Synthetic method of ethyl trichlorosilane and ethyl triacetoxysilane
By using a platinum catalyst in a fixed-bed reactor for coordination addition reactions and reactions with acetic anhydride, the problems of cumbersome steps and low yields in the synthesis of ethyltrichlorosilane and ethyltriacetoxysilane were solved, achieving efficient and simple product synthesis with significantly improved purity and yield.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2023-05-15
- Publication Date
- 2026-04-10
AI Technical Summary
The existing synthesis processes for ethyltrichlorosilane and ethyltriacetoxysilane are cumbersome and result in low product yields and poor purity.
The coordination addition reaction of ethylene and trichlorosilane was carried out in a fixed-bed reactor using a platinum catalyst. The reaction temperature was controlled at 30–160 °C and the pressure at <0.5 MPa. Subsequently, it reacted with acetic anhydride to produce ethyltriacetoxysilane.
The efficient synthesis of ethyltrichlorosilane with a purity ≥99.5% was achieved, and ethyltriacetoxysilane was synthesized efficiently through simple operation with significantly improved yield and purity.
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Figure CN121824593A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The application relates to the technical field of organic synthesis, and particularly relates to a synthesis method of ethyltrichlorosilane and ethyltriacetoxysilane. BACKGROUND
[0002] Ethyltrichlorosilane is an organic compound with a chemical formula of C2H5Cl3Si, and is mainly used as an intermediate for the preparation of silane. Ethyltriacetoxysilane has a CAS registration number of 17689-77-9, and its synthesis method mainly includes the methods of organic chlorosilane acyl oxidation, organic aminosilane acyl oxidation and organic alkoxysilane acyl oxidation for preparing ethyltriacetoxysilane, and the preparation process is complicated and high in energy consumption.
[0003] At present, ethyltrichlorosilane is mainly derived from by-products of the synthesis of ethyldichlorosilane, and has defects such as low product yield and poor purity when used for preparing ethyltriacetoxysilane. SUMMARY
[0004] The application provides a synthesis method of ethyltrichlorosilane and ethyltriacetoxysilane, so as to solve the technical problems of complicated steps and low product yield in the existing synthesis process of ethyltrichlorosilane and ethyltriacetoxysilane.
[0005] In a first aspect, the application provides a synthesis method of ethyltrichlorosilane, and the synthesis method comprises the following steps:
[0006] The coordination addition reaction of ethylene and trichlorosilane is carried out by using a fixed bed reactor to obtain ethyltrichlorosilane.
[0007] The working parameters of the coordination addition reaction include that the catalyst is a platinum catalyst, the reaction pressure is less than 0.5 Mpa, and the reaction temperature is 30-160 DEG C.
[0008] Further, the reaction temperature is 50-125 DEG C.
[0009] Further, the step of carrying out the coordination addition reaction of ethylene and trichlorosilane by using a fixed bed reactor to obtain ethyltrichlorosilane comprises the following steps:
[0010] A fixed bed reactor filled with a catalyst is obtained.
[0011] The fixed bed reactor is fixed above a container containing trichlorosilane, and the coordination addition reaction is carried out under the conditions that the reaction temperature is 30-160 DEG C and the reaction pressure is maintained below 0.5 Mpa, the trichlorosilane continuously passes through the fixed bed reactor, and ethylene is introduced at the same time, and then rectification is carried out after the reaction to obtain ethyltrichlorosilane.
[0012] Further, the reaction rate of the coordination addition reaction is 10-200 kg of ethyltrichlorosilane per hour.
[0013] Further, the purity of the ethyltrichlorosilane is ≥ 99.5%.
[0014] In a second aspect, the application provides a synthesis method of ethyltriacetoxysilane, comprising the following steps:
[0015] The ethyltrichlorosilane is prepared by using the synthesis method of any one of the first aspect;
[0016] The ethyltrichlorosilane and acetic anhydride are reacted at a temperature of 50-110°C to obtain ethyltriacetoxysilane.
[0017] Further, the reaction temperature is 60-95°C.
[0018] Further, the reaction pressure is normal pressure, and the molar ratio of the ethyltrichlorosilane to the acetic anhydride is 1:(1-2.5).
[0019] Further, the step of reacting the ethyltrichlorosilane and acetic anhydride at a temperature of 50-110°C to obtain ethyltriacetoxysilane comprises:
[0020] The ethyltrichlorosilane and acetic anhydride are added into a reaction tower to react at a temperature of 50-110°C, the reaction byproduct acetyl chloride is distilled out from the top of the reaction tower, and the crude ethyltriacetoxysilane is obtained in the reaction tower; then, the unreacted acetic anhydride and acetyl chloride are separated out under reduced pressure to obtain ethyltriacetoxysilane.
[0021] The above technical solution provided by the embodiments of the application has at least the following advantages compared with the prior art:
[0022] The synthesis method of ethyltrichlorosilane provided by the embodiments of the application adopts a fixed bed reactor to perform coordination addition reaction of ethylene and trichlorosilane to obtain ethyltrichlorosilane under a specific reaction temperature and reaction pressure, and the whole preparation process is simple in operation, high in preparation efficiency, and high in yield and purity of the product ethyltrichlorosilane. Further, the obtained product ethyltrichlorosilane is reacted with acetic anhydride to realize high-efficiency synthesis of ethyltriacetoxysilane. BRIEF DESCRIPTION OF DRAWINGS
[0023] The accompanying drawings, which are incorporated into and form a part of the specification, illustrate one embodiment consistent with the application and, together with the description, serve to explain the principles of the application.
[0024] In order to more clearly illustrate the technical solutions of the embodiments of the present application or the prior art, the drawings needed to be used in the embodiments or prior art description will be briefly introduced as follows. Obviously, for those skilled in the art, other drawings can also be obtained without creative labor based on these drawings.
[0025] Figure 1 A flowchart of a synthesis method of ethyltrichlorosilane provided by the embodiments of the present application is shown in the figure.
[0026] Figure 2 A flowchart of a synthesis method of ethyltriacetoxysilane provided by the embodiments of the present application is shown in the figure. DETAILED DESCRIPTION
[0027] In order to make the purposes, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions of the embodiments of the present application will be described clearly and completely in the following with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.
[0028] Unless otherwise specifically stated, the various raw materials, reagents, instruments and equipment, etc. used in the present application can be purchased from the market or can be prepared by the existing methods.
[0029] In a first aspect, the present application provides a synthesis method of ethyltrichlorosilane, as shown in the figure, the synthesis method comprises the following steps: Figure 1
[0030] The coordination addition reaction is carried out by using a fixed bed reactor to obtain ethyltrichlorosilane.
[0031] The working parameters of the coordination addition reaction include: the catalyst is a platinum catalyst, the reaction pressure is <0.5 Mpa, and the reaction temperature is 30-160℃.
[0032] The embodiments of the present application provide a synthesis method of ethyltrichlorosilane. Under specific reaction temperature and reaction pressure, the synthesis method is used to carry out the coordination addition reaction of ethylene and trichlorosilane by using a fixed bed reactor to obtain ethyltrichlorosilane. The whole preparation process is simple in operation, high in preparation efficiency, and high in yield and purity of the product ethyltrichlorosilane. Further, the obtained product ethyltrichlorosilane is reacted with acetic anhydride to realize the efficient synthesis of ethyltriacetoxysilane.
[0033] The reaction conditions controlled in the application are "reaction temperature of 30-160℃ + reaction pressure of <0.5Mpa", which can realize simple operation, high preparation efficiency, high yield and purity of the product ethyltrichlorosilane in the whole preparation process; the adverse effects caused by high or too low reaction temperature are the decrease of reaction speed; the adverse effects caused by too high reaction pressure are the termination of reaction process.
[0034] In some specific embodiments, the reaction temperature can be 30℃, 40℃, 50℃, 60℃, 70℃, 80℃, 90℃, 100℃, 110℃, 120℃, 130℃, 140℃, 150℃, 160℃, etc.; the reaction pressure can be 0.4Mpa, 0.3Mpa, 0.2Mpa and 0.1Mpa, etc.
[0035] The fixed bed reactor described in the application can use commercially available products, which will not be described one by one in the application document.
[0036] As an embodiment of the application, the platinum catalyst is platinum-alumina catalyst.
[0037] In some specific embodiments, the amount of catalyst used can be specifically 0.5wt%-3wt%.
[0038] The platinum-alumina catalyst described in the application can use commercially available products or be prepared according to the prior art disclosure, which will not be described one by one in the application document.
[0039] As an embodiment of the application, the reaction temperature is 50-125℃.
[0040] The reaction temperature of the application is preferably 50-125℃.
[0041] As an embodiment of the application, the step of using a fixed bed reactor to perform coordination addition reaction of ethylene and trichlorosilane to obtain ethyltrichlorosilane includes:
[0042] Obtaining a fixed bed reactor filled with catalyst;
[0043] Fixing the fixed bed reactor above a container containing trichlorosilane under the condition of reaction temperature of 30-160℃ and reaction pressure maintained below 0.5Mpa, continuously passing the trichlorosilane through the fixed bed reactor while introducing ethylene for coordination addition reaction, and performing rectification after the reaction to obtain ethyltrichlorosilane.
[0044] In some embodiments, the above process can specifically include: installing the fixed bed above the container, filling the catalyst, and filling the container with trichlorosilane. The temperature is raised, the pressure is maintained below 0.5 MPa, trichlorosilane continuously passes through the fixed reaction bed, ethylene is introduced, and the reaction occurs on the fixed reaction bed to obtain crude ethyltrichlorosilane. The crude ethyltrichlorosilane is then distilled on a rectifying column to obtain finished ethyltrichlorosilane. It should be noted that the distillation process on the rectifying column can use conventional processes in the art. Specifically, the distillation operation process and specific parameters can include: adding crude ethyltrichlorosilane to the distillation kettle, gradually heating to 100°C, continuously collecting the 100°C front fraction, and collecting finished ethyltrichlorosilane when the top temperature of the distillation kettle reaches 100°C.
[0045] As an embodiment of the present application, the reaction rate of the coordination addition reaction is 10-200 kg of ethyltrichlorosilane per hour.
[0046] Since the present application uses a fixed bed reactor for reaction, the reaction is very efficient, and ethylene and trichlorosilane rapidly react according to the theoretical stoichiometric ratio after contact. In some embodiments, the reaction can be carried out at a rate of 10-200 kg of ethyltrichlorosilane per hour.
[0047] As an embodiment of the present application, the purity of the ethyltrichlorosilane is ≥99.5%.
[0048] The purity of the ethyltrichlorosilane obtained by the present application is ≥99.5%.
[0049] In a second aspect, the present application provides a synthesis method of ethyltriacetoxysilane, as shown in Figure 2 The synthesis method includes the following steps:
[0050] The ethyltrichlorosilane is obtained by using any one of the synthesis methods of the first aspect;
[0051] The ethyltrichlorosilane and acetic anhydride are reacted at a temperature of 50-110°C to obtain ethyltriacetoxysilane.
[0052] The second aspect of the present application provides a synthesis method of ethyltriacetoxysilane. The ethyltrichlorosilane obtained by using any one of the synthesis methods of the first aspect is reacted with acetic anhydride at a specific temperature of 50-110°C to obtain ethyltriacetoxysilane, and the entire preparation process is efficient.
[0053] In some embodiments, the above reaction temperature can be 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, etc.
[0054] As an embodiment of the present application, the reaction temperature is 60-95°C.
[0055] The preferred reaction temperature for synthesizing ethyltriacetoxysilane according to the present application is 60-95°C.
[0056] As one embodiment of the present application, the reaction pressure is normal pressure, and the molar ratio of ethyltrichlorosilane to acetic anhydride is 1:(1-2.5).
[0057] The reaction pressure for synthesizing ethyltriacetoxysilane according to the present application is normal pressure and no additional catalyst is needed, and the reaction process is mild and low in cost.
[0058] As one embodiment of the present application, the reaction of ethyltrichlorosilane and acetic anhydride at a temperature of 50-110°C to obtain ethyltriacetoxysilane includes the following steps:
[0059] At a temperature of 50-110°C, the ethyltrichlorosilane and acetic anhydride are added into a reaction column for reaction, the reaction byproduct acetyl chloride is distilled out from the top of the reaction column, and the crude ethyltriacetoxysilane is obtained in the reaction column; then, the unreacted acetic anhydride and acetyl chloride are separated out under reduced pressure to obtain ethyltriacetoxysilane.
[0060] The above reaction column according to the present application can use the conventional reaction column equipment in the art or use a reaction container with ports at the top and bottom to ensure that the reaction byproduct acetyl chloride is separated out from the reaction system (acetyl chloride can be collected and used later) during the reaction process, and the crude ethyltriacetoxysilane and a small amount of unreacted acetic anhydride and acetyl chloride are left in the reaction container.
[0061] In some specific embodiments, the above process can specifically include: metered acetic anhydride and ethyltrichlorosilane are added into a container with a column, respectively, and heated for reaction, acetyl chloride is distilled out and collected. The remaining material in the container is the crude product, and the unreacted acetic anhydride and acetyl chloride are extracted under negative pressure to obtain the product ethyltriacetoxysilane with a content of not less than 95%.
[0062] The present application is further described below in conjunction with specific examples. It should be understood that these examples are only used to illustrate the present application and not to limit the scope of the present application. The experimental methods in the following examples, if no specific conditions are indicated, are generally determined according to the national standards. If there is no corresponding national standard, the international standard, the conventional conditions, or the conditions suggested by the manufacturer are used.
[0063] Example 1
[0064] The present example provides a method for synthesizing ethyltrichlorosilane, which includes the following steps:
[0065] The fixed bed is installed above a container, which is filled with platinum-alumina catalyst (purchased from the manufacturer Aladdin, product model SKU (platinum content, dry basis 10wt%), and the specific amount is 2wt%), and the container contains trichlorosilane; the temperature is raised to 35℃, the pressure is maintained below 0.5Mpa (specifically 0.4Mpa), trichlorosilane continuously passes through the fixed reaction bed, and ethylene is introduced at the same time, and the reaction occurs on the fixed reaction bed at 100 kilograms of ethyltrichlorosilane per hour, to obtain crude ethyltrichlorosilane, which is then distilled in a rectifying column to obtain finished ethyltrichlorosilane.
[0066] The yield of crude ethyltrichlorosilane obtained in this example 1 is 3%; the purity of crude ethyltrichlorosilane is 3%; the yield of finished ethyltrichlorosilane is 1%; and the purity of finished ethyltrichlorosilane is ≥99.5%.
[0067] Examples 2-6 investigate the effect of reaction temperature on the preparation of ethyltrichlorosilane.
[0068] On the basis of example 1, examples 2-6 only adjust the reaction temperature (the rest of the steps and parameters are the same as example 1), and the reaction temperature in examples 2-6 is shown in table 1.
[0069] Table 1 Effect of reaction temperature on the preparation of ethyltrichlorosilane in examples 2-6
[0070]
[0071]
[0072] Example 7
[0073] On the basis of example 1, example 7 only adjusts the type of catalyst (the rest of the steps and parameters are the same as example 1), and the reaction detection results of example 7 are shown in table 2; wherein, the catalyst A is platinum-activated carbon (purchased from the manufacturer Hubei Weishi Chemical Reagent Co., Ltd., product model HBWS-B245, CAS number: 7440-06-4).
[0074] Table 2 Effect of reaction catalyst type on the preparation of ethyltrichlorosilane in example 7
[0075]
[0076] Example 8
[0077] The present example provides a method for synthesizing ethyltriacetoxysilane, which comprises:
[0078] The ethyltrichlorosilane obtained in Example 1 (1 mol) and acetic anhydride (1.3 mol) were added into a reactor at 50°C and normal pressure to react, the by-product acetyl chloride was evaporated from the top of the reactor, and the crude ethyltriacetoxysilane was obtained in the reactor; then the unreacted acetic anhydride and acetyl chloride were separated under reduced pressure to obtain the finished ethyltriacetoxysilane.
[0079] In this example, the yield of the crude ethyltriacetoxysilane was 90%, the purity of the crude ethyltriacetoxysilane was 70%, the yield of the finished ethyltriacetoxysilane was 95%, and the purity of the finished ethyltriacetoxysilane was 96%.
[0080] Various embodiments of the present application can exist in a range of forms; it should be understood that the description in a range of forms is merely for the convenience and brevity, and should not be understood as a hard limitation on the scope of the present application; therefore, it should be considered that the described range has been specifically disclosed all possible sub-ranges and single values within the range. For example, it should be considered that the range description from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the described range, such as 1, 2, 3, 4, 5, and 6, regardless of the range. In addition, whenever a numerical range is indicated in this document, it refers to any cited number (fraction or integer) within the indicated range.
[0081] In this application, the orientation words such as "upper" and "lower" are specifically the directions of the drawing surface in the drawings, unless otherwise stated. In addition, in the description of the specification of this application, the terms "include", "contain" and the like mean "include but are not limited to". In this document, relational terms such as "first" and "second" and the like are merely used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply that there is any such actual relationship or order between these entities or operations. In this document, "and / or" describes the relationship between the associated objects, which means that there can be three relationships, for example, A and / or B can mean that A exists alone, A and B exist together, and B exists alone. Where A and B can be singular or plural. In this document, "one or more" means one or more, and "multiple" means two or more. "At least one", "at least one of the following", or the like, means any combination of these items, including any combination of single or multiple items. For example, "at least one of a, b, or c", or "at least one of a, b, and c", can mean a, b, c, a-b (i.e. a and b), a-c, b-c, or a-b-c, where a, b, and c can be single or multiple.
[0082] The foregoing detailed description of the application has been presented for purposes of illustration and description. Various modifications and changes can be made to these embodiments without departing from the spirit and scope of the application. It is intended that the scope of the application should not be limited by the particular representative embodiments described above.
Claims
1. A method for the synthesis of ethyltrichlorosilane, characterized in that, The synthesis method comprises the following steps: The coordination addition reaction of ethylene and trichlorosilane is carried out by using a fixed bed reactor to obtain ethyltrichlorosilane; The working parameters of the coordination addition reaction include that the catalyst is platinum / alumina catalyst, the reaction pressure is less than 0.5 Mpa, and the reaction temperature is 30-160 DEG C.
2. The method of synthesis of claim 1, wherein, The reaction temperature is 50-125 DEG C.
3. The method of synthesis of claim 1, wherein, The step of carrying out the coordination addition reaction of ethylene and trichlorosilane by using a fixed bed reactor to obtain ethyltrichlorosilane comprises: A fixed bed reactor filled with catalyst is obtained; The fixed bed reactor is fixed above a container containing trichlorosilane, and the trichlorosilane continuously passes through the fixed bed reactor while ethylene is introduced to carry out the coordination addition reaction under the conditions that the reaction temperature is 30-160 DEG C and the reaction pressure is maintained below 0.5 Mpa, and then the reaction product is subjected to rectification to obtain ethyltrichlorosilane.
4. The method of synthesis of claim 3, wherein, The reaction rate of the coordination addition reaction is 10-200 kg of ethyltrichlorosilane / hour.
5. The method of synthesis of claim 3, wherein, The purity of the ethyltrichlorosilane is greater than or equal to 99.5%.
6. A method of synthesizing ethyltriacetoxysilane, characterized by, The synthesis method comprises the following steps: The ethyltrichlorosilane is obtained by using the synthesis method according to any one of claims 1-5; The ethyltrichlorosilane and acetic anhydride are reacted at a temperature of 50-110 DEG C to obtain ethyltriacetoxysilane.
7. The method of synthesis of claim 6, wherein, The reaction temperature is 60-95 DEG C.
8. The method of synthesis of claim 6, wherein, The reaction pressure is normal pressure, and the molar ratio of the ethyltrichlorosilane to the acetic anhydride is 1:(1-2.5).
9. The method of synthesis according to any one of claims 6 to 8, wherein, The step of reacting the ethyltrichlorosilane and acetic anhydride at a temperature of 50-110 DEG C to obtain ethyltriacetoxysilane comprises: The ethyltrichlorosilane and acetic anhydride are added into a reaction tower to react at a temperature of 50-110 DEG C, the reaction byproduct acetyl chloride is distilled out from the top of the reaction tower, and ethyltriacetoxysilane crude product is obtained in the reaction tower; then, unreacted acetic anhydride and acetyl chloride are separated out under reduced pressure to obtain ethyltriacetoxysilane.