High-activity basic catalyst as well as preparation method and application thereof
By introducing basic anions containing oxygen and nitrogen elements onto the catalyst surface, the catalytic activity and selectivity are improved, solving the problem of easy deactivation of existing catalysts and realizing efficient silane production to meet the needs of the high-precision semiconductor field.
Patent Information
- Application Number
- CN202511264066.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-09-05
- Publication Date
- 2025-11-07
AI Technical Summary
Existing silane production catalysts are prone to deactivation and have poor catalytic performance, resulting in low production efficiency and unstable product quality, making it difficult to meet the needs of the high-precision semiconductor field.
By using organic compounds containing heteroatoms as monomers, high-ionic-loading capacity oxygen-nitrogen-containing basic anions are introduced onto the catalyst surface through polymerization reactions to improve catalytic activity and selectivity, thus preparing highly active basic catalytic materials.
It achieves high stability and high selectivity of catalyst, with silane yield reaching 60-70% and selectivity exceeding 97%. It is suitable for fixed-bed tubular reactors and can replace traditional catalysts to improve silane preparation efficiency.
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Figure CN120900700A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the technical field of functional material synthesis and chemical product preparation, and particularly relates to a high-activity alkaline catalyst and a preparation method and application thereof. BACKGROUND
[0002] Compared with 6N-grade silane special gas, 7N-grade silane special gas has higher purity, which means that the application scenarios of the silane special gas can be transferred from the photovoltaic field to the high-precision semiconductor field. The improvement of the purity of the silane special gas is closely related to the catalyst in the production reaction. The existing silane production catalyst is prone to deactivation in the reaction process, and has low reaction selectivity. The catalytic performance of the catalyst in the production process is poor, and the catalyst needs to be replaced frequently, which seriously affects the production efficiency and product quality of the silane.
[0003] Therefore, developing a high-performance catalyst with high selectivity and high conversion rate can greatly promote the development of the semiconductor industry. SUMMARY
[0004] In view of the deficiencies of the prior art, the purpose of the present application is to provide a high-activity alkaline catalyst and a preparation method and application thereof. A more stable organic compound containing heteroatoms is selected as a monomer to improve the catalytic cycle stability; the high ion loading capacity of the surface of the synthesized solid catalyst material is used, and the alkaline anions containing oxygen and nitrogen elements are combined on the surface of the catalyst through electrostatic action to improve the catalytic activity and selectivity, and a series of alkaline catalyst materials with high catalytic activity are created for the preparation of silane by catalytic chlorosilane disproportionation.
[0005] To achieve the above-mentioned purpose, the technical scheme adopted by the present application is as follows: A preparation method of a high-catalytic-activity alkaline catalyst material, specifically comprising the following steps: 1-vinyl-4-(N-methylene-N, N, N-tripropylamine bromide) benzene and tri(1-methylene-3-vinylpyridine bromide) benzene are added to a solvent in a certain proportion, and a polymerization reaction occurs under the action of an initiator; after the reaction is completed, the obtained product is soaked in a solution containing oxygen and nitrogen element anion alkaline groups for a certain time, and after purification, the alkaline catalyst material is obtained.
[0006] Further, the preparation method of the 1-vinyl-4-(N-methylene-N, N, N-tripropylamine bromide) benzene is as follows: 4-vinylbenzyl bromide and tripropylamine are reacted at a molar ratio of 1:1.5 at 60 DEG C under anhydrous and anaerobic conditions for 3 days, and after the reaction is completed, the 1-vinyl-4-(N-methylene-N, N, N-tripropylamine bromide) benzene is obtained by filtration, washing and drying.
[0007] Further, the preparation method of the tris (1-methylene-3-vinylpyridine bromide) benzene is as follows: tris (bromomethyl) benzene and 3-vinylpyridine are dissolved in anhydrous tetrahydrofuran at a molar ratio of 1:3.3, and then the mixture is refluxed at 80-85 DEG C under nitrogen atmosphere for 2 days; after the reaction is completed, the mixture is cooled to room temperature, and then distilled under reduced pressure, induced to crystallize by ethyl acetate, filtered, and dried in vacuum to obtain the tris (1-methylene-3-vinylpyridine bromide) benzene.
[0008] Further, the molar ratio of the 1-vinyl-4-(N-methylene-N, N, N-tripropylamine bromide) benzene and the tris (1-methylene-3-vinylpyridine bromide) benzene is 1:20-20:1.
[0009] Further, the temperature of the polymerization reaction is 40-80 DEG C, and the reaction time is 6-300 h; the solvent is one or a mixture of several of tetrahydrofuran, acetonitrile and N, N-dimethylformamide.
[0010] Further, the initiator is one or several of azobisisobutyronitrile and dimethyl azobisisobutyrate, and the amount of the initiator is 0.1-5 % of the total mass of the 1-vinyl-4-(N-methylene-N, N, N-tripropylamine bromide) benzene and the tris (1-methylene-3-vinylpyridine bromide) benzene.
[0011] Further, the anion basic group containing oxygen and nitrogen elements is sodium hydroxide, the concentration of the sodium hydroxide is 1 mol / L, the temperature of the soaking is 25-40 DEG C, and the soaking time is 8-24 h, and the stirring is carried out every 4-6 h.
[0012] Further, the step of the purification is that the soaked polymer is washed 2-3 times by a solution containing the anion basic group containing oxygen and nitrogen elements, and then the washed polymer is dried at 50-60 DEG C for 12-16 h.
[0013] The application provides the application of the basic solid catalytic material prepared by the preparation method in the preparation of silane by catalyzing chlorosilane disproportionation.
[0014] The application has the following beneficial effects: The application utilizes the abundant functional active cation sites on the surface of the material, and the electron-withdrawing ability and free ability of the functional anions are reasonably regulated through the cation-anion interaction between the small molecule basic anions containing oxygen or nitrogen and the cations on the surface and in the pores, so that the catalytic process with high catalytic activity and selectivity can be realized. The synthesis method is fast and simple, the synthesized catalytic material can be continuously and stably catalyzed at 75 DEG C in a fixed bed tubular reactor, and the high silane yield of 60-70 % and the high silane selectivity of more than 97 % are realized, so that the application can replace the traditional basic catalyst and become an important basic catalyst in the industrial process of silane preparation. BRIEF DESCRIPTION OF DRAWINGS
[0015] Figure 1 is the 1H NMR of 1-vinyl-4-(N-methylene-N,N,N-tripropylammonium bromide) benzene.
[0016] Figure 2 is the 1H NMR of tris(1-methylene-3-vinylpyridinium bromide) benzene.
[0017] Figure 3 is the infrared spectrum of the solid basic catalytic material.
[0018] Figure 4 is the catalytic performance curve of the solid basic catalytic material.
[0019] Figure 5 is the catalytic stability test result of the solid basic catalytic material. DETAILED DESCRIPTION
[0020] In order to make the content described in the present application more convenient to understand, the technical solutions described in the present application will be further described below in combination with specific embodiments, but the present application is not limited to this.
[0021] Example 1 (1) The preparation method of 1-vinyl-4-(N-methylene-N,N,N-tripropylammonium bromide) benzene is as follows: 1 mmol of 4-vinylbenzyl bromide and 1.5 mmol of tripropylamine are added to 30 ml of anhydrous tetrahydrofuran solvent in a 50 ml pressure-resistant bottle, and the reaction is carried out at 60°C under anhydrous and anaerobic conditions for 3 days. After the reaction is completed, 20 ml of ethyl acetate is added and then filtered, and the solid sample is washed with ethyl acetate for multiple times. Finally, the obtained solid is dried at 60°C, and the 1H NMR (nuclear magnetic resonance hydrogen spectrum) of the obtained sample is as shown in Figure 1 .
[0022] (2) The preparation method of tris(1-methylene-3-vinylpyridinium bromide) benzene is as follows: In a dry three-necked flask, 1 mmol of tris(bromomethyl)benzene and 3.3 mmol of 3-vinylpyridine are added, 30-45 mL of anhydrous tetrahydrofuran is added as a solvent, and the raw materials are fully dissolved by stirring. Nitrogen is introduced to remove air in the system, and the reaction mixture is heated to 80°C and refluxed under nitrogen protection. The reaction is carried out for 2 days. After the reaction is completed, it is cooled to room temperature, and part of the solvent is removed by reduced pressure evaporation. Ethyl acetate is added to induce crystallization. The white solid product is collected by filtration, washed with a small amount of ethyl acetate for 2-3 times, and dried under vacuum to obtain the target product tris(1-methylene-3-vinylpyridinium bromide) benzene. The 1H NMR (nuclear magnetic resonance hydrogen spectrum) of the obtained sample is as shown in Figure 2 .
[0023] (3) 1-vinyl-4-(N-methylene-N, N, N-tripropylammonium bromide) benzene and tris(1-methylene-3-vinylpyridine bromide) benzene with a molar ratio of 8:1 were added into N, N-dimethylformamide, and then 0.7 wt% of azobisisobutyronitrile (AIBN) based on the total mass of the substrate (1-vinyl-4-(N-methylene-N, N, N-tripropylammonium bromide and tris(1-methylene-3-vinylpyridine bromide) benzene) was added, and the polymerization reaction was carried out at 80°C for 12 h. After the reaction was completed, the obtained product was immersed in a 1 mol / L sodium hydroxide solution at room temperature for 24 h to obtain a polymer, and the polymer was stirred every 4-6 h. After the immersion was completed, the polymer was washed with the sodium hydroxide solution for 2-3 times, and then was dried at 60°C for 16 h to obtain a basic solid catalytic material.
[0024] The infrared spectrum of the basic solid catalytic material is shown in Figure 3 , 3300-3500 cm -1 -1, there is a vibration peak of a primary amine group -N-, about 1250 cm -1 -1, there is a vibration peak of =N- on a pyridine group, 1490 cm -1 -1, there is a vibration peak of a benzene ring, which confirms the introduction of pyridine and benzene groups from tris(1-methylene-3-vinylpyridine bromide) benzene; about 1650 cm -1 -1, there is a characteristic vibration peak of -OH, which confirms the successful introduction of hydroxyl functional anions. The results show that the monomers are successfully polymerized and the material is functionalized by the anion-cation interaction.
[0025] Example 2 The basic solid catalytic material was used to catalyze the disproportionation reaction of trichlorosilane, and the results obtained by sampling and analyzing at different reaction times under the conditions of a reaction temperature of 75°C and a catalyst dosage of 10 wt% (TCS) are shown in Figure 4 , Figure 5 The solid basic catalytic material still has high activity, high selectivity and high stability after long-time continuous reaction.
[0026] In addition, the structure and thermal stability change before and after use were further studied, and it was found that the specific surface area of the material is 105 m 2 / g, and the structure remains unchanged at 120°C for one month, indicating that the method of using monomers with high thermal stability to achieve high catalytic activity of the catalyst is feasible.
[0027] The characterization method for sampling and analysis is as follows: The structure of the obtained catalytic material is characterized by Fourier transform infrared spectroscopy; 1 g of the catalyst is placed in a fixed bed reactor, 10 g of chlorosilane raw material is added, and catalytic reaction is carried out at 75 DEG C; 2-3 parallel samples are taken at different time points, so as to characterize the influence of the prepared catalyst on the selectivity and yield of silane in the production of silane.
[0028] The above merely describes preferred embodiments of the present application, and any equivalent changes and modifications made within the scope of the present application should be included in the scope of the present application.
Claims
1. A method for producing a high catalytic activity basic catalytic material, characterized by: The method comprises the following steps: adding 1-vinyl-4-(N-methylene-N, N, N-tripropylamine bromide) benzene and tri(1-methylene-3-vinylpyridine bromide) benzene into a solvent in a certain proportion, and polymerizing under the action of an initiator; and immersing the obtained product in a solution containing an oxygen-nitrogen element anion basic group for a certain time after the reaction is completed, and obtaining the basic catalytic material after purification.
2. The method of claim 1, wherein: The preparation method of the 1-vinyl-4-(N-methylene-N, N, N-tripropylamine bromide) benzene comprises the following steps: reacting 4-vinyl benzyl bromide and tripropylamine at a molar ratio of 1:1.5 under anhydrous and anaerobic conditions at 60 DEG C for 3 days, and obtaining the 1-vinyl-4-(N-methylene-N, N, N-tripropylamine bromide) benzene after filtration, washing and drying.
3. The method of claim 1, wherein: The preparation method of the tri(1-methylene-3-vinylpyridine bromide) benzene comprises the following steps: dissolving tri(bromomethyl) benzene and 3-vinylpyridine in anhydrous tetrahydrofuran at a molar ratio of 1:3.3, refluxing at 80-85 DEG C for 2 days under a nitrogen atmosphere, cooling to room temperature after the reaction is completed, and obtaining the tri(1-methylene-3-vinylpyridine bromide) benzene after pressure reduction distillation, ethyl acetate induced crystallization, filtration and vacuum drying.
4. The method of claim 1, wherein: The molar ratio of the 1-vinyl-4-(N-methylene-N, N, N-tripropylamine bromide) benzene to the tri(1-methylene-3-vinylpyridine bromide) benzene is 1:20-20:
1.
5. The method of claim 1, wherein: The temperature of the polymerization reaction is 40-80 DEG C, and the reaction time is 6-300 h; and the solvent is one or a mixture of several of tetrahydrofuran, acetonitrile and N, N-dimethylformamide.
6. The method of claim 1, wherein: The initiator is one or several of azobisdimethyl isobutyronitrile and dimethyl azobis isobutyrate, and the amount of the initiator is 0.1-5 % of the total mass of the 1-vinyl-4-(N-methylene-N, N, N-tripropylamine bromide) benzene and the tri(1-methylene-3-vinylpyridine bromide) benzene.
7. The method of claim 1, wherein: The oxygen-nitrogen element anion basic group is sodium hydroxide, the concentration of the sodium hydroxide is 1 mol / L, the immersion temperature is 25-40 DEG C, and the immersion time is 8-24 h, and the stirring is carried out every 4-6 h.
8. The method of claim 1, wherein: The purification step is that the polymer after immersion is washed 2-3 times with a solution containing an oxygen-nitrogen element anion basic group, and is dried at 50-60 DEG C for 12-16 h after washing.
9. The basic solid catalytic material prepared by the preparation method in any one of claims 1-8.
10. The application of the basic catalytic material in claim 9 in the catalytic chlorosilane disproportionation method for preparing silane.