Efficient synthesis method of acetoxime and 2-pentanone oxime

Abstract

The invention relates to an efficient synthesis method of acetoxime and 2-pentanone oxime, and belongs to the technical field of ketoxime synthesis. The method comprises the following steps: adding acetone or 2-pentanone, ammonia water and a catalyst into a reaction kettle, stirring and heating, slowly dropwise adding hydrogen peroxide, and reacting in a closed system; after the reaction is finished, filtering and carrying out reduced pressure distillation to obtain acetoxime or 2-pentanone oxime; the catalyst provided by the invention is a boron modified TS-1 molecular sieve, and is obtained through the reaction of the TS-1 molecular sieve, vinyltris (methylethylketoxime) silane, strontium methacrylate, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11-undeca-hydro-12-mercaptododecane, toluene and triethylamine. The acetoxime and the 2-pentanone oxime prepared by the invention have higher purity and yield.

Description

Technical Field

[0001] The invention relates to the technical field of ketoxime synthesis, in particular to a high-efficiency synthesis method of acetone oxime and 2-pentanone oxime. Background Art

[0002] Acetone oxime is an organic compound, white needle-shaped crystals. It is easily soluble in water, ethanol, ether and acetone, soluble in acid and alkali, and easily hydrolyzed in dilute acid. It evaporates quickly in the air. It is a raw material for medicine, pesticides, dyes and organosilicon coupling agents. It can also be used as an analytical reagent to identify nickel, cobalt, etc.; a chemical deoxidizer for water supply, a protective agent for thermal equipment shutdown (standby), and a passivating agent.

[0003] 2-Pentanone oxime is a colorless or light yellow transparent oily liquid. It is an important organic chemical intermediate. The cross-linking agent synthesized from 2-pentanone oxime is less toxic than the cross-linking agent synthesized from butanone oxime and has better performance. It will gradually replace butanone oxime.

[0004] Chinese patent CN106831486A: discloses a process for synthesizing ketoxime, in which ketone, ammonia and hydrogen peroxide are reacted to generate ketoxime in a carbonate aqueous solution system with titanium silicon molecular sieve as a catalyst; and during the reaction, the pH value of the reaction system is monitored in real time to judge the reaction progress and determine the optimal reaction ratio.

[0005] Chinese patent CN108069873A: relates to a method for preparing acetone oxime, which comprises the following steps: a) preparation of a reaction system: adding ketone oxime and acetone in a reactor at a molar ratio of 1.0:5.0-35.0, then adding an acid catalyst and a solvent, stirring and mixing in the reactor to form a reaction system, wherein the pH value of the reaction system is 1-5; b) synthesis reaction of acetone oxime: heating the reaction system obtained in step a), controlling the reaction temperature at 5-100°C, reacting at a pressure of 0-2 atm for 5-10 hours; c) purification of acetone oxime: purifying the product obtained in step b) to obtain acetone oxime.

[0006] Chinese patent CN110981750A: discloses a method for synthesizing 2-pentanone oxime by ammoxidation reaction of 2-pentanone, wherein 2-pentanone is reacted with hydrogen peroxide and ammonia water in the presence of a catalyst to generate 2-pentanone oxime, wherein the reaction is carried out in a closed system, the reaction temperature is 40-100°C, the reaction time is 3-6 hours, and the catalyst is a fluorine-modified titanium silicon molecular sieve; after the reaction is completed, the reaction liquid is filtered to recover the catalyst, the organic layer is separated, and then dried over anhydrous sodium sulfate and distilled under reduced pressure to obtain pure 2-pentanone oxime.

[0007] The ketoxime prepared by the above patents and prior art has complex processes, long processes, high costs, and the generation of by-products. The purity and yield of the products also need to be further improved. Summary of the invention

[0008] In order to solve the above problems, the present invention provides an efficient synthesis method of acetone oxime and 2-pentanone oxime, and the operation steps are as follows: S1: After adding 80-90 parts of acetone or 2-pentanone, 260-280 parts of ammonia water, and 8-14 parts of a catalyst into a reaction kettle, stirring and heating, slowly dropwise adding 160-200 parts of hydrogen peroxide, and reacting in a closed system; S2: After the reaction is completed, filter and distill under reduced pressure to obtain acetone oxime or 2-pentanone oxime.

[0009] The mass concentration of the ammonia water is 20-25%.

[0010] The mass concentration of the hydrogen peroxide is 25-30%.

[0011] The reaction temperature is 70-90°C and the reaction time is 4-7h.

[0012] The catalyst is boron-modified TS-1 molecular sieve, and its preparation method is as follows: A1: Weigh 120-150 parts of TS-1 molecular sieve by weight, slowly add it to 1000-1200 parts of water and stir, then add 2-5 parts of vinyltributylidene oxime silane, heat and stir to react, filter and spin dry; A2: Add 0.01-0.1 parts of strontium methacrylate CAS No. 16436-33-2, 3-11 parts of 1,2,3,4,5,6,7,8,9,10,11-undecyl-12-mercapto-dodecaborane CAS No. 12294-22-3, 1000-1200 parts of toluene, and 3-6 parts of triethylamine, stir to react at room temperature, filter, centrifuge and wash several times using a high-speed centrifuge, and dry the obtained sample in a vacuum drying oven to obtain a boron-modified TS-1 molecular sieve.

[0013] The reaction temperature of A1 is 40-50°C and the reaction time is 100-150 minutes.

[0014] The reaction time of S2 is 60-120 minutes.

[0015] Reaction mechanism The boron modification mechanism of TS-1 molecular sieve is achieved through mercapto-olefin addition reaction. Specifically, strontium methacrylate and undecahydro-12-mercapto-dodecane borane undergo mercapto-olefin addition reaction to obtain TS-1 molecular sieve with surface grafted strontium complex, dodecane and other functional groups. Subsequently, mercapto-olefin addition reaction is carried out with undecahydro-12-mercapto-dodecane borane to obtain TS-1 molecular sieve with surface grafted strontium complex, dodecane and other functional groups.

[0016] Boron-modified TS-1 molecular sieve (B-TS-1) is achieved by introducing heteroatom B into TS-1 molecular sieve. Specifically, strontium methacrylate and undecahydro-12-mercapto-dodecaborane undergo a mercapto-olefin addition reaction to obtain a TS-1 molecular sieve with surface grafted strontium complexes, dodecaborane and other functional groups. Subsequently, it reacts with vinyl trisbutyl oxime silane to obtain the final B-TS-1 molecular sieve.

[0017] Technical Effects The invention discloses a highly efficient synthesis method of acetone oxime and 2-pentanone oxime. Compared with the prior art, the invention has the following significant effects: 1. This surface grafting technology can significantly improve the catalytic performance of TS-1 molecular sieves, making them show higher activity and selectivity in the catalytic preparation process of acetone and hydrogen peroxide. For example, the TS-1 molecular sieves with surface grafted strontium complexes, dodecaborane and other functional groups prepared by this method showed high catalytic activity and selectivity in phenol hydroxylation and n-hexene epoxidation reactions.

[0018] 2. From the perspective of molecular structure, the modification of B-TS-1 molecular sieve is mainly achieved by introducing B atoms. The introduction of B atoms changes the surface properties and pore structure of TS-1 molecular sieve, thereby affecting its catalytic performance. Specifically, the introduction of B atoms may increase the acid sites of the molecular sieve, thereby improving its activity and selectivity in specific reactions.

[0019] 3. From the perspective of catalytic effect, B-TS-1 molecular sieve exhibits excellent catalytic performance in a variety of oxidation reactions. Since the introduction of B atoms changes the pore structure of the molecular sieve, it will affect the diffusion of reactants and the formation of products.

[0020] In summary, boron-modified TS-1 molecular sieves have unique advantages in molecular structure, catalytic effect, and steric hindrance. These advantages make B-TS-1 molecular sieves have broad application prospects in the field of catalysis, especially in chemical reactions that require efficient and environmentally friendly catalysts. DETAILED DESCRIPTION

[0021] In order to further explain the technical means and effects adopted by the present invention to achieve the predetermined invention purpose, the following is a detailed description in combination with embodiments and comparative examples: Acetone oxime and 2-pentanone oxime were detected by liquid chromatography. The detection results are shown in Table 1.

[0022] Example 1 An efficient synthesis method of acetone oxime and 2-pentanone oxime, the operation steps of which are: S1: After adding 80g of acetone, 260g of ammonia water and 8g of catalyst into a reactor, stirring and heating, 160g of hydrogen peroxide solution was slowly added dropwise to react in a closed system; S2: After the reaction is completed, filter and distill under reduced pressure to obtain acetone oxime.

[0023] The mass concentration of the ammonia water is 20%.

[0024] The mass concentration of the hydrogen peroxide is 25%.

[0025] The reaction temperature is 70°C and the reaction time is 4 hours.

[0026] The catalyst is boron-modified TS-1 molecular sieve, and its preparation method is as follows: A1: Weigh 120g of TS-1 molecular sieve, slowly add it to 1000g of water and stir, then add 2g of vinyltributylidene oxime silane, heat and stir to react, filter and spin dry; A2: Add 0.01 g of strontium methacrylate CAS No. 16436-33-2, 3 g of 1,2,3,4,5,6,7,8,9,10,11-undecyl-12-mercapto-dodecaborane CAS No. 12294-22-3, 1000 g of toluene, and 3 g of triethylamine, stir to react at room temperature, filter, centrifuge and wash several times using a high-speed centrifuge, and dry the obtained sample in a vacuum drying oven to obtain a boron-modified TS-1 molecular sieve.

[0027] The reaction temperature of A1 is 40°C and the reaction time is 100 minutes.

[0028] The reaction time of A2 is 60 minutes.

[0029] Example 2 An efficient synthesis method of acetone oxime and 2-pentanone oxime, the operation steps of which are: S1: After adding 83g acetone, 265g ammonia water and 10g catalyst into the reactor, stirring and heating, 170g hydrogen peroxide was slowly added dropwise to react in a closed system; S2: After the reaction is completed, filter and distill under reduced pressure to obtain acetone oxime.

[0030] The mass concentration of the ammonia water is 21%.

[0031] The mass concentration of the hydrogen peroxide is 26%.

[0032] The reaction temperature is 75°C and the reaction time is 5h.

[0033] The catalyst is boron-modified TS-1 molecular sieve, and its preparation method is as follows: A1: Weigh 130g of TS-1 molecular sieve, slowly add it to 1050g of water and stir, then add 3g of vinyltributylidene oxime silane, heat and stir to react, filter and spin dry; A2: Add 0.05 g of strontium methacrylate CAS No. 16436-33-2, 5 g of 1,2,3,4,5,6,7,8,9,10,11-undecyl-12-mercapto-dodecaborane CAS No. 12294-22-3, 1050 g of toluene, and 4 g of triethylamine, react at room temperature with stirring, filter, centrifuge and wash several times using a high-speed centrifuge, and dry the obtained sample in a vacuum drying oven to obtain a boron-modified TS-1 molecular sieve.

[0034] The reaction temperature of A1 is 45°C and the reaction time is 110 minutes.

[0035] The reaction time of A2 is 80 minutes.

[0036] Example 3 An efficient synthesis method of acetone oxime and 2-pentanone oxime, the operation steps of which are: S1: After adding 88g 2-pentanone, 275g ammonia water and 12g catalyst into a reactor, stirring and heating, 190g hydrogen peroxide was slowly added dropwise to react in a closed system; S2: After the reaction is completed, filter and distill under reduced pressure to obtain 2-pentanone oxime.

[0037] The mass concentration of the ammonia water is 24%.

[0038] The mass concentration of the hydrogen peroxide is 28%.

[0039] The reaction temperature is 85°C and the reaction time is 6 hours.

[0040] The catalyst is boron-modified TS-1 molecular sieve, and its preparation method is as follows: A1: Weigh 140g of TS-1 molecular sieve, slowly add it to 1150g of water and stir, then add 4g of vinyltributylidene oxime silane, heat and stir to react, filter and spin dry; A2: Add 0.08 g of strontium methacrylate CAS No. 16436-33-2, 9 g of 1,2,3,4,5,6,7,8,9,10,11-undecyl-12-mercaptododecaborane CAS No. 12294-22-3, 1150 g of toluene, and 5 g of triethylamine, stir to react at room temperature, filter, centrifuge and wash several times using a high-speed centrifuge, and dry the obtained sample in a vacuum drying oven to obtain a boron-modified TS-1 molecular sieve.

[0041] The reaction temperature of A1 is 45°C and the reaction time is 140 minutes.

[0042] The reaction time of A2 is 100 minutes.

[0043] Example 4 An efficient synthesis method of acetone oxime and 2-pentanone oxime, the operation steps of which are: S1: After adding 90g 2-pentanone, 280g ammonia water and 14g catalyst into a reactor, stirring and heating, 200g hydrogen peroxide was slowly added dropwise to react in a closed system; S2: After the reaction is completed, filter and distill under reduced pressure to obtain 2-pentanone oxime.

[0044] The mass concentration of the ammonia water is 25%.

[0045] The mass concentration of the hydrogen peroxide is 30%.

[0046] The reaction temperature is 90°C and the reaction time is 7h.

[0047] The catalyst is boron-modified TS-1 molecular sieve, and its preparation method is as follows: A1: Weigh 150g of TS-1 molecular sieve, slowly add it into 1200g of water and stir, then add 5g of vinyltributylidene oxime silane, heat and stir to react, filter and spin dry; A2: Add 0.1 g of strontium methacrylate CAS No. 16436-33-2, 11 g of 1,2,3,4,5,6,7,8,9,10,11-undecyl-12-mercapto-dodecaborane CAS No. 12294-22-3, 1200 g of toluene, and 6 g of triethylamine, stir to react at room temperature, filter, centrifuge and wash several times using a high-speed centrifuge, and dry the obtained sample in a vacuum drying oven to obtain a boron-modified TS-1 molecular sieve.

[0048] The reaction temperature of A1 is 50°C and the reaction time is 150 minutes.

[0049] The reaction time of A2 is 120 minutes.

[0050] Comparative Example 1 The TS-1 molecular sieve was not modified, and the other steps were the same as in Example 1.

[0051] Comparative Example 2 The other steps were the same as in Example 1 except that strontium methacrylate was not added.

[0052] Comparative Example 3 The other steps were the same as in Example 1 except that 1,2,3,4,5,6,7,8,9,10,11-undecylhydro-12-mercaptododecaborane was not added.

[0053] Table 1 purity / % Yield / % Example 1 99.85 96.61 Example 2 99.87 96.75 Example 3 99.90 96.88 Example 4 99.93 97.13 Comparative Example 1 88.10 83.57 Comparative Example 2 93.84 90.75 Comparative Example 3 95.22 92.36 Through the data analysis of the above examples and comparative examples, the acetone oxime and 2-pentanone oxime prepared by the present invention have higher purity and yield.

[0054] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. Although the present invention has been disclosed as a preferred embodiment as above, it is not used to limit the present invention. Any technical personnel in this field can make some changes or modify the technical contents disclosed above into equivalent embodiments without departing from the scope of the technical solution of the present invention. However, any brief modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention are still within the scope of the technical solution of the present invention.

Claims

1. An efficient synthesis method of acetone oxime and 2-pentanone oxime, the operation steps of which are: S1: After adding 80-90 parts of acetone or 2-pentanone, 260-280 parts of ammonia water, and 8-14 parts of a catalyst into a reaction kettle, stirring and heating, slowly dropwise adding 160-200 parts of hydrogen peroxide, and reacting in a closed system; S2: After the reaction is completed, filtering and distilling under reduced pressure to obtain acetone oxime or 2-pentanone oxime; The catalyst is a boron-modified TS-1 molecular sieve, which is obtained by reacting TS-1 molecular sieve, vinyl tributylidene oxime silane, strontium methacrylate, and 1,2,3,4,5,6,7,8,9,10,11-undecylhydro-12-mercapto dodecaborane.

2. The method for efficiently synthesizing acetone oxime and 2-pentanone oxime according to claim 1, characterized in that: The mass concentration of the ammonia water is 20-25%.

3. The efficient synthesis method of acetone oxime and 2-pentanone oxime according to claim 1, characterized in that: The mass concentration of the hydrogen peroxide is 25-30%.

4. The efficient synthesis method of acetone oxime and 2-pentanone oxime according to claim 1, characterized in that: The reaction temperature is 70-90°C and the reaction time is 4-7h.

5. The efficient synthesis method of acetone oxime and 2-pentanone oxime according to claim 1, characterized in that: The catalyst is boron-modified TS-1 molecular sieve, and its preparation method is as follows: A1: Weigh 120-150 parts of TS-1 molecular sieve by weight, slowly add it to 1000-1200 parts of water and stir, then add 2-5 parts of vinyltributylidene oxime silane, heat and stir to react, filter and spin dry; A2: Add 0.01-0.1 parts of strontium methacrylate, 3-11 parts of 1,2,3,4,5,6,7,8,9,10,11-undecyl-12-mercapto-dodecaborane, 1000-1200 parts of toluene, and 3-6 parts of triethylamine, stir and react at room temperature, filter, centrifuge and wash several times using a high-speed centrifuge, and dry the obtained sample in a vacuum drying oven to obtain a boron-modified TS-1 molecular sieve.

6. The method for efficiently synthesizing acetone oxime and 2-pentanone oxime according to claim 5, characterized in that: The reaction temperature of A1 is 40-50°C and the reaction time is 100-150 minutes.

7. The efficient synthesis method of acetone oxime and 2-pentanone oxime according to claim 5, characterized in that: The reaction time of A2 is 60-120 minutes.