Method for efficiently preparing UV-1577 through tubular continuous reaction
By using a tubular continuous reactor to perform continuous reaction in the production of UV-1577, the problems of insufficient reaction and inorganic salts in the etherification reaction step in the prior art are solved, and an efficient and safe UV-1577 preparation process is achieved, which improves production efficiency and product quality.
Patent Information
- Application Number
- CN202510003388.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-01-02
- Publication Date
- 2025-04-29
AI Technical Summary
The existing industrial methods for producing UV-1577 have insufficient local reactions that lead to reduced efficiency, and a large amount of inorganic salts are generated in the etherification reaction step. The traditional process conditions are harsh, inconvenient to operate and risk of poisoning.
A tubular continuous reactor is used to replace conventional reactors, and the production efficiency is improved through continuous reactions, and Fuker alkylation and etherification reactions are carried out by controlling the reaction temperature and flow rate, reducing the water washing and extraction process of the solid catalyst and simplifying the process.
It realizes efficient preparation of UV-1577, improves production efficiency, reduces reaction risks, simplifies the process, reduces the generation of process wastewater, and improves the purity and yield of the product.
Smart Images
Figure BDA0005226123740000011 
Figure BDA0005226123740000012
Abstract
Description
Technical Field
[0001] The invention relates to the field of organic synthesis chemical industry, and in particular to a method for efficiently preparing UV-1577 by tubular continuous reaction. Background Art
[0002] UV absorber UV-1577 (chemical name: 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-hexyloxy-phenol, structural formula as shown below) belongs to the triazine class of UV absorbers, and has good compatibility with polymers and other additives. It is particularly suitable for materials such as engineering plastics, polycarbonate, laminated films, etc., and can improve the long-lasting light stability of products.
[0003]
[0004] At present, the industrial production method of UV-1577 is mainly to use cyanuric chloride as the starting material, and synthesize it through a two-step Friedel-Crafts alkylation reaction and a one-step etherification reaction, that is, cheap and easily available benzene and cyanuric chloride are subjected to a Friedel-Crafts alkylation reaction under the catalysis of aluminum trichloride to obtain a monochlorodiphenyl-s-triazine intermediate, which is separated and purified and subjected to a secondary Friedel-Crafts alkylation reaction with diphenol under the catalysis of aluminum trichloride to obtain 2,4-diphenyl-6-(1-diphenolyl)-1,3,5-triazine, which is separated and purified and then further subjected to an etherification reaction with a halogenated hexane to obtain UV-1577.
[0005]
[0006] This route is mature, low-cost, and uses conventional autoclave reactions. Due to the influence of stirring characteristics, there will be insufficient local reactions during the production process, resulting in reduced overall efficiency and ultimately increased production costs. In the etherification reaction step, a large amount of inorganic salts will be produced. In the traditional production process, DMF reflux salt pressing is used, which has harsh conditions, inconvenient operation, and a risk of poisoning. Summary of the invention
[0007] The technical problem to be solved by the present invention is to provide a method for efficiently preparing UV-1577 by tubular continuous reaction with high efficiency and low reaction risk.
[0008] To solve the above problems, the method for efficiently preparing UV-1577 by a tubular continuous reaction according to the present invention comprises the following steps:
[0009] Step 1: preparing a solution of cyanuric chloride, aluminum chloride and chlorobenzene, and continuously introducing the solution into a tubular reactor with benzene, respectively, with the flow rate controlled at 0.2 to 1.0 mL / min and the reaction temperature at 80 to 150° C., and synthesizing 2-chloro-4,6-di(2',4'-diphenyl)-1,3,5-s-triazine through a single Friedel-Crafts alkylation reaction;
[0010] Step 2: The chlorobenzene solution of 2-chloro-4,6-di(2',4'-diphenyl)-1,3,5-s-triazine and resorcinol is continuously introduced into a tubular reactor respectively, and the flow rate is controlled to be 0.2-1.0 mL / min and the reaction temperature is 80-150° C. to perform a secondary Friedel-Crafts alkylation reaction to synthesize 2-(2',4'-dihydroxybenzene)-4,6-di(2',4'-diphenyl)-1,3,5-s-triazine;
[0011] Step 3: 2-(2',4'-dihydroxybenzene)-4,6-bis(2',4'-diphenyl)-1,3,5-s-triazine, a suspension prepared with potassium carbonate and DMF and bromohexane are continuously introduced into a tubular reactor respectively, and the flow rate is controlled to be 0.1-1.2 mL / min and the reaction temperature is 50-100° C. to carry out etherification reaction to obtain UV-1577 reaction solution. The UV-1577 reaction solution is subjected to reduced pressure distillation to remove low-boiling point components to obtain the product UV-1577.
[0012] In the step 1, the mass ratio of aluminum chloride to cyanuric chloride is 1.45-2.89:1; the mass ratio of chlorobenzene to cyanuric chloride is 7.18-21.25:1; and the mass ratio of benzene to cyanuric chloride is 0.85-1.27:1.
[0013] The chlorobenzene solution of resorcinol in step 2 refers to a solution obtained by uniformly mixing resorcinol and chlorobenzene; the mass ratio of the resorcinol to the cyanuric chloride is 0.60-1.19:1; the mass ratio of the chlorobenzene to the cyanuric chloride is 7.18-21.25:1.
[0014] In the step 3, the mass ratio of potassium carbonate to 2-(2',4'-dihydroxybenzene)-4,6-bis(2',4'-diphenyl)-1,3,5-s-triazine is 0.04-0.12:1; the mass ratio of DMF to 2-(2',4'-dihydroxybenzene)-4,6-bis(2',4'-diphenyl)-1,3,5-s-triazine is 2.78-8.34:1; the mass ratio of hexyl bromide to 2-(2',4'-dihydroxybenzene)-4,6-bis(2',4'-diphenyl)-1,3,5-s-triazine is 0.48-0.97:1.
[0015] Compared with the prior art, the present invention has the following advantages:
[0016] 1. The present invention replaces the conventional reactor with a tubular reactor, which not only reduces the danger of the alkylation reaction, but also realizes a continuous reaction, thereby improving production efficiency.
[0017] 2. The solid catalyst in the present invention does not need to be removed by washing, extraction or the like, and can be directly separated from the tubular reactor, which simplifies the process and reduces the generation of process wastewater. DETAILED DESCRIPTION
[0018] A method for efficiently preparing UV-1577 by tubular continuous reaction, comprising the following steps:
[0019] Step 1: Prepare cyanuric chloride, aluminum chloride and chlorobenzene into a solution, and continuously introduce it into a tubular reactor with benzene, control the flow rate to 0.2-1.0 mL / min, and the reaction temperature to 80-150° C., and synthesize 2-chloro-4,6-di(2',4'-diphenyl)-1,3,5-s-triazine through a single Friedel-Crafts alkylation reaction.
[0020] Wherein: the mass ratio of aluminum chloride to cyanuric chloride is 1.45-2.89:1; the mass ratio of chlorobenzene to cyanuric chloride is 7.18-21.25:1; the mass ratio of benzene to cyanuric chloride is 0.85-1.27:1.
[0021] Step 2: 2-chloro-4,6-di(2',4'-diphenyl)-1,3,5-s-triazine and chlorobenzene solution of resorcinol are continuously introduced into a tubular reactor respectively, and the flow rate is controlled at 0.2-1.0 mL / min and the reaction temperature is 80-150° C. to perform a secondary Friedel-Crafts alkylation reaction to synthesize 2-(2',4'-dihydroxybenzene)-4,6-di(2',4'-diphenyl)-1,3,5-s-triazine.
[0022] Wherein: the chlorobenzene solution of resorcinol refers to a solution obtained by uniformly mixing resorcinol and chlorobenzene; the mass ratio of the resorcinol to the cyanuric chloride is 0.60-1.19:1; the mass ratio of the chlorobenzene to the cyanuric chloride is 7.18-21.25:1.
[0023] Step 3: 2-(2',4'-dihydroxybenzene)-4,6-bis(2',4'-diphenyl)-1,3,5-s-triazine, a suspension prepared with potassium carbonate and DMF and bromohexane are continuously introduced into a tubular reactor respectively, and the flow rate is controlled to be 0.1-1.2 mL / min and the reaction temperature is 50-100° C. to carry out etherification reaction to obtain UV-1577 reaction solution. The UV-1577 reaction solution is subjected to reduced pressure distillation to remove low-boiling point components to obtain the product UV-1577.
[0024] Among them: the mass ratio of potassium carbonate to 2-(2',4'-dihydroxybenzene)-4,6-bis(2',4'-diphenyl)-1,3,5-s-triazine is 0.04-0.12:1; the mass ratio of DMF to 2-(2',4'-dihydroxybenzene)-4,6-bis(2',4'-diphenyl)-1,3,5-s-triazine is 2.78-8.34:1; the mass ratio of hexyl bromide to 2-(2',4'-dihydroxybenzene)-4,6-bis(2',4'-diphenyl)-1,3,5-s-triazine is 0.48-0.97:1.
[0025] The mass ratios in the present invention are all g / g.
[0026] Example 1
[0027] Step 1: 184.4 g of cyanuric chloride, 267.38 g of aluminum chloride and 1.32 kg of chlorobenzene were prepared into a solution, and continuously introduced into a tubular reactor with 156.74 g of benzene, and the flow rate was controlled to be 0.2 mL / min and the reaction temperature was 80°C. 2-chloro-4,6-di(2',4'-diphenyl)-1,3,5-s-triazine was synthesized through a Friedel-Crafts alkylation reaction.
[0028] Step 2: 2-chloro-4,6-di(2',4'-diphenyl)-1,3,5-s-triazine and chlorobenzene solution of resorcinol were continuously introduced into a tubular reactor, respectively, and the flow rate was controlled to be 0.2 mL / min and the reaction temperature was 80°C to carry out a secondary Friedel-Crafts alkylation reaction. After the reaction was completed, the reaction solution was poured into a pre-cooled acid in an ice bath to quench, and the separated organic layer was distilled under reduced pressure to recover the solvent, and filtered to obtain the intermediate 2-(2',4'-dihydroxybenzene)-4,6-di(2',4'-diphenyl)-1,3,5-s-triazine.
[0029] Wherein: the chlorobenzene solution of resorcinol refers to a solution obtained by uniformly mixing 110.64 g of resorcinol and 1.32 kg of chlorobenzene.
[0030] Step 3: 341.37g of 2-(2',4'-dihydroxybenzene)-4,6-bis(2',4'-diphenyl)-1,3,5-s-triazine, 13.65g of potassium carbonate and a suspension prepared with 949.00g of DMF and 163.86g of bromohexane were continuously introduced into a tubular reactor respectively, and the flow rate was controlled to be 0.1mL / min and the reaction temperature was 50°C to carry out an etherification reaction to obtain a UV-1577 reaction liquid, and the UV-1577 reaction liquid was subjected to reduced pressure distillation to remove low-boiling point components to obtain 324.77g of product UV-1577. The yield was 76.32% and the purity was 99.11%.
[0031] Example 2
[0032] Step 1: 184.4 g of cyanuric chloride, 401.07 g of aluminum chloride and 2.65 kg of chlorobenzene were prepared into a solution, and continuously introduced into a tubular reactor with 195 g of benzene, respectively, with the flow rate controlled at 0.4 mL / min and the reaction temperature at 90° C., and 2-chloro-4,6-di(2',4'-diphenyl)-1,3,5-s-triazine was synthesized through a single Friedel-Crafts alkylation reaction.
[0033] Step 2: 2-chloro-4,6-di(2',4'-diphenyl)-1,3,5-s-triazine and chlorobenzene solution of resorcinol were continuously introduced into a tubular reactor, respectively, and the flow rate was controlled to be 0.4 mL / min and the reaction temperature was 90°C to carry out a secondary Friedel-Crafts alkylation reaction. After the reaction was completed, the reaction solution was poured into a pre-cooled acid in an ice bath to quench, and the separated organic layer was distilled under reduced pressure to recover the solvent, and filtered to obtain 2-(2',4'-dihydroxybenzene)-4,6-di(2',4'-diphenyl)-1,3,5-s-triazine.
[0034] Wherein: the chlorobenzene solution of resorcinol refers to a solution obtained by uniformly mixing 147.52 g of resorcinol and 2.65 kg of chlorobenzene.
[0035] Step 3: 341.37 g of 2-(2',4'-dihydroxybenzene)-4,6-bis(2',4'-diphenyl)-1,3,5-s-triazine, 20.48 g of potassium carbonate and 1.42 kg of DMF prepared suspension and 245.79 g of bromohexane were continuously introduced into a tubular reactor, respectively, and the flow rate was controlled to be 0.3 mL / min and the reaction temperature was 60° C. to carry out etherification reaction to obtain UV-1577 reaction liquid, and the UV-1577 reaction liquid was subjected to reduced pressure distillation to remove low-boiling point components to obtain 354.25 g of product UV-1577. The yield was 83.25% and the purity was 99.14%.
[0036] Example 3
[0037] Step 1: 184.4 g of cyanuric chloride, 532.92 g of aluminum chloride and 3.92 kg of chlorobenzene were prepared into a solution, and continuously introduced into a tubular reactor with 234.00 g of benzene, respectively, with the flow rate controlled at 0.6 mL / min and the reaction temperature at 100 ° C., and 2-chloro-4,6-di(2',4'-diphenyl)-1,3,5-s-triazine was synthesized through a Friedel-Crafts alkylation reaction.
[0038] Step 2: 2-chloro-4,6-di(2',4'-diphenyl)-1,3,5-s-triazine and chlorobenzene solution of resorcinol were continuously introduced into a tubular reactor, respectively, and the flow rate was controlled to be 0.6 mL / min and the reaction temperature was 100°C to carry out a secondary Friedel-Crafts alkylation reaction. After the reaction was completed, the reaction solution was poured into a pre-cooled acid in an ice bath to quench, and the separated organic layer was distilled under reduced pressure to recover the solvent, and filtered to obtain 2-(2',4'-dihydroxybenzene)-4,6-di(2',4'-diphenyl)-1,3,5-s-triazine.
[0039] Wherein: the chlorobenzene solution of resorcinol refers to a solution obtained by uniformly mixing 307.23 g of resorcinol and 3.92 kg of chlorobenzene.
[0040] Step 3: 341.37 g of 2-(2',4'-dihydroxybenzene)-4,6-bis(2',4'-diphenyl)-1,3,5-s-triazine, 27.31 g of potassium carbonate and a suspension prepared with 1.90 kg of DMF and 331.13 g of bromohexane were continuously introduced into a tubular reactor respectively, and the flow rate was controlled to be 0.5 mL / min and the reaction temperature was 70° C. to carry out an etherification reaction to obtain a UV-1577 reaction liquid, and the UV-1577 reaction liquid was subjected to reduced pressure distillation to remove low-boiling point components to obtain 350.84 g of product UV-1577. The yield was 82.45% and the purity was 99.12%.
[0041] Example 4
[0042] Step 1: 184.4 g of cyanuric chloride, 401.07 g of aluminum chloride and 2.65 kg of chlorobenzene were prepared into a solution, and continuously introduced into a tubular reactor with 195 g of benzene, respectively, with the flow rate controlled at 0.8 mL / min and the reaction temperature at 110° C., and 2-chloro-4,6-di(2',4'-diphenyl)-1,3,5-s-triazine was synthesized through a Friedel-Crafts alkylation reaction.
[0043] Step 2: 2-chloro-4,6-di(2',4'-diphenyl)-1,3,5-s-triazine and chlorobenzene solution of resorcinol were continuously introduced into a tubular reactor, respectively, and the flow rate was controlled to be 0.8 mL / min and the reaction temperature was 110°C to carry out a secondary Friedel-Crafts alkylation reaction. After the reaction was completed, the reaction solution was poured into a pre-cooled acid in an ice bath to quench, and the separated organic layer was distilled under reduced pressure to recover the solvent, and filtered to obtain 2-(2',4'-dihydroxybenzene)-4,6-di(2',4'-diphenyl)-1,3,5-s-triazine.
[0044] Wherein: the chlorobenzene solution of resorcinol refers to a solution obtained by uniformly mixing 147.52 g of resorcinol and 2.65 kg of chlorobenzene.
[0045] Step 3: 341.37 g of 2-(2',4'-dihydroxybenzene)-4,6-bis(2',4'-diphenyl)-1,3,5-s-triazine, 34.14 g of potassium carbonate and a suspension prepared with 2.37 kg of DMF and 245.79 g of bromohexane were continuously introduced into a tubular reactor, respectively, and the flow rate was controlled to be 0.5 mL / min and the reaction temperature was 70° C. to carry out an etherification reaction to obtain a UV-1577 reaction liquid, and the UV-1577 reaction liquid was subjected to reduced pressure distillation to remove low-boiling point components to obtain 357.22 g of product UV-1577. The yield was 83.95% and the purity was 99.20%.
[0046] Example 5
[0047] Step 1: 184.4 g of cyanuric chloride, 401.07 g of aluminum chloride and 2.65 kg of chlorobenzene were prepared into a solution, and continuously introduced into a tubular reactor with 195 g of benzene, respectively, with the flow rate controlled at 1.0 mL / min and the reaction temperature at 130° C., and 2-chloro-4,6-di(2',4'-diphenyl)-1,3,5-s-triazine was synthesized through a single Friedel-Crafts alkylation reaction.
[0048] Step 2: 2-chloro-4,6-di(2',4'-diphenyl)-1,3,5-s-triazine and chlorobenzene solution of resorcinol were continuously introduced into a tubular reactor, respectively, and the flow rate was controlled to be 1.0 mL / min and the reaction temperature was 130°C to carry out a secondary Friedel-Crafts alkylation reaction. After the reaction was completed, the reaction solution was poured into a pre-cooled acid in an ice bath to quench, and the separated organic layer was distilled under reduced pressure to recover the solvent, and filtered to obtain 2-(2',4'-dihydroxybenzene)-4,6-di(2',4'-diphenyl)-1,3,5-s-triazine.
[0049] Wherein: the chlorobenzene solution of resorcinol refers to a solution obtained by uniformly mixing 147.52 g of resorcinol and 2.65 kg of chlorobenzene.
[0050] Step 3: 341.37 g of 2-(2',4'-dihydroxybenzene)-4,6-bis(2',4'-diphenyl)-1,3,5-s-triazine, 40.96 g of potassium carbonate and a suspension prepared with 2.85 kg of DMF and 245.79 g of bromohexane were continuously introduced into a tubular reactor, respectively, and the flow rate was controlled to be 0.8 mL / min and the reaction temperature was 90° C. to carry out an etherification reaction to obtain a UV-1577 reaction liquid, and the UV-1577 reaction liquid was subjected to reduced pressure distillation to remove low-boiling point components to obtain 358.84 g of product UV-1577. The yield was 84.33% and the purity was 99.16%.
[0051] Example 6
[0052] Step 1: 184.4 g of cyanuric chloride, 401.07 g of aluminum chloride and 2.65 kg of chlorobenzene were prepared into a solution, and continuously introduced into a tubular reactor with 195 g of benzene, respectively, with the flow rate controlled at 0.4 mL / min and the reaction temperature at 150 ° C., and 2-chloro-4,6-di(2',4'-diphenyl)-1,3,5-s-triazine was synthesized through a Friedel-Crafts alkylation reaction.
[0053] Step 2: 2-chloro-4,6-di(2',4'-diphenyl)-1,3,5-s-triazine and chlorobenzene solution of resorcinol were continuously introduced into a tubular reactor, respectively, and the flow rate was controlled to be 0.4 mL / min and the reaction temperature was 150°C to carry out a secondary Friedel-Crafts alkylation reaction. After the reaction was completed, the reaction solution was poured into a pre-cooled acid in an ice bath to quench, and the separated organic layer was distilled under reduced pressure to recover the solvent, and filtered to obtain 2-(2',4'-dihydroxybenzene)-4,6-di(2',4'-diphenyl)-1,3,5-s-triazine.
[0054] Wherein: the chlorobenzene solution of resorcinol refers to a solution obtained by uniformly mixing 147.52 g of resorcinol and 2.65 kg of chlorobenzene.
[0055] Step 3: 341.37 g of 2-(2',4'-dihydroxybenzene)-4,6-bis(2',4'-diphenyl)-1,3,5-s-triazine, 34.14 g of potassium carbonate and a suspension prepared with 2.37 kg of DMF and 245.79 g of bromohexane were continuously introduced into a tubular reactor, respectively, and the flow rate was controlled to be 0.5 mL / min and the reaction temperature was 70° C. to carry out an etherification reaction to obtain a UV-1577 reaction liquid, and the UV-1577 reaction liquid was subjected to reduced pressure distillation to remove low-boiling point components to obtain 345.78 g of product UV-1577. The yield was 81.26% and the purity was 99.18%.
Claims
1. A method for efficiently preparing UV-1577 by tubular continuous reaction, comprising the following steps: Step 1: prepare cyanuric chloride, aluminum chloride and chlorobenzene into a solution, and continuously introduce it into a tubular reactor with benzene, control the flow rate to be 0.2-1.0 mL / min, and the reaction temperature to be 80-150° C., and synthesize 2-chloro-4,6-di(2',4'-diphenyl)-1,3,5-s-triazine through a Friedel-Crafts alkylation reaction; Step 2: The chlorobenzene solution of 2-chloro-4,6-di(2',4'-diphenyl)-1,3,5-s-triazine and resorcinol is continuously introduced into a tubular reactor respectively, and the flow rate is controlled to be 0.2-1.0 mL / min and the reaction temperature is 80-150° C. to perform a secondary Friedel-Crafts alkylation reaction to synthesize 2-(2',4'-dihydroxybenzene)-4,6-di(2',4'-diphenyl)-1,3,5-s-triazine; Step 3: A suspension prepared by 2-(2',4'-dihydroxybenzene)-4,6-bis(2',4'-diphenyl)-1,3,5-s-triazine, potassium carbonate and DMF and bromohexane are continuously introduced into a tubular reactor respectively, and the flow rate is controlled to be 0.1-1.2 mL / min and the reaction temperature is 50-100°C to carry out an etherification reaction to obtain a UV-1577 reaction solution. The UV-1577 reaction solution is subjected to reduced pressure distillation to remove low-boiling point components to obtain the product UV-1577.
2. The method for efficiently preparing UV-1577 by a tubular continuous reaction as claimed in claim 1, characterized in that: In the step 1, the mass ratio of aluminum chloride to cyanuric chloride is 1.45-2.89:1; the mass ratio of chlorobenzene to cyanuric chloride is 7.18-21.25:1; and the mass ratio of benzene to cyanuric chloride is 0.85-1.27:
1.
3. The method for efficiently preparing UV-1577 by a tubular continuous reaction as claimed in claim 1, characterized in that: The chlorobenzene solution of resorcinol in step 2 refers to a solution obtained by uniformly mixing resorcinol and chlorobenzene; the mass ratio of the resorcinol to the cyanuric chloride is 0.60-1.19:1; the mass ratio of the chlorobenzene to the cyanuric chloride is 7.18-21.25:
1.
4. The method for efficiently preparing UV-1577 by a tubular continuous reaction as claimed in claim 1, characterized in that: In the step 3, the mass ratio of potassium carbonate to 2-(2',4'-dihydroxybenzene)-4,6-bis(2',4'-diphenyl)-1,3,5-s-triazine is 0.04-0.12:1; the mass ratio of DMF to 2-(2',4'-dihydroxybenzene)-4,6-bis(2',4'-diphenyl)-1,3,5-s-triazine is 2.78-8.34:1; the mass ratio of hexyl bromide to 2-(2',4'-dihydroxybenzene)-4,6-bis(2',4'-diphenyl)-1,3,5-s-triazine is 0.48-0.97:1.