A kind of acid-base bifunctional solid catalyst and synthesis method of chlorobenzene glycol ether
By modifying UiO-66-NH2 with acid-base bifunctional properties, an acid-base bifunctional solid catalyst was prepared, which solved the problems of high equipment corrosion and difficult product purification in the existing chlorophenoxylate synthesis, and realized efficient and safe chlorophenoxylate production.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- HAIKE GRP RES INST OF INNOVATION & TECH
- Filing Date
- 2026-03-16
- Publication Date
- 2026-06-30
AI Technical Summary
Existing methods for synthesizing chlorophenoxylate use strong acid or strong base catalysts, which lead to problems such as high equipment corrosion, numerous side reactions, difficulty in product purification, and the use of flammable and explosive raw materials, making it difficult to achieve large-scale safe production.
A bifunctional acid-base solid catalyst, UiO-66-NH2, was used for modification. Through imidization and phosphoric acid modification, a bifunctional acid-base catalyst was formed for the synthesis of chlorophenoxylate, avoiding the use of strong acids and bases. High-purity product purification was achieved by slurry washing with dichloromethane.
This approach achieves easy catalyst recovery and environmental friendliness, reduces raw material and equipment losses, avoids flammability and explosion risks, simplifies the production process, and improves product purity and safety.
Smart Images
Figure CN121847236B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of organic chemical preparation technology, and particularly relates to a method for synthesizing an acid-base bifunctional solid catalyst and chlorophenoxylate. Background Technology
[0002] Chlorphenesin, also known as chlorophenol ether or chlorophenesin glycerol ether, has the molecular formula C9H. 11 ClO3 is a fine chemical product that is widely used in pharmaceuticals, daily chemicals, and fine chemical products.
[0003] Currently, chlorophenoxylate is mostly prepared by chemical methods. Chinese patent CN101445436A discloses a method for synthesizing chlorophenoxylate using epichlorohydrin and p-chlorophenol as raw materials via sulfuric acid catalysis. This method uses corrosive reagents such as strong acids, making post-processing difficult. GB628497 uses p-chlorophenol and glycidol as raw materials, reacting them in the presence of pyridine. The resulting product is purified with a mixture of diethyl ether and petroleum ether, and then extracted with chloroform. In this method, diethyl ether-petroleum ether and chloroform are volatile, flammable, and explosive, making them unsuitable for large-scale production. CN113979841A uses 3-chloro-1,2-propanediol and p-chlorophenol as raw materials, catalyzing the synthesis with an inorganic base. This method uses a strong base catalyst, is highly hazardous, and cannot be recovered. Summary of the Invention
[0004] To address the shortcomings of existing technologies, this invention proposes a method for synthesizing chlorophenoxylate using an acid-base bifunctional solid catalyst. The synthesis of chlorophenoxylate using the acid-base bifunctional catalyst provided by this invention not only allows for easy catalyst recovery and environmental friendliness, but also eliminates corrosion to production equipment, effectively reducing raw material and equipment losses, and effectively suppressing side reactions.
[0005] To solve the aforementioned technical problem, the present invention adopts the following technical solution: an acid-base bifunctional solid catalyst, prepared by the following steps:
[0006] 1) Disperse UiO-66-NH2 in dimethylformamide, add 2-chloroethylamine hydrochloride to react, and obtain imine-modified UiO-66-NH2;
[0007] 2) The imide-modified UiO-66-NH2 was dispersed in methanol, formaldehyde was added, and the reaction was carried out to obtain a solid product;
[0008] 3) The solid product is dispersed in acetonitrile, hypophosphoric acid is added, and the reaction is carried out to obtain a bifunctional acid-base solid catalyst.
[0009] Preferably, the molar ratio of UiO-66-NH2 and 2-chloroethylamine hydrochloride in step 1) is 0.5-1 g: 0.5-1 mmol.
[0010] Preferably, the reaction in step 1) is carried out at a temperature of 75-85°C for 22-26 hours.
[0011] Preferably, in step 2), the mass molar ratio of imidized UiO-66-NH2 to formaldehyde is 0.5-1 g: 1-2 mmol.
[0012] Preferably, the reaction in step 2) is carried out at a temperature of 20-30°C for 22-26 hours.
[0013] Preferably, in step 3), the mass molar ratio of imidized UiO-66-NH2 to hypophosphoric acid is 0.5-1 g: 1-2 mmol.
[0014] Preferably, the reaction in step 3) is carried out at a temperature of 20-30°C for 22-26 hours.
[0015] This invention provides a method for synthesizing chlorophenoxylate, comprising the following steps:
[0016] a. Mix epichlorohydrin, water and any one of the above-mentioned acid-base bifunctional solid catalysts, and heat under reflux for 1-3 hours. Then add p-chlorophenol and continue to reflux for 1-3 hours to obtain a reaction solution.
[0017] b. Filter the reaction solution, add the filtrate to the crystallization solution to crystallize, and obtain chlorophenoxylate.
[0018] Preferably, the mass ratio of epichlorohydrin to the acid-base bifunctional solid catalyst in step a is 1:0.1 to 1:0.8.
[0019] Preferably, the temperature during the heating and reflux process in step a is 80-120°C.
[0020] Preferably, the crystallization solution in step b is a mixed solution of dichloromethane and water, wherein the mass ratio of dichloromethane to water is 1:1 to 1:4.
[0021] Compared with the prior art, the beneficial effects of the present invention are as follows:
[0022] This invention utilizes a bifunctional acid-base catalyst to synthesize chlorophenoxylate. The reaction process requires no strong acid or base, is non-corrosive to production equipment, effectively reduces raw material and equipment losses, and is environmentally friendly. The bifunctional solid catalyst is easily recoverable after the reaction, effectively suppresses side reactions, and the product is easy to purify. High-purity products can be obtained by slurry washing with dichloromethane. The process is simple, requires no recrystallization, and poses no risk of flammability or explosion. Attached Figure Description
[0023] Figure 1The image shows an electron microscope (EM) image of the catalyst obtained in Example 1.
[0024] Figure 2 The image shows the chlorophenoxylate product obtained in Example 4;
[0025] Figure 3 The liquid chromatogram of the chlorophenoxylate product obtained in Example 4;
[0026] Figure 4 The liquid chromatogram of the chlorophenoxylate product obtained in Example 5;
[0027] Figure 5 The liquid chromatogram of the chlorophenoxylate product obtained in Example 6;
[0028] Figure 6 The image shows the liquid chromatogram of the chlorophenoxylate product obtained in Comparative Example 1. Detailed Implementation
[0029] The technical solutions in specific embodiments of the present invention will be described in detail and completely below. Obviously, the described embodiments are only some specific implementations of the overall technical solution of the present invention, and not all implementations. Based on the overall concept of the present invention, all other embodiments obtained by those skilled in the art fall within the protection scope of the present invention.
[0030] This invention provides an acid-base bifunctional solid catalyst, which is prepared by the following steps:
[0031] 1) Disperse UiO-66-NH2 in dimethylformamide, add 2-chloroethylamine hydrochloride to react, and obtain imine-modified UiO-66-NH2;
[0032] 2) The imide-modified UiO-66-NH2 was dispersed in methanol, formaldehyde was added, and the reaction was carried out to obtain a solid product;
[0033] 3) The solid product is dispersed in acetonitrile, hypophosphoric acid is added, and the reaction is carried out to obtain a bifunctional acid-base solid catalyst.
[0034] This invention disperses UiO-66-NH2 in dimethylformamide (DMF), and then reacts it with 2-chloroethylamine hydrochloride to obtain imine-modified UiO-66-NH2. In this invention, the dispersion method is preferably ultrasonic. In this invention, the mass-to-volume ratio of UiO-66-NH2 to DMF is preferably 0.5-1 g: 50-100 mL. In this invention, the molar ratio of UiO-66-NH2 to 2-chloroethylamine hydrochloride is preferably 0.5-1 g: 0.5-1 mmol. In this invention, the reaction temperature is preferably 75-85°C, and the reaction time is preferably 22-26 h. In this invention, stirring is preferably performed during the reaction. This invention does not have a specific limitation on the stirring speed, as long as it ensures thorough mixing of the materials. In this invention, after the reaction, the obtained solid is preferably washed with DMF and ethanol respectively, and the washed solid is dried overnight in an oven at 80°C.
[0035] After obtaining the imino-modified UiO-66-NH2, the present invention disperses the imino-modified UiO-66-NH2 in methanol, adds formaldehyde, and reacts to obtain a solid product. In the present invention, the preferred mass-to-volume ratio of the imino-modified UiO-66-NH2 to methanol is 0.5-1 g: 50-100 mL. In the present invention, the preferred molar ratio of the imino-modified UiO-66-NH2 to formaldehyde is 0.5-1 g: 1-2 mmol. In the present invention, the preferred reaction temperature is 20-30℃, and the preferred reaction time is 22-26 h. In the present invention, stirring is preferred during the reaction. In the present invention, the obtained solid is preferably washed with methanol and then dried overnight at 60℃. In the present invention, the imino-modified UiO-66-NH2 reacts with formaldehyde to condense with an amino group to form a highly reactive imine intermediate, which is used for subsequent functional group introduction.
[0036] After obtaining the solid product, the present invention disperses the solid product in acetonitrile, adds hypophosphoric acid, and reacts to obtain an acid-base bifunctional solid catalyst. In the present invention, the dispersion method is preferably ultrasonic. In the present invention, the mass-to-volume ratio of the iminolated UiO-66-NH2 to acetonitrile is preferably 0.5-1 g: 5-10 mL. In the present invention, the mass-to-molar ratio of the iminolated UiO-66-NH2 to hypophosphoric acid is preferably 0.5-1 g: 1-2 mmol. In the present invention, the reaction temperature is preferably 20-30℃, and the reaction time is preferably 22-26 h. In the present invention, stirring is preferably performed during the reaction. In the present invention, after the reaction is completed, the reaction solution is preferably centrifuged, the obtained solid is washed with acetonitrile, and then dried overnight at 80℃ to obtain the acid-base bifunctional solid catalyst.
[0037] The catalyst provided by this invention uses UiO-66-NH2 as a support. UiO-66-NH2, as a MOF material, is resistant to water, organic solvents, and acids and alkalis, exhibiting high stability. Acid-base modification of UiO-66-NH2 yields an acid-base bifunctional solid catalyst with pore sizes that allow for substrate molecular-scale sieving, effectively improving reaction selectivity.
[0038] This invention also provides a method for synthesizing chlorophenoxylate, comprising the following steps:
[0039] a. Mix epichlorohydrin, water and any one of the above-mentioned acid-base bifunctional solid catalysts, and heat under reflux for 1-3 hours. Then add p-chlorophenol and continue to reflux for 1-3 hours to obtain a reaction solution.
[0040] b. Filter the reaction solution, add the filtrate to the crystallization solution to crystallize, and obtain chlorophenoxylate.
[0041] This invention involves mixing epichlorohydrin, water, and any one of the acid-base bifunctional solid catalysts described above, and subjecting the mixture to reflux for 1-3 hours. Subsequently, p-chlorophenol is added, and the mixture is refluxed for another 1-3 hours to obtain a reaction solution. In this invention, the mass ratio of epichlorohydrin to the acid-base bifunctional solid catalyst is preferably 1:0.1-1:0.8, more preferably 1:0.15-1:0.5. In this invention, the molar ratio of epichlorohydrin to p-chlorophenol is preferably 1:0.7-2.0. In this invention, the reflux temperature is preferably 80-120°C, more preferably 100-110°C.
[0042] After obtaining the reaction solution, the present invention filters the reaction solution and adds the filtrate to a crystallization solution for crystallization. The obtained crystals are chlorophenoxylate, and the catalyst is recovered after washing. In the present invention, the crystallization solution is preferably a mixed solution of dichloromethane and water, and the mass ratio of dichloromethane to water is preferably 1:1 to 1:4. In the present invention, after obtaining chlorophenoxylate crystals, the obtained crystals are preferably added to dichloromethane sequentially for slurry washing, filtration, and drying, thereby further purifying the obtained chlorophenoxylate.
[0043] This invention utilizes a bifunctional acid-base catalyst to synthesize chlorophenoxylate. The reaction process requires no strong acid or base, is non-corrosive to production equipment, effectively reduces raw material and equipment losses, and is environmentally friendly. The bifunctional solid catalyst is easily recoverable after the reaction, effectively suppresses side reactions, and the product is easy to purify. High-purity products can be obtained by slurry washing with dichloromethane. The process is simple, requires no recrystallization, and poses no risk of flammability or explosion.
[0044] To further illustrate the present invention, the technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.
[0045] Example 1
[0046] 0.5 g of UiO-66-NH2 was ultrasonically dispersed in 50 mL of DMF, and 0.75 mmol of 2-chloroethylamine hydrochloride was added. The mixture was stirred at 80 °C for 24 h. After the reaction was completed, the solid obtained was washed with DMF and ethanol in sequence. The washed solid was placed in an oven and dried at 80 °C overnight to obtain imide-modified UiO-66-NH2.
[0047] 0.5 g of the modified UiO-66-NH2 solid was dispersed in 50 mL of methanol and ultrasonically dispersed. 1.60 mmol of formaldehyde was added, and the mixture was stirred at 25 °C for 24 h. After centrifugation, the resulting solid was washed with methanol and dried overnight at 60 °C. The dried solid was dispersed in 5 mL of acetonitrile and ultrasonically dispersed. 1.60 mmol of hypophosphoric acid was added, and the mixture was stirred at 25 °C for 24 h. After centrifugation, the resulting solid was washed with acetonitrile and dried at 80 °C to obtain solid catalyst 1, which simultaneously possesses acid-base dual sites. Its electron micrograph is shown below. Figure 1 As shown.
[0048] Example 2
[0049] 1 g of UiO-66-NH2 was ultrasonically dispersed in 100 mL of DMF, and 1 mmol of 2-chloroethylamine hydrochloride was added. The mixture was stirred at 85 °C for 22 h. After the reaction was completed, the solid obtained was washed with DMF and ethanol in sequence. The washed solid was placed in an oven and dried at 80 °C overnight to obtain imide-modified UiO-66-NH2.
[0050] 1 g of the modified UiO-66-NH2 solid was dispersed in 100 mL of methanol and ultrasonically dispersed. 2 mmol of formaldehyde was added, and the mixture was stirred at 20 °C for 26 h. After centrifugation, the solid was washed with methanol and dried at 60 °C overnight. The dried solid was dispersed in 10 mL of acetonitrile and ultrasonically dispersed. 2 mmol of hypophosphoric acid was added, and the mixture was stirred at 20 °C for 22 h. After centrifugation, the solid was washed with acetonitrile and dried at 80 °C to obtain solid catalyst 2, which simultaneously possesses acid-base dual sites.
[0051] Example 3
[0052] 0.5 g of UiO-66-NH2 was ultrasonically dispersed in 50 mL of DMF, and 0.5 mmol of 2-chloroethylamine hydrochloride was added. The mixture was stirred at 75 °C for 22 h. After the reaction was completed, the solid obtained was washed with DMF and ethanol in sequence. The washed solid was placed in an oven and dried at 80 °C overnight to obtain imide-modified UiO-66-NH2.
[0053] 0.5 g of the modified UiO-66-NH2 solid was dispersed in 50 mL of methanol and ultrasonically dispersed. 1 mmol of formaldehyde was added, and the mixture was stirred at 30 °C for 24 h. After centrifugation, the solid was washed with methanol and dried at 60 °C overnight. The dried solid was dispersed in 5 mL of acetonitrile and ultrasonically dispersed. 1 mmol of hypophosphoric acid was added, and the mixture was stirred at 30 °C for 24 h. After centrifugation, the solid was washed with acetonitrile and dried at 80 °C to obtain solid catalyst 3, which simultaneously possesses acid-base dual sites.
[0054] Example 4
[0055] (1) Add 100 ml of water, 15 g of catalyst 1, and 83.8 g of epichlorohydrin to the reactor, heat to 100 °C, and reflux for 1 h. Then add 128.8 g of p-chlorophenol and continue to heat and reflux for 1 h. After the reaction is complete, allow the mixture to cool naturally, filter and separate the catalyst from the reaction solution, and recover the catalyst after washing and drying.
[0056] (2) Add the filtrate obtained by filtration to a mixture of dichloromethane and water (mass ratio 1:1) while stirring. A white solid precipitates out of the solution. After filtration, crude chlorphenesin is obtained.
[0057] (3) The crude product was added to 800 mL of dichloromethane, heated to 30°C, and slurried and washed for 30 min. After cooling naturally to room temperature, it was filtered. The resulting solid was dried at 40°C overnight to obtain 148.3 g of purified chlorphenesin solid (the obtained chlorphenesin product is as follows). Figure 2 The product was detected by liquid chromatography (chromatogram shown). Figure 3 As shown), the content was 98.21%, and the yield was 71.7% calculated using the amount of p-chlorophenol.
[0058] Example 5
[0059] (1) Add 100 ml of water, 20 g of catalyst 2, and 40 g of epichlorohydrin to the reactor, heat to 110 °C, and reflux for 1 h. Then add 40 g of p-chlorophenol and continue to heat and reflux for 1 h. After the reaction is complete, allow the mixture to cool naturally, filter and separate the catalyst from the reaction solution, and clean and dry the catalyst for recovery.
[0060] (2) Add the filtrate obtained by filtration to a mixture of dichloromethane and water (mass ratio 1:2) while stirring. A white solid precipitates out of the solution. After filtration, crude chlorphenesin is obtained.
[0061] (3) The crude product was added to 800 mL of dichloromethane, heated to 35°C, stirred and washed for 30 min, then cooled naturally to room temperature and filtered. The resulting solid was dried at 40°C overnight to obtain 52.1 g of purified chlorophenoxylate. The product was detected by liquid chromatography (chromatogram as shown). Figure 4 As shown), the content is 99.08%, and the yield is 81.87% calculated using the amount of p-chlorophenol.
[0062] Example 6
[0063] (1) Add 100 ml of water, 50 g of catalyst 3, and 83.8 g of epichlorohydrin to the reactor, heat to 85 °C, and reflux for 3 h. Then add 128.8 g of p-chlorophenol and continue to heat and reflux for 3 h. After the reaction is completed, allow it to cool naturally, filter and separate the catalyst from the reaction solution, and recover the catalyst after washing and drying.
[0064] (2) Add the filtrate obtained by filtration to a mixture of dichloromethane and water (mass ratio 1:4) while stirring. A white solid precipitates out of the solution. After filtration, crude chlorphenesin is obtained.
[0065] (3) The crude product was added to 800 mL of dichloromethane, heated to 30°C, stirred and washed for 30 min, then cooled naturally to room temperature and filtered. The resulting solid was dried at 40°C overnight to obtain 144.5 g of purified chlorophenoxylate solid. The product was detected by liquid chromatography (chromatogram as shown). Figure 5 As shown), the content is 99.10%, and the yield is 70.54% calculated using the amount of p-chlorophenol.
[0066] Comparative Example 1
[0067] (1) Add 200 g of 0.2% sulfuric acid aqueous solution and 83.8 g of epichlorohydrin to the reactor, heat to 100°C, and reflux for 3 h. Cool down to 80°C, add 77.1 g of p-chlorophenol and 110 g of 28.6% sodium hydroxide aqueous solution, heat to 110°C, and reflux for 3 h.
[0068] (2) After the reaction is complete, the reaction solution is dispersed into 1000 mL of water while stirring. Dilute hydrochloric acid is added to the dispersed reaction solution to adjust the solution to neutral. The solution is cooled to 10°C while stirring. A white solid precipitates out of the solution. Stirring is stopped after 1 h, and the solution is filtered to obtain crude chlorphenesin.
[0069] (3) The crude product was added to 800 mL of dichloromethane, heated to 30°C, stirred and slurried for 30 min, then cooled naturally to room temperature and filtered. The resulting solid was dried overnight at 40°C to obtain 87.9 g of purified chlorophenoxylate solid. The product was detected by liquid chromatography (chromatogram as shown). Figure 6 As shown), the content is 99.01%, and the yield is 71.65% calculated using the amount of p-chlorophenol.
[0070] It can be seen that Comparative Example 1 requires the addition of strong acids and bases during the reaction process, which is corrosive to the production equipment and causes wear and tear. Compared with the examples, Comparative Example 1 requires the addition of a large amount of water for dispersion after the reaction, and also requires the addition of additional acid for acid-base neutralization. The process is relatively complex and energy-intensive. Although the yields of Comparative Example 1 and the examples are similar, the yields in this application are calculated based on the amount of p-chlorophenol. Comparative Example 1 uses a larger amount of epichlorohydrin, meaning that the loss of epichlorohydrin is high.
[0071] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.
Claims
1. The application of an acid-base bifunctional solid catalyst in the synthesis of chlorophenoxylate, characterized in that, The method for synthesizing the phenylephrine includes the following steps: a. Epichlorohydrin, water, and an acid-base bifunctional solid catalyst are mixed and refluxed for 1-3 hours. Then, p-chlorophenol is added, and the reflux reaction is continued for another 1-3 hours to obtain a reaction solution. The mass ratio of epichlorohydrin to the acid-base bifunctional solid catalyst in step a is 1:0.1-1:0.
8. The reflux temperature in step a is 80-120℃. b. Filter the reaction solution and add the filtrate to the crystallization solution to obtain chlorophenoxylate; The acid-base bifunctional solid catalyst was prepared using the following steps: 1) Disperse UiO-66-NH2 in dimethylformamide, add 2-chloroethylamine hydrochloride to react, and obtain imine-modified UiO-66-NH2; 2) The imide-modified UiO-66-NH2 was dispersed in methanol, formaldehyde was added, and the reaction was carried out to obtain a solid product; 3) The solid product is dispersed in acetonitrile, hypophosphoric acid is added, and the reaction is carried out to obtain a bifunctional acid-base solid catalyst.
2. The application according to claim 1, characterized in that, The molar ratio of UiO-66-NH2 and 2-chloroethylamine hydrochloride in step 1) is 0.5-1 g: 0.5-1 mmol.
3. The application according to claim 1, characterized in that, The reaction in step 1) takes place at a temperature of 75-85℃ for 22-26 hours.
4. The application according to claim 1, characterized in that, In step 2), the molar ratio of imidized UiO-66-NH2 to formaldehyde is 0.5-1 g: 1-2 mmol.
5. The application according to claim 1, characterized in that, The reaction in step 2) is carried out at a temperature of 20-30℃ for 22-26 hours.
6. The application according to claim 1, characterized in that, In step 3), the mass molar ratio of imidized UiO-66-NH2 to hypophosphoric acid is 0.5-1 g: 1-2 mmol.
7. The application according to claim 1, characterized in that, The reaction in step 3) is carried out at a temperature of 20-30℃ for 22-26 hours.
8. The application according to claim 1, characterized in that, The crystallization solution mentioned in step b is a mixed solution of dichloromethane and water, wherein the mass ratio of dichloromethane to water is 1:1 to 1:4.