A highly efficient synthesis method of acetone oxime and 2-pentanone oxime

Abstract

The present application relates to a kind of high-efficiency synthesis method of acetone oxime and 2-pentanone oxime, belong to ketoxime synthesis technical field.The present application is added to reactor ketone or 2-pentanone, ammonia, catalyst, stir and heat, slowly drop hydrogen peroxide, reaction is carried out under closed system;After reaction, filtration, distillation under reduced pressure, obtain acetone oxime or 2-pentanone oxime;The catalyst of the present application is boron modified TS-1 molecular sieve, by TS-1 molecular sieve, vinyl tributyl ketoxime silane, methacrylic acid ester strontium, 1,2,3,4,5,6,7,8,9,10,11-undecahydro-12-mercaptododecanesulfonic acid borane, toluene, triethylamine, response is obtained;Acetone oxime and 2-pentanone oxime prepared by the present application have higher purity and yield.

Description

Technical Field

[0001] This invention relates to the field of ketoxime synthesis technology, and in particular to an efficient method for synthesizing acetone oxime and 2-pentanone oxime. Background Technology

[0002] Acetone oxime is an organic compound, appearing as white needle-like crystals. It is readily soluble in water, ethanol, ether, and acetone, and soluble in acids and alkalis, but readily hydrolyzes in dilute acids. It evaporates rapidly in air. It is a raw material for pharmaceuticals, pesticides, dyes, and organosilicon coupling agents. It can also be used as an analytical reagent to identify nickel, cobalt, etc.; as a chemical deoxygenating agent for water supply; as a protective agent for thermal equipment during shutdown (standby); and as a passivating agent.

[0003] 2-Pentanone oxime is a colorless or pale yellow transparent oily liquid. It is an important organic chemical intermediate. Crosslinking agents synthesized from 2-pentanone oxime are less toxic and have better performance than those synthesized from butanone oxime, and will gradually replace butanone oxime.

[0004] Chinese patent CN106831486A discloses a process for synthesizing ketoximes, which involves reacting ketones, ammonia, and hydrogen peroxide in a carbonate aqueous solution system using titanium silicate molecular sieves as catalysts to generate ketoximes; and the process involves real-time monitoring of the pH value of the reaction system to determine the reaction progress and the optimal reaction ratio.

[0005] Chinese Patent CN108069873A: This invention relates to a method for preparing acetone oxime, comprising the following steps: a) Preparation of the reaction system: adding acetone oxime and acetone in a reactor at a molar ratio of 1.0:5.0 to 35.0, then adding an acid catalyst and a solvent, and stirring and mixing evenly in the reactor to form a reaction system with a pH value of 1 to 5; b) Synthesis reaction of acetone oxime: heating the reaction system obtained in step a), controlling the reaction temperature at 5 to 100°C, and reacting for 5 to 10 hours under a pressure of 0 to 2 atm; 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 via ammonia oxidation of 2-pentanone. The method involves reacting 2-pentanone with hydrogen peroxide and ammonia in the presence of a catalyst to generate 2-pentanone oxime. The reaction is carried out in a closed system at a temperature of 40-100℃ for 3-6 hours. The catalyst is a fluorine-modified titanium-silicon molecular sieve. After the reaction, the reaction solution is filtered to recover the catalyst, and the organic layer is separated. The organic layer is then dried with anhydrous sodium sulfate and distilled under reduced pressure to obtain pure 2-pentanone oxime.

[0007] The ketoximes prepared by the above patents and existing technologies have complex processes, long procedures, high costs, and generate by-products. The purity and yield of the products also need to be further improved. Summary of the Invention

[0008] To address the above problems, this invention provides an efficient method for synthesizing acetone oxime and 2-pentanone oxime, the steps of which are as follows:

[0009] S1: Add 80-90 parts of acetone or 2-pentanone, 260-280 parts of ammonia water, and 8-14 parts of catalyst to the reactor, stir and heat, slowly add 160-200 parts of hydrogen peroxide, and carry out the reaction in a closed system.

[0010] S2: After the reaction is complete, filter and distill under reduced pressure to obtain acetone oxime or 2-pentanone oxime.

[0011] The mass concentration of the ammonia water is 20-25%.

[0012] The hydrogen peroxide has a mass concentration of 25-30%.

[0013] The reaction temperature is 70-90℃ and the reaction time is 4-7h.

[0014] The catalyst is a boron-modified TS-1 molecular sieve, and its preparation method is as follows:

[0015] 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 vinyltributylone oxime silane, heat and stir to react, filter, and spin dry;

[0016] 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-undecylhydro-12-mercaptododecylborane (CAS No. 12294-22-3), 1000-1200 parts of toluene, and 3-6 parts of triethylamine. Stir the reaction at room temperature, filter, centrifuge and wash multiple times using a high-speed centrifuge, and dry the resulting sample in a vacuum drying oven to obtain boron-modified TS-1 molecular sieve.

[0017] The reaction temperature of A1 is 40-50℃, and the reaction time is 100-150 minutes.

[0018] The reaction time of S2 is 60-120 minutes.

[0019] Reaction mechanism

[0020] The boron modification mechanism of TS-1 molecular sieve is achieved through a mercapto-olefin addition reaction. Specifically, strontium methacrylate undergoes a mercapto-olefin addition reaction with undecylhydro-12-mercaptododecanoborane to obtain a TS-1 molecular sieve with surface-grafted strontium complexes and functional groups such as dodecanoborane. Subsequently, it undergoes a mercapto-olefin addition reaction with undecylhydro-12-mercaptododecanoborane to obtain another TS-1 molecular sieve with surface-grafted strontium complexes and functional groups such as dodecanoborane.

[0021] Boron-modified TS-1 molecular sieves (B-TS-1) are achieved by introducing heteroatoms (B) into TS-1 molecular sieves. Specifically, strontium methacrylate undergoes a mercapto-olefin addition reaction with undecylhydro-12-mercaptododecorane to obtain TS-1 molecular sieves with surface-grafted strontium complexes and functional groups such as dodecorane. Subsequently, it is reacted with vinyltributanone oxime silane to obtain the final B-TS-1 molecular sieve.

[0022] Technical effect

[0023] This invention provides an efficient method for the synthesis of acetone oxime and 2-pentanone oxime. Compared with existing technologies, this invention has the following significant advantages:

[0024] 1. This surface grafting technology can significantly improve the catalytic performance of TS-1 molecular sieves, enabling them to exhibit higher activity and selectivity in the catalytic preparation of acetone and hydrogen peroxide. For example, TS-1 molecular sieves with surface-grafted strontium complexes and functional groups such as dodecorane prepared by this method show high catalytic activity and selectivity in the hydroxylation of phenol and the epoxidation of n-hexene.

[0025] 2. From a molecular structure perspective, the modification of B-TS-1 molecular sieves is mainly achieved through the introduction of boron (B) atoms. The introduction of B atoms alters the surface properties and pore structure of the TS-1 molecular sieve, thereby affecting its catalytic performance. Specifically, the introduction of B atoms may increase the acidic sites of the molecular sieve, thus improving its activity and selectivity in specific reactions.

[0026] 3. From the perspective of catalytic effect, B-TS-1 molecular sieve exhibits excellent catalytic performance in various oxidation reactions. The introduction of boron atoms alters the pore structure of the molecular sieve, affecting the diffusion of reactants and the formation of products.

[0027] In summary, boron-modified TS-1 molecular sieves exhibit unique advantages in terms of molecular structure, catalytic efficacy, and steric hindrance. These advantages make B-TS-1 molecular sieves promising for broad applications in catalysis, particularly in chemical reactions requiring efficient and environmentally friendly catalysts. Detailed Implementation

[0028] To further illustrate the technical means and effects adopted by the present invention to achieve the intended purpose, the following detailed description is provided in conjunction with embodiments and comparative examples:

[0029] Acetone oxime and 2-pentanone oxime were detected by liquid chromatography, and the results are shown in Table 1.

[0030] Example 1

[0031] An efficient method for the synthesis of acetone oxime and 2-pentanone oxime, comprising the following steps:

[0032] S1: Add 80g of acetone, 260g of ammonia and 8g of catalyst to the reactor, stir and heat, slowly add 160g of hydrogen peroxide, and carry out the reaction in a closed system.

[0033] S2: After the reaction is complete, filter and distill under reduced pressure to obtain acetone oxime.

[0034] The mass concentration of the ammonia solution is 20%.

[0035] The hydrogen peroxide has a mass concentration of 25%.

[0036] The reaction temperature is 70℃ and the reaction time is 4 hours.

[0037] The catalyst is a boron-modified TS-1 molecular sieve, and its preparation method is as follows:

[0038] A1: Weigh 120g of TS-1 molecular sieve, slowly add it to 1000g of water and stir, then add 2g of vinyltributylone oxime silane, heat and stir to react, filter, and spin dry;

[0039] A2: Add 0.01g of strontium methacrylate (CAS No. 16436-33-2), 3g of 1,2,3,4,5,6,7,8,9,10,11-undecylhydro-12-mercaptododecylborane (CAS No. 12294-22-3), 1000g of toluene, and 3g of triethylamine. Stir the reaction at room temperature, filter, centrifuge and wash multiple times using a high-speed centrifuge, and dry the resulting sample in a vacuum drying oven to obtain boron-modified TS-1 molecular sieve.

[0040] The reaction temperature of A1 is 40°C and the reaction time is 100 minutes.

[0041] The reaction time of A2 is 60 minutes.

[0042] Example 2

[0043] An efficient method for the synthesis of acetone oxime and 2-pentanone oxime, comprising the following steps:

[0044] S1: Add 83g of acetone, 265g of ammonia and 10g of catalyst to the reactor, stir and heat, slowly add 170g of hydrogen peroxide, and carry out the reaction in a closed system.

[0045] S2: After the reaction is complete, filter and distill under reduced pressure to obtain acetone oxime.

[0046] The mass concentration of the ammonia solution is 21%.

[0047] The hydrogen peroxide has a mass concentration of 26%.

[0048] The reaction temperature is 75℃ and the reaction time is 5h.

[0049] The catalyst is a boron-modified TS-1 molecular sieve, and its preparation method is as follows:

[0050] A1: Weigh 130g of TS-1 molecular sieve, slowly add it to 1050g of water and stir, then add 3g of vinyltributylone oxime silane, heat and stir to react, filter, and spin dry;

[0051] A2: Add 0.05g of strontium methacrylate (CAS No. 16436-33-2), 5g of 1,2,3,4,5,6,7,8,9,10,11-undecylhydro-12-mercaptododecylborane (CAS No. 12294-22-3), 1050g of toluene, and 4g of triethylamine. Stir the reaction at room temperature, filter, centrifuge and wash multiple times using a high-speed centrifuge, and dry the resulting sample in a vacuum drying oven to obtain boron-modified TS-1 molecular sieve.

[0052] The reaction temperature of A1 is 45°C and the reaction time is 110 minutes.

[0053] The reaction time of A2 is 80 minutes.

[0054] Example 3

[0055] An efficient method for the synthesis of acetone oxime and 2-pentanone oxime, comprising the following steps:

[0056] S1: Add 88g of 2-pentanone, 275g of ammonia, and 12g of catalyst to the reactor, stir and heat, slowly add 190g of hydrogen peroxide, and carry out the reaction in a closed system.

[0057] S2: After the reaction is complete, filter and distill under reduced pressure to obtain 2-pentanone oxime.

[0058] The mass concentration of the ammonia solution is 24%.

[0059] The hydrogen peroxide has a mass concentration of 28%.

[0060] The reaction temperature is 85℃ and the reaction time is 6 hours.

[0061] The catalyst is a boron-modified TS-1 molecular sieve, and its preparation method is as follows:

[0062] A1: Weigh 140g of TS-1 molecular sieve, slowly add it to 1150g of water and stir, then add 4g of vinyltributylone oxime silane, heat and stir to react, filter, and spin dry;

[0063] A2: Add 0.08g of strontium methacrylate (CAS No. 16436-33-2), 9g of 1,2,3,4,5,6,7,8,9,10,11-undecylhydro-12-mercaptododecylborane (CAS No. 12294-22-3), 1150g of toluene, and 5g of triethylamine. Stir the reaction at room temperature, filter, centrifuge and wash multiple times using a high-speed centrifuge, and dry the resulting sample in a vacuum drying oven to obtain boron-modified TS-1 molecular sieve.

[0064] The reaction temperature of A1 is 45°C and the reaction time is 140 minutes.

[0065] The reaction time of A2 is 100 minutes.

[0066] Example 4

[0067] An efficient method for the synthesis of acetone oxime and 2-pentanone oxime, comprising the following steps:

[0068] S1: Add 90g of 2-pentanone, 280g of ammonia, and 14g of catalyst to the reactor, stir and heat, slowly add 200g of hydrogen peroxide, and carry out the reaction in a closed system.

[0069] S2: After the reaction is complete, filter and distill under reduced pressure to obtain 2-pentanone oxime.

[0070] The mass concentration of the ammonia solution is 25%.

[0071] The hydrogen peroxide has a mass concentration of 30%.

[0072] The reaction temperature is 90℃ and the reaction time is 7h.

[0073] The catalyst is a boron-modified TS-1 molecular sieve, and its preparation method is as follows:

[0074] A1: Weigh 150g of TS-1 molecular sieve, slowly add it to 1200g of water and stir, then add 5g of vinyltributylone oxime silane, heat and stir to react, filter, and spin dry;

[0075] A2: Add 0.1g of strontium methacrylate (CAS No. 16436-33-2), 11g of 1,2,3,4,5,6,7,8,9,10,11-undecylhydro-12-mercaptododecylborane (CAS No. 12294-22-3), 1200g of toluene, and 6g of triethylamine. Stir the reaction at room temperature, filter, centrifuge and wash multiple times using a high-speed centrifuge, and dry the resulting sample in a vacuum drying oven to obtain boron-modified TS-1 molecular sieve.

[0076] The reaction temperature of A1 is 50°C and the reaction time is 150 minutes.

[0077] The reaction time of A2 is 120 minutes.

[0078] Comparative Example 1

[0079] No modification was made to the TS-1 molecular sieve; otherwise, it was the same as in Example 1.

[0080] Comparative Example 2

[0081] Without the addition of strontium methacrylate, the rest is the same as in Example 1.

[0082] Comparative Example 3

[0083] The same as in Example 1 was used, but without the addition of 1,2,3,4,5,6,7,8,9,10,11-undecylhydro-12-mercaptododecylane.

[0084] Table 1

[0085] 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

[0086] Based on the data analysis of the above examples and comparative examples, the acetone oxime and 2-pentanone oxime prepared by the present invention have high purity and yield.

[0087] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or alterations to the above-disclosed technical content to create equivalent embodiments without departing from the scope of the present invention. Any simple modifications, equivalent changes and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.

Claims

1. A highly efficient method for the synthesis of acetone oxime and 2-pentanone oxime, comprising the following steps: S1: Add 80-90 parts of acetone or 2-pentanone, 260-280 parts of ammonia water, and 8-14 parts of catalyst to the reactor, stir and heat, slowly add 160-200 parts of hydrogen peroxide, and carry out the reaction in a closed system. S2: After the reaction is complete, filter and distill 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, vinyltributylone oxime silane, strontium methacrylate, and 1,2,3,4,5,6,7,8,9,10,11-undecylhydro-12-mercaptododecorane.

2. The efficient synthesis method of 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 hydrogen peroxide has a mass concentration of 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℃ and the reaction time is 4-7h.

5. The efficient method for synthesizing acetone oxime and 2-pentanone oxime according to claim 1, characterized in that: The catalyst is a 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 vinyltributylone 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-undecylhydro-12-mercaptododecylborane, 1000-1200 parts of toluene, and 3-6 parts of triethylamine. Stir the reaction at room temperature, filter, centrifuge and wash multiple times using a high-speed centrifuge, and dry the resulting sample in a vacuum drying oven to obtain boron-modified TS-1 molecular sieve.

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

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