Preparation method of cyano chlorosilane compound

Abstract

The invention provides a preparation method of a cyano chlorosilane compound, and the preparation method of the cyano chlorosilane compound comprises the following steps: reacting methyl dichlorosilane with a cyano-containing olefin compound under the action of a catalyst to obtain the cyano chlorosilane compound, the catalyst comprises a combination of cuprous salt, organic alkali and tetramethylethylenediamine. According to the method, methyl dichlorosilane and cyano-containing olefin are used as raw materials to react, and the cyano chlorosilane compound is prepared under the action of a specific catalyst; the preparation method is simple in reaction operation, the yield is 76% or above, the purity is 99.1% or above, and the preparation method is suitable for industrial production.

Description

Technical Field

[0001] The present invention relates to the technical field of organic synthesis, and in particular to a method for preparing a chlorocyanosilane compound. Background Art

[0002] Driven by the development of electric vehicles and renewable energy, lithium-ion battery technology is constantly advancing, placing higher demands on the safety, cycle stability, and service life of lithium-ion batteries. This is particularly true in applications involving high voltages, wide temperature ranges, and long cycle life. Traditional carbonate electrolytes are susceptible to decomposition at high voltages, leading to an unstable electrode / electrolyte interface and compromising battery performance.

[0003] Organosilicon compounds containing cyano groups play an important role in improving electrolyte stability and enhancing ionic conductivity. They can form a stable solid electrolyte interface (SEI) or cathode electrolyte interface (CEI) on the electrode surface, thereby inhibiting electrolyte decomposition and improving the high-voltage stability and cycle life of the battery.

[0004] CN109942618A discloses a method for synthesizing 3-cyanopropyldimethylchlorosilane, which uses acrylonitrile and methyldichlorosilane as raw materials for a hydrosilylation reaction. The catalyst is chloroplatinic acid or a platinum-vinylsiloxane chelate, which is expensive, difficult to obtain, and cannot be recycled. In addition, the yield of the product obtained by this synthesis method is only 77-84%, which is low and difficult to achieve industrial production.

[0005] CN106632448A discloses a method for synthesizing cyanochlorosilane, which uses hydrogen-containing chlorosilane and cyano-containing olefin as raw materials and copper chloride and tertiary amine as catalysts. The raw materials of this method are simple and easy to obtain, but the reaction time is long and the yield is unstable.

[0006] CN103288863A discloses a method for a hydrosilylation reaction, which uses olefins and hydrosilanes as raw materials, rhodium trichloride as a catalyst, and a triphenylphosphine derivative as a ligand to obtain two addition products. The separation of the two products is difficult, the yield of the main product is low, and the catalyst is expensive, making the method unsuitable for industrial production.

[0007] Therefore, developing a method for preparing chlorocyanosilane compounds with high yield, high purity and simple reaction operation is a technical problem to be solved urgently in this field. Summary of the Invention

[0008] In view of the shortcomings of the prior art, the object of the present invention is to provide a method for preparing a cyanochlorosilane compound, which uses methyldichlorosilane and cyano-containing olefins as raw materials, has simple reaction operation, high yield, high purity, and is suitable for industrial production.

[0009] To achieve this object, the present invention adopts the following technical solutions:

[0010] In a first aspect, the present invention provides a method for preparing a chlorocyanosilane compound, the method for preparing the chlorocyanosilane compound comprising the following steps:

[0011] Methyldichlorosilane reacts with a cyano group-containing olefin compound in the presence of a catalyst to obtain a cyanochlorosilane compound;

[0012] The catalyst includes a combination of a cuprous salt, an organic base and tetramethylethylenediamine.

[0013] The invention uses methyldichlorosilane and cyano-containing olefin as raw materials to carry out a reaction under the action of a specific catalyst to prepare a cyanochlorosilane compound. The preparation method of the invention has simple reaction operation, high yield, high purity, and is suitable for industrial production.

[0014] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. Through the following preferred technical solutions, the objectives and beneficial effects of the present invention can be better achieved and realized.

[0015] Preferably, the cyanochlorosilane compound has a structure shown in the following formula I or formula II:

[0016]

[0017]

[0018] Wherein, n is any integer between 1 and 4, for example, 1, 2, 3 or 4, and R is methyl or ethyl.

[0019] Preferably, the cuprous salt includes any one of cuprous chloride, cuprous sulfate or cuprous acetate, or a combination of at least two thereof, and is more preferably cuprous chloride.

[0020] Preferably, the organic base includes any one or a combination of at least two of 1,8-diazabicyclo[5.4.0]undec-7-ene, triethylamine or 1,5,7-triazabicyclo[4.4.0]dec-5-ene, and more preferably 1,8-diazabicyclo[5.4.0]undec-7-ene.

[0021] Preferably, the cyano group-containing olefin compound has the following structure:

[0022]

[0023] Preferably, the reaction temperature is 70-100°C, for example, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C or 100°C, more preferably 80-90°C.

[0024] Preferably, the reaction time is 8-14 h, for example, 8 h, 9 h, 10 h, 11 h, 12 h, 13 h or 14 h, and more preferably 9-10 h.

[0025] Preferably, the reaction pressure is 1.8 MPa-2.5 MPa, for example, 1.8 MPa, 1.9 MPa, 2.0 MPa, 2.1 MPa, 2.2 MPa, 2.3 MPa, 2.4 MPa or 2.5 MPa.

[0026] Preferably, the molar ratio of the cyano group-containing olefin compound to methyldichlorosilane is 1:(1.0-1.15), for example, 1:1.0, 1:1.03, 1:1.06, 1:1.09, 1:1.12 or 1:1.15, and more preferably 1:(1.05-1.10).

[0027] Preferably, the molar ratio of the cyano group-containing olefin compound, cuprous salt, organic base and tetramethylethylenediamine is 1:(0.01-0.1):(0.01-0.1):(0.05-0.2), for example, it can be 1:0.02:0.03:0.07, 1:0.04:0.05:0.09, 1:0.05:0.06:0.13, 1:0.03:0.08:0.15 or 1:0.07:0.09:0.17, etc., and more preferably 1:(0.03-0.08):(0.03-0.08):(0.10-0.15).

[0028] Preferably, the reaction further comprises a post-treatment step.

[0029] Preferably, the post-treatment includes filtration and distillation.

[0030] Preferably, the rectification comprises vacuum distillation.

[0031] Preferably, the distillation temperature is 105-125°C, for example, 105°C, 110°C, 115°C, 120°C or 125°C, and more preferably 110-115°C.

[0032] Preferably, the distillation pressure is 1-20 mbar, for example, 1 mbar, 5 mbar, 10 mbar, 15 mbar or 20 mbar, etc., more preferably 5-10 mbar.

[0033] As a preferred technical solution of the present invention, the preparation method of the cyanochlorosilane compound specifically comprises the following steps:

[0034] Methyldichlorosilane and a cyano-containing olefin compound are reacted with a catalyst at 70-100°C and 1.8 MPa-2.5 MPa for 8-14 hours, filtered, and distilled at 105-125°C and 1-20 mbar to obtain a cyanochlorosilane compound;

[0035] The catalyst comprises a combination of a cuprous salt, an organic base and tetramethylethylenediamine;

[0036] The molar ratio of the cyano group-containing olefin compound to methyldichlorosilane is 1:(1.0-1.15);

[0037] The molar ratio of the cyano group-containing olefin compound, cuprous salt, organic base and tetramethylethylenediamine is 1:

[0038] (0.01-0.1):(0.01-0.1):(0.05-0.2).

[0039] Compared with the prior art, the present invention has the following beneficial effects:

[0040] The invention uses methyldichlorosilane and cyano-containing olefin as raw materials to react under the action of a specific catalyst to prepare a cyanochlorosilane compound. The preparation method of the invention has simple reaction operation, a yield of more than 76%, a purity of more than 99.1%, and is suitable for industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1 The compound prepared in Example 1 1 H NMR spectrum.

[0042] Figure 2 The compound prepared in Example 1 13 C NMR spectrum. DETAILED DESCRIPTION

[0043] The technical solution of the present invention will be further described below with reference to the accompanying drawings and through specific embodiments. However, the following examples are merely simplified examples of the present invention and do not represent or limit the scope of protection of the present invention. The scope of protection of the present invention shall be subject to the claims.

[0044] Example 1

[0045] This embodiment provides a 2-cyanoethylmethyldichlorosilane and a preparation method thereof, wherein the preparation method comprises the following steps:

[0046] In a 500 mL high-pressure reaction apparatus, under nitrogen protection, acrylonitrile (79.5 g, 1.5 mol), cuprous chloride (7.4 g, 0.075 mol), tetramethylethylenediamine (26.2 g, 0.225 mol), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) (4.6 g, 0.03 mol), and methyldichlorosilane (181.2 g, 1.575 mol) were added. After mixing evenly, the mixture was kept at 80 ° C and a pressure of 2.0 MPa for 10 hours. After the reaction was completed, the mixture was slowly cooled to room temperature, filtered under nitrogen protection, and distilled to obtain 2-cyanoethylmethyldichlorosilane.

[0047] 2-Cyanoethylmethyldichlorosilane was characterized by H NMR spectroscopy. Figure 1 As shown, its NMR data are as follows:

[0048] 1 H NMR (500MHz, Chloroform-d) δ2.48 (t, J = 8.0 Hz, 2H), 1.58 (d, J = 16.0 Hz, 2H), 0.79 (s, 3H).

[0049] 2-Cyanoethylmethyldichlorosilane was characterized by NMR carbon spectroscopy. Figure 2 As shown, its NMR data are as follows:

[0050] 13 C NMR (125MHz, Chloroform-d) δ 119.73, 16.11, 10.76, 5.51.

[0051] Example 2

[0052] This embodiment provides 2-cyanoethylmethyldichlorosilane and a preparation method thereof. The preparation method is different from that of Example 1 only in that cuprous chloride is replaced with cuprous sulfate (16.7 g, 0.075 mol). The rest is the same as that of Example 1.

[0053] Example 3

[0054] This embodiment provides 2-cyanoethylmethyldichlorosilane and a preparation method thereof. The preparation method is different from that of Example 1 only in that DBU is replaced with triethylamine (3.0 g, 0.03 mol). The rest is the same as that of Example 1.

[0055] Example 4

[0056] This example provides a 2-cyanoethylmethyldichlorosilane and a method for preparing the same, the method for preparing the same being different from example 1 only in that the amount of methyl dichlorosilane used is (189.8 g, 1.65 mol) (the molar ratio of the cyano group-containing olefin compound to the methyl dichlorosilane is 1:1.1), and the rest is the same as example 1.

[0057] Example 5

[0058] This example provides a 2-cyanoethylmethyldichlorosilane and a method for preparing the same, the method for preparing the same being different from example 1 only in that the amount of cuprous chloride used is (1.5 g, 0.015 mol), the amount of DBU used is (2.3 g, 0.015 mol), and the amount of tetramethylethylenediamine used is (8.7 g, 0.075 mol) (the molar ratio of the cyano group-containing olefin compound, the cuprous salt, the organic base, and the tetramethylethylenediamine is 1:0.01:0.01:0.05), and the rest is the same as example 1.

[0059] Example 6

[0060] This example provides a 2-cyanoethylmethyldichlorosilane and a method for preparing the same, the method for preparing the same being different from example 1 only in that the amount of cuprous chloride used is (14.9 g, 0.15 mol), the amount of DBU used is (22.8 g, 0.15 mol), and the amount of tetramethylethylenediamine used is (34.9 g, 0.3 mol) (the molar ratio of the cyano group-containing olefin compound, the cuprous salt, the organic base, and the tetramethylethylenediamine is 1:0.1:0.1:0.2), and the rest is the same as example 1.

[0061] Example 7

[0062] This example provides a 2-cyanoethylmethyldichlorosilane and a method for preparing the same, the method for preparing the same being different from example 1 only in that the amount of methyl dichlorosilane used is (198.4 g, 1.725 mol) (the molar ratio of the cyano group-containing olefin compound to the methyl dichlorosilane is 1:1.15), and the rest is the same as example 1.

[0063] Example 8

[0064] This example provides a 2-cyanoethylmethyldichlorosilane and a method for preparing the same, the method for preparing the same being different from example 1 only in that the amount of methyl dichlorosilane used is (172.6 g, 1.5 mol) (the molar ratio of the cyano group-containing olefin compound to the methyl dichlorosilane is 1:1), and the rest is the same as example 1.

[0065] Example 9

[0066] This example provides a 2-cyanoethylmethyldichlorosilane and a method for preparing the same, the method for preparing the same being identical to that of Example 1 except that the temperature of the reaction is 70°C and the pressure is 1.8 MPa.

[0067] Example 10

[0068] This example provides a 2-cyanoethylmethyldichlorosilane and a method for preparing the same, the method for preparing the same being identical to that of Example 1 except that the temperature of the reaction is 100°C and the pressure is 2.5 MPa.

[0069] Example 11

[0070] This example provides a 2-cyanoethylmethyldichlorosilane and a method for preparing the same, the method for preparing the same being identical to that of Example 1 except that the reaction time is 14 hours.

[0071] Example 12

[0072] This example provides a 2-cyanoethylmethyldichlorosilane and a method for preparing the same, the method for preparing the same being identical to that of Example 1 except that the reaction time is 18 hours.

[0073] Example 13

[0074] This example provides a 3-cyanopropylmethyldichlorosilane and a method for preparing the same, the method for preparing the same being identical to that of Example 1 except that acrylonitrile is replaced by 3-butenenitrile (100.6 g, 1.5 mol).

[0075] The NMR data of the 3-cyanopropylmethyldichlorosilane is characterized as follows:

[0076] 1 H NMR (500 MHz, Chloroform-d) δ 2.42 (t, J = 7.0 Hz, 2H), 1.88 - 1.69 (m, 2H), 1.18 (t, J = 9.0 Hz, 2H), 0.77 (s, 3H).

[0077] 13 C NMR (125 MHz, Chloroform-d) δ 119.63, 20.35, 19.50, 18.14, 5.56.

[0078] Example 14

[0079] This embodiment provides 1-methyl-2-cyanoethylmethyldichlorosilane and a preparation method thereof. The preparation method differs from that of Example 1 only in that acrylonitrile is replaced with 2-butenenitrile (100.6 g, 1.5 mol). The rest is the same as that of Example 1.

[0080] The nuclear magnetic resonance data of the 1-methyl-2-cyanoethylmethyldichlorosilane are characterized as follows:

[0081] 1 H NMR (500 MHz, Chloroform-d) δ2.68 (dd, J = 10.4, 4.6 Hz, 1H), 2.43 (dd, J = 10.5, 4.5 Hz, 1H), 1.67-1.49 (m, 1H), 1.32 (d, J = 6.5 Hz, 3H), 0.68 (d, J = 1.4 Hz, 3H).

[0082] 13 C NMR (125MHz, Chloroform-d) δ 115.86, 20.86, 16.91, 13.45, 2.13.

[0083] Example 15

[0084] This embodiment provides 2-cyanoethylmethyldichlorosilane and a preparation method thereof. The preparation method is different from that of Example 1 only in that the reaction temperature is 65° C., and the rest is the same as that of Example 1.

[0085] Example 16

[0086] This embodiment provides 2-cyanoethylmethyldichlorosilane and a preparation method thereof. The preparation method is different from that of Example 1 only in that the reaction time is 6 hours, and the rest is the same as that of Example 1.

[0087] Example 17

[0088] This embodiment provides 2-cyanoethylmethyldichlorosilane and a preparation method thereof. The preparation method differs from that of Example 1 only in that the amount of cuprous chloride used is (1.2 g, 0.012 mol), and (the molar ratio of the cyano olefin compound, cuprous salt, organic base, and tetramethylethylenediamine is 1:0.008:0.02:0.15). The rest is the same as that of Example 1.

[0089] Example 18

[0090] This embodiment provides 2-cyanoethylmethyldichlorosilane and a preparation method thereof. The preparation method differs from that of Example 1 only in that the amount of tetramethylethylenediamine used is 5.2 g, 0.045 mol, and the molar ratio of the cyano olefin compound, cuprous salt, organic base, and tetramethylethylenediamine is 1:0.05:0.02:0.03. The rest is the same as that of Example 1.

[0091] Example 19

[0092] This example provides 2-cyanoethylmethyldichlorosilane and a preparation method thereof. The preparation method differs from that in Example 1 only in that the amount of DBU used is 1.8 g, 0.012 mol, and the molar ratio of the cyano olefin compound, cuprous salt, organic base, and tetramethylethylenediamine is 1:0.05:0.008:0.15. The rest is the same as in Example 1.

[0093] Comparative Example 1

[0094] This comparative example provides a 2-cyanoethylmethyldichlorosilane and a preparation method thereof. The preparation method is different from that of Example 1 only in that tetramethylethylenediamine is not added, and the rest is the same as that of Example 1.

[0095] Comparative Example 2

[0096] This comparative example provides a 2-cyanoethylmethyldichlorosilane and a preparation method thereof. The preparation method differs from that in Example 1 only in that tetramethylethylenediamine is replaced with N,N-dimethylcyclohexylamine (28.6 g, 0.225 mol). The rest is the same as in Example 1.

[0097] The yield and purity of the chlorocyanosilane compounds prepared in the above examples and comparative examples are shown in Table 1:

[0098] Table 1

[0099]

[0100]

[0101] As can be seen from the data in Table 1, the yield of the chlorocyanosilane compound obtained by the preparation method of the present invention is above 76%, and the preferred solution reaches above 84%, and the purity is above 99.1%. The reaction operation is simple and suitable for industrial production.

[0102] From the comparison between Example 1 and Examples 15-16, it can be seen that if the reaction temperature is too low or the reaction time is too short, the reaction rate will decrease or the reaction will be insufficient, thereby causing the yield of the product to decrease.

[0103] As can be seen from the comparison of Example 1 and Comparative Examples 17-19, if the amount of cuprous chloride, organic base or tetramethyl ethylenediamine is too small, the catalytic effect becomes poor, and thus the yield of the product is reduced.

[0104] As can be seen from the comparison of Example 1 and Comparative Example 1, if tetramethyl ethylenediamine is not added, the catalytic reaction activity of cuprous salt cannot be improved, and thus the yield is reduced.

[0105] As can be seen from the comparison of Example 1 and Comparative Example 2, if tetramethyl ethylenediamine is replaced by N,N-dimethylcyclohexylamine in Comparative Example 2, the catalytic reaction activity of cuprous salt is reduced, and thus the yield is reduced.

[0106] The applicant declares that the above description is only a specific embodiment of the present application, but the protection scope of the present application is not limited thereto. It should be understood by those skilled in the art that any changes or replacements within the technical scope disclosed by the present application can be easily thought out by those skilled in the art, and all of them fall within the protection scope and disclosure scope of the present application.

Claims

1. A method for preparing a chlorocyanosilane compound, characterized in that: The preparation method of the cyanochlorosilane compound comprises the following steps: Methyldichlorosilane reacts with a cyano group-containing olefin compound in the presence of a catalyst to obtain a cyanochlorosilane compound; The catalyst includes a combination of a cuprous salt, an organic base and tetramethylethylenediamine.

2. The method for preparing a chlorocyanosilane compound according to claim 1, wherein The cyanochlorosilane compound has a structure shown in the following formula I or formula II: Wherein, n is any integer between 1 and 4, and R is a methyl group or an ethyl group.

3. The method for preparing a chlorocyanosilane compound according to claim 1 or 2, wherein: The cuprous salt includes any one of cuprous chloride, cuprous sulfate or cuprous acetate, or a combination of at least two thereof, and is more preferably cuprous chloride; Preferably, the organic base includes any one or a combination of at least two of 1,8-diazabicyclo[5.4.0]undec-7-ene, triethylamine or 1,5,7-triazabicyclo[4.4.0]dec-5-ene, and more preferably 1,8-diazabicyclo[5.4.0]undec-7-ene.

4. The method for preparing a chlorocyanosilane compound according to any one of claims 1 to 3, wherein: The cyano group-containing olefin compound has the following structure:

5. The method for preparing a chlorocyanosilane compound according to any one of claims 1 to 4, wherein: The reaction temperature is 70-100°C, preferably 80-90°C; Preferably, the reaction time is 8-14 h, more preferably 9-10 h; Preferably, the reaction pressure is 1.8 MPa-2.5 MPa.

6. The method for preparing a chlorocyanosilane compound according to any one of claims 1 to 5, wherein: The molar ratio of the cyano group-containing olefin compound to methyldichlorosilane is 1:(1.0-1.15), preferably 1:(1.05-1.10).

7. The method for preparing a chlorocyanosilane compound according to any one of claims 1 to 6, wherein: The molar ratio of the cyano group-containing olefin compound, cuprous salt, organic base and tetramethylethylenediamine is 1:(0.01-0.1):(0.01-0.1):(0.05-0.2), and more preferably 1:(0.03-0.08):(0.03-0.08):(0.10-0.15).

8. The method for preparing a chlorocyanosilane compound according to any one of claims 1 to 7, wherein: The reaction further comprises a post-treatment step; Preferably, the post-treatment includes filtration and distillation.

9. The method for preparing a chlorocyanosilane compound according to any one of claims 1 to 8, wherein: The rectification includes vacuum rectification; Preferably, the distillation temperature is 105-125°C, more preferably 110-115°C; Preferably, the distillation pressure is 1-20 mbar, more preferably 5-10 mbar.

10. The method for preparing a chlorocyanosilane compound according to any one of claims 1 to 9, characterized in that: The preparation method of the cyanochlorosilane compound specifically comprises the following steps: Methyldichlorosilane and a cyano-containing olefin compound are reacted with a catalyst at 70-100°C and 1.8 MPa-2.5 MPa for 8-14 hours, filtered, and distilled at 105-125°C and 1-20 mbar to obtain a cyanochlorosilane compound; The catalyst comprises a combination of a cuprous salt, an organic base and tetramethylethylenediamine; The molar ratio of the cyano group-containing olefin compound to methyldichlorosilane is 1:(1.0-1.15); The molar ratio of the cyano group-containing olefin compound, cuprous salt, organic base and tetramethylethylenediamine is 1:(0.01-0.1):(0.01-0.1):(0.05-0.2).

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