and desolventized, and the vacuum degree was controlled to be greater than or equal to 0.090Mpa. The distillation temperature was gradually increased to 150°C until there was no obvious fraction. 150g of xylene was added to the distillation bottom residue, and the mixture was stirred for 1h. Then the reaction solution was cooled to 15°C. After crystallization was completed, the filter cake was obtained by suction filtration, i.e., the wet crude product.
[0095] The obtained wet crude product was added to 155.0g of ethyl acetate, stirred at 75-80℃ for 1h, filtered by suction, cooled to 5℃ for crystallization, and after the crystallization was completed, a dark yellow filter cake was obtained by suction filtration, i.e., the wet fine product. The obtained wet fine product was placed in a 100℃ forced air oven for drying to obtain 26.68g of 2-(2,4-dihydroxyphenyl)-4,6-di(2,4-dimethylphenyl)-S-triazine, with a yield of 67.12% based on cyanuric chloride and a purity of 99.54%.
[0096] Comparative Example 1
[0097] This comparative example provides a method for purifying 2-(2,4-dihydroxyphenyl)-4,6-di(2,4-dimethylphenyl)-S-triazine, wherein the step of obtaining the second reaction solution is the same as that of Example 1, and the subsequent steps are as follows:
[0098] 150.00g of water and 100.00g of ethyl acetate are stirred at room temperature to prepare a mixed solution, and the above-mentioned second reaction liquid is slowly added to the mixed solution. After the addition is completed, stirring is continued at 70-80°C for thorough stratification, and the aqueous phase and the organic phase are separated. 60g of water is added to the organic phase, and after stirring at 70°C-80°C, the aqueous phase and the organic phase are separated.
[0099] The organic phase was decompressed and desolventized, and the vacuum degree was controlled to be greater than or equal to 0.090Mpa. The distillation temperature was gradually increased to 150°C until there was no obvious fraction. 150g of xylene was added to the distillation bottom residue, and the mixture was stirred for 1h. Then the reaction solution was cooled to 10°C. After crystallization was completed, the filter cake was obtained by suction filtration, i.e., the wet crude product.
[0100] The obtained wet crude product was added to a mixture of 1.50g activated carbon and 155.0g ethyl acetate, stirred at 75-80℃ for 1h, filtered, cooled to 0℃ for crystallization, and after crystallization, a brown filter cake was obtained by suction filtration, i.e., the wet fine product. The obtained wet fine product was placed in a 100℃ forced air oven for drying to obtain 26.40g of 2-(2,4-dihydroxyphenyl)-4,6-di(2,4-dimethylphenyl)-S-triazine, with a yield of 66.42% and a purity of 98.86%.
[0101] Comparative Example 2
[0102] This comparative example provides a method for purifying 2-(2,4-dihydroxyphenyl)-4,6-di(2,4-dimethylphenyl)-S-triazine, wherein the step of obtaining the second reaction solution is the same as that of Example 1, and the subsequent steps are as follows:
[0103] 150.00g of water and 5g of concentrated hydrochloric acid were stirred at room temperature to obtain a mixed solution, and the above-mentioned second reaction liquid was slowly added to the mixed solution. After the addition was completed, stirring was continued at 70-80°C for full stirring, and the filter cake was rinsed with an appropriate amount of hot water. The filter cake was mixed with 40g of o-dichlorobenzene, and the temperature was raised to 70°C-80°C with stirring for decompression and solvent removal. The vacuum degree was controlled to be greater than or equal to 0.090Mpa, and the distillation temperature was gradually raised to 150°C until there was no obvious fraction. 150g of xylene was added to the distillation bottom residue, and the mixture was stirred for 1h. Then the reaction solution was cooled to 15°C. After the crystallization was completed, the filter cake was filtered out with suction, i.e., the wet crude product.
[0104] The obtained wet crude product was added to a mixture of 1.50g activated carbon and 155.0g ethyl acetate, stirred at 75-80℃ for 1h, filtered, cooled to 0℃ for crystallization, and after crystallization, a yellow-brown filter cake was obtained by suction filtration, i.e., the wet fine product. The obtained wet fine product was placed in a 100℃ forced air oven for drying to obtain 27.03g of 2-(2,4-dihydroxyphenyl)-4,6-di(2,4-dimethylphenyl)-S-triazine, with a yield of 68.00% and a purity of 96.56%.
[0105] Comparative Example 3
[0106] This comparative example provides a method for purifying 2-(2,4-dihydroxyphenyl)-4,6-di(2,4-dimethylphenyl)-S-triazine, wherein the step of obtaining the second reaction solution is the same as that of Example 1, and the subsequent steps are as follows:
[0107] 150.00g of water and 100.00g of ethanol are stirred at room temperature to obtain a mixed solution, and the above-mentioned second reaction liquid is slowly added to the mixed solution. After the addition is completed, stirring is continued at 70-80°C for sufficient time, and the mixture is allowed to stand for stratification to separate the aqueous phase and the organic phase. 60g of water is added to the organic phase, and after stirring at 70°C-80°C, the mixture is allowed to stand for stratification to separate the aqueous phase and the organic phase.
[0108] The organic phase was decompressed and desolventized, and the vacuum degree was controlled to be greater than or equal to 0.090Mpa. The distillation temperature was gradually increased to 150°C until there was no obvious distillate. 150g of xylene and 1.50g of activated carbon were added to the distillation bottom residue, and the mixture was stirred for 1h. Then the reaction solution was cooled to 5°C. After crystallization was completed, the filter cake, i.e., the wet crude product, was obtained by suction filtration.
[0109] Figure 5 This is a physical picture of the 2-(2,4-dihydroxyphenyl)-4,6-di(2,4-dimethylphenyl)-S-triazine product in Examples 1 to 8.
[0110] Figure 6 This is a physical picture of the 2-(2,4-dihydroxyphenyl)-4,6-di(2,4-dimethylphenyl)-S-triazine product in Comparative Examples 1 to 3.
[0111] From the above results, it can be seen that in Example 1-8 of the present invention, a mixed solution of water, ethyl acetate and hydrochloric acid is used to remove impurities from the reaction solution containing 2-(2,4-dihydroxyphenyl)-4,6-di(2,4-dimethylphenyl)-S-triazine, and the reaction solvent and water-soluble impurities are removed before crystallization, which can ensure that the purity of the 2-(2,4-dihydroxyphenyl)-4,6-di(2,4-dimethylphenyl)-S-triazine product is above 99.5%, and the color is relatively pure. Among them, Example 1-4 uses a mixed solution of ethyl acetate and an adsorbent material to crystallize the wet crude product again, so the color of the obtained product is yellow, which is better than the brown or dark yellow in Examples 5-8.
[0112] In Comparative Examples 1-3, the reaction solution containing 2-(2,4-dihydroxyphenyl)-4,6-di(2,4-dimethylphenyl)-S-triazine was not treated with a mixed solution of water, ethyl acetate and hydrochloric acid. Specifically, Comparative Example 1 used a mixed solution of water and ethyl acetate, Comparative Example 2 used a mixed solution of water and hydrochloric acid, and Comparative Example 3 used a mixed solution of water and ethanol. As a result, no product with ideal color and purity could be obtained. Among them, even if the adsorbent material activated carbon was added during the first crystallization in Comparative Example 3, the product color was still not improved, and the obtained product was brown-black. In view of this, the subsequent yield and purity data have no reference significance.
[0113] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims
1. A method for purifying 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-S-triazine, characterized in that: include: The reaction liquid containing 2-(2,4-dihydroxyphenyl)-4,6-di(2,4-dimethylphenyl)-S-triazine is decontaminated with a mixed solution of water, ethyl acetate and hydrochloric acid to remove the solvent and water-soluble impurities to obtain a solid base material; the solid base material is crystallized, and the crystallization solvent is xylene, toluene, n-heptane or cyclohexane.
2. The method for purifying 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-S-triazine according to claim 1, characterized in that: The crystallization step comprises: The solid base material is mixed with a crystallization solvent, stirred at a temperature below 140° C. for 1-2 hours to dissolve, and then cooled to 5-15° C. to crystallize. After the crystallization is completed, the filter cake is filtered to obtain a wet crude product.
3. The method for purifying 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-S-triazine according to claim 2, characterized in that: Also includes: The wet crude product is mixed with a mixed solution of a recrystallization solvent and an adsorbent material, stirred at a temperature of 1-2 hours, the filtrate is filtered out, the filtrate is cooled to -10-10°C and crystallized again, and after the crystallization is completed, the filter cake is filtered out to obtain a yellow wet fine product with a purity greater than or equal to 99.5%.
4. The method for purifying 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-S-triazine according to claim 3, characterized in that: The re-crystallization solvent is ethyl acetate, methanol, ethanol or methyl isobutyl ketone; Preferably, the re-crystallization solvent is ethyl acetate, and the temperature of the heat preservation and stirring is 70-90°C.
5. The method for purifying 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-S-triazine according to claim 3, characterized in that: The amount of the re-crystallization solvent used is based on the amount of the wet crude product that is completely dissolved; The adsorption material is activated carbon, diatomaceous earth, primary silica gel or activated white clay; Preferably, the adsorption material is activated carbon with a particle size of 100-200 mesh, which is 5%-10% of the mass of the wet crude product.
6. The method for purifying 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-S-triazine according to any one of claims 1 to 5, characterized in that: The step of obtaining the solid base material comprises: Using cyanuric chloride and m-xylene as raw materials, adding a reaction solvent to react under the catalytic action of aluminum chloride to generate an intermediate, and the intermediate reacts with resorcinol to generate 2-(2,4-dihydroxyphenyl)-4,6-di(2,4-dimethylphenyl)-S-triazine; The reaction solution containing 2-(2,4-dihydroxyphenyl)-4,6-di(2,4-dimethylphenyl)-S-triazine is extracted with a mixed solution of water, ethyl acetate and hydrochloric acid at an extraction temperature of 70-90° C., the aqueous phase is removed, the organic phase is retained and desolventized under reduced pressure to obtain the solid base material.
7. The method for purifying 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-S-triazine according to claim 6, characterized in that: The amount of water used is calculated to be 100g / 0.1mol-150g / 0.1mol cyanuric chloride relative to the molar amount of cyanuric chloride; The amount of ethyl acetate used is calculated to be 80 g / 0.1 mol-150 g / 0.1 mol cyanuric chloride relative to the molar amount of cyanuric chloride; The hydrochloric acid is concentrated hydrochloric acid, and its usage is calculated as 2g / 0.1mol-8g / 0.1mol cyanuric chloride relative to the molar amount of cyanuric chloride.
8. The method for purifying 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-S-triazine according to claim 6, characterized in that: The extraction step comprises: The mixture was stirred fully at a temperature of 70-90°C, allowed to stand for stratification, and the aqueous phase and the organic phase were separated. The organic phase was washed twice with water at a temperature of 70-90°C.
9. The method for purifying 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-S-triazine according to claim 6, characterized in that: The step of decompression desolventizing comprises: The organic phase was desolventized and the vacuum degree was controlled to be greater than or equal to 0.090 MPa. The distillation temperature was gradually increased to above 150°C until there was no obvious fraction to obtain a solid bottom material.
10. A triazine ultraviolet absorber product, characterized in that: The triazine ultraviolet absorber product is 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine prepared by reacting 1-chlorooctane and 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-S-triazine obtained by the purification method according to any one of claims 1 to 9 as raw materials.