Composite catalyst and synthetic method of disiloxane compound
By reacting the composite catalyst with silicon powder and silicate, the problem of residual chloride ions in the production of disiloxane compounds is solved, and high-purity and high-yield disiloxane products are achieved, which are suitable for high-end technology fields.
Patent Information
- Application Number
- CN202510929599.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-07
- Publication Date
- 2025-10-03
AI Technical Summary
Existing disiloxane compounds have the problem of residual chloride ions causing equipment corrosion during the production process, and the production process generates wastewater, affecting environmental protection.
A composite catalyst is used, including metallic iron and/or iron oxide, metallic aluminum and/or aluminum oxide, metallic calcium, alkali metal hydroxide and metal alkoxide, which are mixed in a specific proportion and reacted with silicon powder and silicate under certain conditions to generate high-purity disiloxane compounds.
It achieves high conversion rate and high selectivity, with product purity reaching 99.9%. It does not require acid-base neutralization, simplifies operation, and is suitable for high-end technology fields such as cleaning agents for precision electronic equipment.
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Abstract
Description
Technical Field
[0001] The invention relates to a composite catalyst and a method for synthesizing a disiloxane compound, and belongs to the technical field of organic chemical industry. Background Art
[0002] As the primary raw material for the production of downstream silicone products, disiloxane plays a vital role in the production of organic chemicals and pharmaceutical chemicals. For example, it is used as a sealing agent in silicone oil production, a medical defoaming agent and lubricant, a release agent in the food industry, a damping fluid and brake fluid for transportation equipment and instruments, an additive for coatings, rubber and plastics, and a cleaning agent for precision electronic equipment used in the medical, defense and aviation industries.
[0003] Currently, disiloxane is primarily derived from chlorosilanes. However, achieving 100% purity is difficult during the production and separation process, as disiloxane often contains silanols and chloride ions. Silanols are highly acidic, and the product also contains residual chlorosilanes and impurities from the chlorosilane raw materials, making their removal challenging. If used as a cleaning agent for precision electronic equipment, it can cause corrosion, severely impacting performance and service life. Summary of the Invention
[0004] Existing methods for preparing disiloxane compounds suffer from corrosion problems caused by residual chloride ions, and the production process generates wastewater that requires neutralization, impacting environmental protection. To address these issues, the present invention provides a composite catalyst and method for preparing disiloxane organic compounds, which exhibit high conversion and selectivity, resulting in a disiloxane product with a purity exceeding 99.9%.
[0005] The present invention provides a composite catalyst comprising the following components: (1) Metallic iron and / or iron oxides; (2) Aluminum metal and / or aluminum oxide; (3) Metallic calcium; (4) Alkali metal hydroxides; (5) Metal alkoxides.
[0006] Furthermore, the ratio of the composite catalyst, calculated on a metal atom basis, is metallic iron and / or iron oxide: metallic aluminum and / or aluminum oxide: metallic calcium: alkali metal hydroxide: metal alkoxide = 1: (1-2): (0.01-0.2): (0.01-0.2): (1-10).
[0007] Furthermore, the ratio of the composite catalyst, calculated on a metal atom basis, is metallic iron and / or iron oxide: metallic aluminum and / or aluminum oxide: metallic calcium: alkali metal hydroxide: metal alkoxide = 1: (1-1.2): (0.05-0.15): (0.05-0.15): (2-7).
[0008] Furthermore, the metal alkoxide is an alkali metal alkoxide.
[0009] The present invention also provides a method for preparing the composite catalyst, which comprises mixing and stirring the components to obtain the composite catalyst.
[0010] The present invention also provides a method for synthesizing disiloxane compounds, comprising preparing materials containing silicon powder and silicate, mixing them uniformly, adding alcohol and the composite catalyst, filtering and rectifying after reaction, and obtaining the disiloxane compounds.
[0011] Furthermore, the purity of the silicon powder is 85% to 99%, and the particle size is 200 to 400 meshes.
[0012] Furthermore, the silicate is selected from at least one of methyl silicate, ethyl silicate and propyl silicate.
[0013] Furthermore, the mass ratio of the silicon powder to the silicate is 1:(3~8).
[0014] Furthermore, the mass ratio of the silicon powder to the silicate is 1:(4~6).
[0015] Furthermore, the mass ratio of the silicon powder to the silicate is 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, or any value between any two of the above points.
[0016] Furthermore, the alcohol is selected from at least one of methanol, ethanol and propanol.
[0017] Furthermore, the molar ratio of the alcohol to the silicon powder is 1:(3~8).
[0018] Furthermore, the molar ratio of the alcohol to the silicon powder is 1:(4~6).
[0019] Furthermore, the molar ratio of the alcohol to the silicon powder is 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, or any value between any two of the above points.
[0020] Furthermore, the mass of the composite catalyst accounts for 0.1% to 20% of the mass of the silicon powder.
[0021] Furthermore, the mass of the composite catalyst accounts for 5% to 12% of the mass of the silicon powder.
[0022] Furthermore, the mass of the composite catalyst accounts for 0.5%, 1%, 1.5%, 2%, 3%, 4%, 5%, 8%, 10%, 12%, 15%, 16%, 18%, 20% of the mass of the silicon powder, or any value between any two of the above points.
[0023] Furthermore, the mixing is carried out by ultrasonic mixing, and the ultrasonic mixing conditions include 50-100 Hz and maintaining for 0.5-2 hours.
[0024] Furthermore, the reaction comprises reacting at 50-170° C. for 10-12 hours and then reacting at 170-180° C. for 4-6 hours; the reaction pressure is 1-5 MPa.
[0025] Furthermore, the reaction pressure is 2-4 MPa.
[0026] Furthermore, the reaction temperature is 50°C, 60°C, 80°C, 100°C, 110°C, 130°C, 150°C, 170°C, or any value between any two of the above points.
[0027] Furthermore, the reaction pressure is 1 MPa, 2 MPa, 3 MPa, 4 MPa, 5 MPa, or any value between any two of the above points.
[0028] Furthermore, the materials after the reaction are filtered and distilled, and the composite catalyst is recovered for reuse.
[0029] The present invention filters the reactants to recover iron and / or iron oxide, metallic aluminum and / or aluminum oxide, metallic calcium, and alkali metal hydroxides, and distills the filtered liquid to recover metal alkoxides, thereby recovering the composite catalyst for reuse.
[0030] Furthermore, the purity of the disiloxane compound is greater than 99.9%, and the yield is greater than 85%.
[0031] The present invention has the following beneficial effects: The present invention first ultrasonically mixes silicon powder and alkoxysilane, adds them to a reactor, then adds the composite catalyst described herein and alcohol for a temperature- and pressure-controlled reaction. Hydrogen and dimethyl ether are produced during the reaction. After completion, the reaction materials are filtered and distilled to obtain a disiloxane product with a purity greater than 99.9%. The preparation method of the present invention eliminates the need for chlorine in the product and the need for multiple acid-base neutralizations. The method is simple to operate, with high conversion and selectivity. The pre-distillation product yield can reach 90% to 95%. It can be applied to high-tech fields, including the preparation of organosilicon products that come into contact with the human body, cleaning of precision electrical instruments, and cleaning of outer space equipment. DETAILED DESCRIPTION
[0032] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.
[0033] The reagents and drugs used in the following examples can all be obtained commercially, wherein the mesh size of the silicon powder is 200 mesh and the purity is 99%.
[0034] In the present invention, Silicon powder conversion rate = (initial silicon powder mass - remaining silicon powder mass) / initial silicon powder mass × 100%, Alkoxysilane conversion rate = (initial alkoxysilane mass + alkoxysilane mass synthesized from silicon powder - remaining alkoxysilane mass) / (initial alkoxysilane mass + alkoxysilane mass synthesized from silicon powder) × 100%, Selectivity of disiloxane compounds = actual mass of disiloxane compounds generated / (actual mass of disiloxane compounds generated + mass of impurities) × 100%, Yield of disiloxane compounds = mass of disiloxane compounds obtained after distillation / (mass of disiloxane compounds theoretically generated from alkoxysilane + mass of disiloxane compounds theoretically generated from silicon powder) × 100%, The purity of disiloxane compounds was measured using an Agilent 7820 chromatograph. Example 1
[0035] 1) Preparation of catalyst Weigh 0.22 g of iron, 0.1 g of aluminum, 0.015 g of calcium, 0.015 g of sodium hydroxide, and 1.05 g of sodium methoxide and grind them together to obtain a catalyst for later use. 2) Ultrasound preparation Weigh 28 g of silicon powder and 112 g of tetramethoxysilane, mix them, add them to an ultrasonic bath, set the temperature to 50° C., and the ultrasonic setting to 80 Hz. After ultrasonication for 1 h, obtain material 1 for use; 3) Reaction synthesis The prepared catalyst and material 1 were mixed and added to a high-pressure reactor, 128 g of anhydrous methanol was added, the reactor was sealed, nitrogen was pressurized to 5 MPa, and a leak test was performed to confirm that the reactor was leak-proof, and the nitrogen was discharged. The reaction pressure was set to 3 MPa; the temperature was started, and a temperature program was set to increase the temperature of the reactor from 25°C to 160°C within 1 hour, and the insulation reaction was started. When the reaction pressure reached 3 MPa, the exhaust reaction was started. After 12 hours, the reaction temperature was set to 180°C, and the insulation reaction was carried out for 5 hours. The temperature was then naturally cooled to 30°C, the reactor was opened, and the reaction liquid was recovered and weighed; 4) Post-processing The reaction liquid was filtered, and the filter cake was washed with methanol to obtain a recovered catalyst. The filtered reaction liquid was distilled to obtain 190.5 g of pure hexamethoxydisiloxane.
[0036] The experimental results are shown in Table 1. Example 2
[0037] 1) Preparation of catalyst Weigh 0.44g of iron, 0.4g of aluminum, 0.03g of calcium, 0.03g of sodium hydroxide and 2.1g of sodium methoxide and grind them to obtain a catalyst for later use; 2) Ultrasound preparation Weigh 28 g of silicon powder and 140 g of tetramethoxysilane, mix them, add them to an ultrasonic bath, set the temperature to 50° C., and the ultrasonic setting to 80 Hz. After ultrasonication for 1 h, obtain material 1 for use; 3) Reaction synthesis The prepared catalyst and material 1 were mixed and added to a high-pressure reactor, 192 g of anhydrous methanol was added, the reactor was sealed, nitrogen was pressurized to 5 MPa, and a leak test was performed to confirm that the reactor was leak-proof, and the nitrogen was discharged. The reaction pressure was set to 3 MPa; the temperature was started, and a temperature program was set to increase the temperature of the reactor from 25°C to 155°C within 1 hour, and the insulation reaction was started. When the reaction pressure reached 3 MPa, the exhaust reaction was started. After 12 hours, the reaction temperature was set to 180°C, and the insulation reaction was carried out for 5 hours. The temperature was then naturally cooled to 30°C, the reactor was opened, and the reaction liquid was recovered and weighed; 4) Post-processing The reaction liquid was filtered, and the filter cake was washed with methanol to obtain a recovered catalyst. The filtered reaction liquid was distilled to obtain 221 g of pure hexamethoxydisiloxane.
[0038] The experimental results are shown in Table 1.
[0039] Example 3 1) Preparation of catalyst Weigh 0.33g of iron, 0.19g of aluminum, 0.035g of calcium, 0.035g of sodium hydroxide and 2.21g of sodium methoxide and grind them to obtain a catalyst for later use; 2) Ultrasound preparation Weigh 28 g of silicon powder and 140 g of tetramethoxysilane, mix them, add them to an ultrasonic bath, set the temperature to 50° C., and the ultrasonic setting to 80 Hz. After ultrasonication for 1 h, obtain material 1 for use; 3) Reaction synthesis The prepared catalyst and material 1 were mixed and added to a high-pressure reactor, 192 g of anhydrous methanol was added, the reactor was sealed, nitrogen was pressurized to 5 MPa, and a leak test was performed to confirm that the reactor was leak-proof, and the nitrogen was discharged. The reaction pressure was set to 3 MPa; the temperature was started, and a temperature program was set to increase the temperature of the reactor from 25°C to 165°C within 1 hour, and the insulation reaction was started. When the reaction pressure reached 3 MPa, the exhaust reaction was started. After 12 hours, the reaction temperature was set to 180°C, and the insulation reaction was carried out for 5 hours. The temperature was then naturally cooled to 30°C, the reactor was opened, and the reaction liquid was recovered and weighed; 4) Post-processing The reaction liquid was filtered, and the filter cake was washed with methanol to obtain a recovered catalyst. The filtered reaction liquid was distilled to obtain 225 g of hexamethoxydisiloxane.
[0040] The experimental results are shown in Table 1. Example 4
[0041] 1) Preparation of catalyst Weigh 0.49 g of iron, 0.28 g of aluminum, 0.07 g of calcium, 0.07 g of sodium hydroxide, and 3.29 g of sodium methoxide and grind them together to obtain a catalyst for later use. 2) Ultrasound preparation Weigh 28 g of silicon powder and 168 g of tetramethoxysilane, mix them, add them to an ultrasonic bath, set the temperature to 50° C., and the ultrasonic setting to 80 Hz. After ultrasonication for 1 h, obtain material 1 for use; 3) Reaction synthesis The prepared catalyst and material 1 were mixed and added to a high-pressure reactor, 276 g of anhydrous methanol was added, the reactor was sealed, nitrogen was pressurized to 5 MPa, and a leak test was performed to confirm that the reactor was leak-proof, and the nitrogen was discharged. The reaction pressure was set to 3 MPa; the temperature was started, and a temperature program was set to increase the temperature of the reactor from 25°C to 165°C within 1 hour, and the insulation reaction was started. When the reaction pressure reached 3 MPa, the exhaust reaction was started. After 12 hours, the reaction temperature was set to 180°C, and the insulation reaction was carried out for 5 hours. The temperature was then naturally cooled to 30°C, the reactor was opened, and the reaction liquid was recovered and weighed; 4) Post-processing The reaction liquid was filtered, and the filter cake was washed with methanol to obtain a recovered catalyst. The filtered reaction liquid was distilled to obtain 245 g of hexamethoxydisiloxane.
[0042] The experimental results are shown in Table 1. Example 5
[0043] 1) Preparation of catalyst Weigh 0.456g of ferric oxide, 0.154g of aluminum, 0.023g of calcium, 0.023g of sodium hydroxide and 2.16g of sodium methoxide and grind them to obtain a catalyst for later use; 2) Ultrasound preparation Weigh 28 g of silicon powder and 112 g of tetramethoxysilane, mix them, add them to an ultrasonic bath, set the temperature to 50° C., and the ultrasonic setting to 80 Hz. After ultrasonication for 1 h, obtain material 1 for use; 3) Reaction synthesis The prepared catalyst and material 1 were mixed and added to a high-pressure reactor, 192 g of anhydrous methanol was added, the reactor was sealed, nitrogen was pressurized to 5 MPa, and a leak test was performed to confirm that the reactor was leak-proof, and the nitrogen was discharged. The reaction pressure was set to 3 MPa; the temperature was started, and a temperature program was set to increase the temperature of the reactor from 25°C to 165°C within 1 hour, and the insulation reaction was started. When the reaction pressure reached 3 MPa, the exhaust reaction was started. After 12 hours, the reaction temperature was set to 180°C, and the insulation reaction was carried out for 5 hours. The temperature was then naturally cooled to 30°C, the reactor was opened, and the reaction liquid was recovered and weighed; 4) Post-processing The reaction liquid was filtered, and the filter cake was washed with methanol to obtain a recovered catalyst. The filtered reaction liquid was distilled to obtain 193 g of hexamethoxydisiloxane.
[0044] The experimental results are shown in Table 1. Example 6
[0045] 1) Preparation of catalyst Weigh 0.47 g of ferric oxide, 0.46 g of aluminum, 0.047 g of calcium, 0.067 g of sodium hydroxide, and 4.54 g of sodium methoxide and grind them to obtain a catalyst for later use; 2) Ultrasound preparation Weigh 28 g of silicon powder and 112 g of tetramethoxysilane, mix them, add them to an ultrasonic bath, set the temperature to 50° C., and the ultrasonic setting to 80 Hz. After ultrasonication for 1 h, obtain material 1 for use; 3) Reaction synthesis The prepared catalyst and material 1 were mixed and added to a high-pressure reactor, 192 g of anhydrous methanol was added, the reactor was sealed, nitrogen was pressurized to 5 MPa, and a leak test was performed to confirm that the reactor was leak-proof, and the nitrogen was discharged. The reaction pressure was set to 3 MPa; the temperature was started, and a temperature program was set to increase the temperature of the reactor from 25°C to 165°C within 1 hour, and the insulation reaction was started. When the reaction pressure reached 3 MPa, the exhaust reaction was started. After 12 hours, the reaction temperature was set to 180°C, and the insulation reaction was carried out for 5 hours. The temperature was then naturally cooled to 30°C, the reactor was opened, and the reaction liquid was recovered and weighed; 4) Post-processing The reaction liquid was filtered, and the filter cake was washed with methanol to obtain a recovered catalyst. The filtered reaction liquid was distilled to obtain 199 g of hexamethoxydisiloxane.
[0046] The experimental results are shown in Table 1. Example 7
[0047] 1) Preparation of catalyst Weigh 0.33g of iron, 0.19g of aluminum, 0.035g of calcium, 0.035g of sodium hydroxide and 2.76g of sodium ethoxide and grind them to obtain a catalyst for later use; 2) Ultrasound preparation Weigh 28 g of silicon powder and 168 g of tetraethoxysilane, mix them, add them to an ultrasonic bath, set the temperature to 50° C., and the ultrasonic setting to 80 Hz. After ultrasonication for 1 hour, obtain material 1 for use; 3) Reaction synthesis The prepared catalyst and material 1 were mixed and added to a high-pressure reactor, 276 g of anhydrous ethanol was added, the reactor was sealed, nitrogen was pressurized to 5 MPa, and a leak test was performed to confirm that the reactor was leak-proof, and the nitrogen was discharged. The reaction pressure was set to 3 MPa; the temperature was started, and a temperature program was set to increase the temperature of the reactor from 25°C to 165°C within 1 hour, and the insulation reaction was started. When the reaction pressure reached 3 MPa, the exhaust reaction was started. After 12 hours, the reaction temperature was set to 180°C, and the insulation reaction was carried out for 5 hours. The temperature was then naturally cooled to 30°C, the reactor was opened, and the reaction liquid was recovered and weighed; 4) Post-processing The reaction liquid was filtered, and the filter cake was washed with ethanol to obtain a recovered catalyst. The filtered reaction liquid was distilled to obtain 272 g of hexaethoxydisiloxane.
[0048] The experimental results are shown in Table 1.
[0049] Table 1
[0050] While particular aspects of the present invention have been illustrated and described, it will be apparent to those skilled in the art that various other changes and modifications may be made without departing from the spirit and scope of the invention. It is therefore intended that the appended claims cover all such changes and modifications as fall within the scope of the invention.
Claims
1. A composite catalyst, characterized in that: The composite catalyst comprises the following components: (1) Metallic iron and / or iron oxides; (2) Aluminum metal and / or aluminum oxide; (3) Metallic calcium; (4) Alkali metal hydroxides; (5) Metal alkoxides.
2. The composite catalyst according to claim 1, characterized in that The ratio of the composite catalyst is calculated on a metal atom basis as follows: metallic iron and / or iron oxide: metallic aluminum and / or aluminum oxide: metallic calcium: alkali metal hydroxide: metal alkoxide = 1: (1-2): (0.01-0.2): (0.01-0.2): (1-10), preferably 1: (1-1.2): (0.05-0.15): (0.05-0.15): (2-7).
3. The composite catalyst according to claim 1 or 2, characterized in that The metal alkoxide is an alkali metal alkoxide.
4. A method for preparing the composite catalyst according to any one of claims 1 to 3, characterized in that: The preparation method comprises mixing and stirring the components to obtain the composite catalyst.
5. A method for synthesizing a disiloxane compound, characterized in that: Materials containing silicon powder and silicate are prepared, mixed evenly, and then alcohol and the composite catalyst according to any one of claims 1 to 3 are added. After the reaction, the mixture is filtered and distilled to obtain a disiloxane compound.
6. The synthesis method according to claim 5, characterized in that The purity of the silicon powder is 85% to 99%, and the particle size is 200 to 400 mesh; And / or, the silicate is selected from at least one of methyl silicate, ethyl silicate and propyl silicate; And / or, the mass ratio of the silicon powder to the silicate is 1:(3-8), preferably 1:(4-6).
7. The synthesis method according to claim 5 or 6, characterized in that The alcohol is selected from at least one of methanol, ethanol, and propanol; and / or, the molar ratio of the alcohol to the silicon powder is 1:(3-8), preferably 1:(4-6); And / or, the mass of the composite catalyst accounts for 0.1% to 20% of the mass of the silicon powder, preferably 5% to 12%.
8. The synthesis method according to any one of claims 5 to 7, characterized in that The mixing is carried out by ultrasonic mixing, and the ultrasonic mixing conditions include maintaining 50-100 Hz for 0.5-2 hours; And / or, the reaction comprises reacting at 50-170° C. for 10-12 hours and then reacting at 170-180° C. for 4-6 hours; the reaction pressure is 1-5 MPa, preferably 2-4 MPa.
9. The synthesis method according to any one of claims 5 to 8, characterized in that The materials after the reaction are filtered and distilled, and the composite catalyst is recovered for reuse.
10. The synthesis method according to any one of claims 5 to 9, characterized in that The purity of the disiloxane compound is greater than 99.9%, and the yield is greater than 85%.