Synthesis method of silane containing polyfluorine and cyano groups

Abstract

The invention belongs to the technical field of fine chemicals, medicines and materials, and particularly relates to a synthesis method of silane containing polyfluorine and cyano groups. The synthesis method comprises the following steps: reacting a compound I and a compound II under the action of a catalyst, and then adding a fluorination reagent for reaction to obtain the silane containing polyfluorine and cyano groups as shown in a formula III. The synthesis method has the advantages of low cost, environment friendliness, high reaction yield, easiness in separation and the like, and industrial production can be realized.

Description

Technical Field

[0001] This invention belongs to the fields of fine chemicals, pharmaceuticals, and materials technology. More specifically, this invention relates to a method for synthesizing silanes containing polyfluorine and cyano groups. Background Technology

[0002] Liquid electrolytes in lithium-ion batteries typically contain lithium salts, usually LiPF6, in a blend of ethylene carbonate (EC) and one or more co-solvents such as dimethyl carbonate (DMC), diethyl carbonate (DEC), or ethyl methyl carbonate (EMC). Unfortunately, LiPF6 is unstable in these carbonate solvents above 60°C and at charging voltages exceeding 4.3 volts. Operating lithium-ion batteries above these temperatures or pressures leads to rapid degradation of electrode materials and battery performance. Furthermore, current lithium-ion electrolyte solvents exhibit a flash point of approximately 35°C and are a major source of energy released during extreme lithium-ion battery failures. Given these significant limitations, current electrolytes hinder the development of advanced lithium-ion batteries for all applications, including portable products, electric vehicles (EDVs), and utility-scale use. Large-scale lithium-ion batteries also require significantly reduced battery failure rates to effectively serve applications in EDVs and grid storage. Therefore, there is a long-standing and unmet need for improved electrolyte solutions in energy storage devices such as lithium-ion batteries.

[0003] CN106795184 describes organosilicon compounds as liquid electrolyte solvents that can replace carbonate-based solvent systems in conventional lithium-ion batteries. These organosilicon-based solvents offer significant improvements in performance and abuse tolerance in Li-ion batteries, including increased thermal stability for extended lifespan at high temperatures, increased electrolyte flash point for improved safety, increased voltage stability to allow the use of high-voltage cathode materials and achieve higher energy densities, reduced battery failure rates to meet the requirements of large-scale lithium-ion batteries used in EDV and grid storage applications, and compatibility with materials currently used in Li-ion batteries for easy adoption in current designs. The functionality of electric double-layer capacitor (EDLC) devices using organosilicon-based electrolytes has also been demonstrated.

[0004] Fluorosilicone compounds, especially cyanoalkyl-containing fluorosilanes, are used in a variety of applications, such as battery manufacturing, semiconductor deposition, fluorosilicone glass formation, and semiconductor etchants. Therefore, developing economically viable and industrially applicable methods for synthesizing such compounds is of great interest. However, existing reports mainly concern cyanoalkyl dimethylfluorosilanes, with very little research on cyanoalkyl trifluorosilanes.

[0005] CN118515703 reports the preparation of cyanoethyltrifluorosilane via the fluorination of antimony trifluoride after the reaction of acrylonitrile and trichlorosilane. This route uses expensive and highly toxic fluorinating reagents, resulting in high reaction costs and low industrialization potential. US12230751 reports the synthesis of cyanopropyltrifluorosilane by reacting cyanopropyltrichlorosilane with hydrogen fluoride gas. Due to the low vapor pressure and high volatility of cyanopropyltrifluorosilane, the separation of hydrogen fluoride gas and the product is difficult, and incomplete reaction leads to unsatisfactory yields and purification. The hydrogen fluoride system is highly hazardous and environmentally unfriendly.

[0006] Therefore, there is an urgent need for a method that can efficiently and cost-effectively synthesize cyano- and polyfluorinated silanes. Summary of the Invention

[0007] In view of the shortcomings of the prior art described above, the purpose of this invention is to provide a method for synthesizing silanes containing polyfluorinated and cyano groups, which mainly solves the problems of high environmental hazards, high cost and harsh reaction conditions of existing synthesis methods.

[0008] The technical solution of this invention is:

[0009] This invention provides a method for synthesizing silanes containing polyfluorinated and cyano groups, the method comprising the following steps:

[0010] After compounds I and II react under the action of a catalyst, a fluorinating agent is added to react and give the silane containing polyfluorinated and cyano groups as shown in formula III;

[0011]

[0012] In formulas I and II, R is independently selected from C1-C5 alkyl groups; in formulas I and III, X is a cyano group and n is 0-6.

[0013] By adopting the aforementioned technical solution, the beneficial effects of the present invention are:

[0014] The present invention provides a method for synthesizing silanes containing polyfluorine and cyano groups. This method has advantages such as low cost, environmental friendliness, high reaction yield, and easy separation, and can realize industrial production. Detailed Implementation

[0015] The following describes in detail the embodiments of the method for synthesizing polyfluorinated and cyano-containing silanes provided by the present invention.

[0016] The "range" disclosed in this application is defined by a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, which define the boundaries of a particular range. Ranges defined in this way can include or exclude endpoints and can be arbitrarily combined; that is, any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60–120 and 80–110 are listed for a specific parameter, it is understood that ranges of 60–110 and 80–120 are also expected. Furthermore, if minimum range values ​​of 1 and 2 are listed, and if maximum range values ​​of 3, 4, and 5 are listed, then the following ranges are all expected: 1–3, 1–4, 1–5, 2–3, 2–4, and 2–5. In this application, unless otherwise stated, the numerical range "a–b" represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0~5" indicates that all real numbers between "0~5" have been listed in this article; "0~5" is simply a shortened representation of these numerical combinations. Furthermore, when a parameter is stated as an integer ≥2, it is equivalent to disclosing that the parameter is, for example, an integer such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0017] Through extensive research and exploration, the inventors of this invention have provided a method for synthesizing silanes containing polyfluorinated and cyano groups. This method uses oxysilanes and allyl compounds as raw materials, and achieves a hydrosilylation reaction under the action of a catalyst; the target product is then obtained through a fluorination reaction. This method has many advantages, including low cost, environmental friendliness, high reaction yield, and easy separation. Based on this, this application has been completed.

[0018] Synthesis methods for silanes containing polyfluorinated and cyano groups.

[0019] This invention provides a method for synthesizing silanes containing polyfluorinated and cyano groups, the method comprising the following steps:

[0020] After compounds I and II react under the action of a catalyst, a fluorinating agent is added to react and give the silane containing polyfluorinated and cyano groups as shown in formula III;

[0021]

[0022] In formulas I and II, R is independently selected from C1-C5 alkyl groups; in formulas I and III, X is a cyano group and n is 0-6.

[0023] In the synthetic method provided by this invention, compounds I and II react with a catalyst to obtain intermediate IV, which then reacts with a fluorinating reagent to yield a silane containing polyfluorinated and cyano groups as shown in Formula III. Specifically:

[0024]

[0025] In formulas I to II and IV, R is independently selected from C1-C5 alkyl groups; it can be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.

[0026] In formulas I to II and IV, X is a cyano group.

[0027] In equations I through IV, n ranges from 0 to 6, and can be any value of 0, 1, 2, 3, 4, 5, or 6. When n is 0, equation II is...

[0028] In this invention, by way of example (not exhaustive), compound I is selected from one or more of the following structures:

[0029]

[0030] In this invention, by way of example (not exhaustive), compound II is selected from one or more of the following structures:

[0031] In this invention, by way of example (not exhaustive), compound IV is selected from one or more of the following structures:

[0032]

[0033]

[0034] In this invention, by way of example (not exhaustive), the silanes containing polyfluorinated and cyano groups represented by Formula III are selected from one or more of the following structures:

[0035]

[0036] In the preparation method provided by this invention, the catalyst is a cobalt catalyst or an iron catalyst. Optionally, the cobalt catalyst is selected from one or more of cobalt octacarbonyl, cobalt acetate, bis(salicylic acid) ethyl cobalt, and cobalt acetylacetonate. The iron catalyst is selected from one or more of tetraphenylporphyrin iron, ferrocene, and phthalocyanine iron.

[0037] In the preparation method provided by this invention, the reaction of compound I and compound II under the action of a catalyst also includes a reaction solvent, wherein the reaction solvent is selected from one or more of toluene, chlorobenzene, xylene, p-chlorotrifluorotoluene, tetrahydrofuran, acetonitrile, and dioxane. Optionally, the mass ratio of compound I to the reaction solvent is 1:(2-5) and any value between them or any range between two values, and may be selected as 1:(2-3), 1:(3-5), 1:(2-4), or 1:(4-5).

[0038] In the preparation method provided by this invention, during the reaction of compound I and compound II under the action of a catalyst, the reaction temperature is 40-100℃ or any value between them, or any two values, and can be selected as 40-60℃, 60-90℃, or 90-100℃. The reaction time is 18-25h or any value between them, or any two values, and can be selected as 18-20h, 20-21h, or 21-25h.

[0039] In the preparation method provided by the present invention, the fluorinating reagent is selected from one or more of the following: aqueous hydrofluoric acid solution, pyridine hydrogen fluoride, triethylamine hydrofluoric acid salt, potassium hydrofluoride, and ammonium fluoride hydrofluoric acid salt.

[0040] In the preparation method provided by the present invention, the molar ratio of compound I to fluorinating reagent is 1:(1-6) and any value between them or any range between any two values, which can be selected as 1:(1-3), 1:(3-6), 1:(1-2), 1:(2-4), 1:(4-6).

[0041] In the preparation method provided by the present invention, the reaction temperature is 25℃-100℃ and any value between them or any two values, and can be selected as 25℃-30℃, 30℃-70℃, or 70℃-100℃.

[0042] In the preparation method provided by the present invention, the reaction time is 3 to 12 hours and any value between them or any two values, and can be selected as 3 to 10 hours or 10 to 12 hours.

[0043] Silanes containing polyfluorinated and cyano groups

[0044] The present invention also provides a silane containing polyfluorine and cyano groups, synthesized using the method described in the first aspect of the present invention.

[0045] The beneficial effects of the present invention will be further illustrated below with reference to the embodiments.

[0046] To make the inventive objectives, technical solutions, and beneficial effects of this invention clearer, the invention is further described in detail below with reference to embodiments. However, it should be understood that the embodiments of this invention are merely for illustrative purposes and not for limiting the invention, and the embodiments are not limited to those given in the specification. Unless otherwise specified, specific experimental or operational conditions in the embodiments were prepared under conventional conditions or according to the conditions recommended by the material supplier.

[0047] Furthermore, it should be understood that the existence of other method steps before or after the combined steps, or the insertion of other method steps between these explicitly mentioned steps, does not preclude the existence of other method steps before or after the combined steps, or the insertion of other method steps between these explicitly mentioned steps, unless otherwise stated. It should also be understood that the combined connection relationship between one or more devices / apparatus mentioned in this invention does not preclude the existence of other devices / apparatus before or after the combined devices / apparatus, or the insertion of other devices / apparatus between these explicitly mentioned devices / apparatus, unless otherwise stated. Moreover, unless otherwise stated, the numbering of each method step is merely a convenient tool for identifying each method step, and not for limiting the order of the method steps or limiting the scope of the invention. Changes or adjustments to their relative relationships, without substantially altering the technical content, should also be considered within the scope of the invention.

[0048] In the following embodiments, unless otherwise specified, all the raw materials of the present invention are commercially available or prepared according to conventional methods in the art.

[0049] Example 1

[0050] Example 1 provides a method for preparing 3-cyanopropyltrifluorosilane using trimethoxysilane and butenonitrile as raw materials, cobalt acetylacetonate as catalyst, and triethylamine hydrofluoric acid as fluorinating agent. The synthesis reaction formula is as follows:

[0051]

[0052] The preparation steps include:

[0053] 122 g of trimethoxysilane, 73.7 g of butenonitrile, and 244 g of toluene were accurately weighed into a 1000 ml four-necked flask. Under nitrogen protection, 2.57 g of cobalt acetylacetonate was added, and the mixture was slowly heated to 100 °C and reacted for 25 hours. Then, 161 g of triethylamine hydrofluoric acid was added dropwise while maintaining the temperature at 100 °C. After reacting for 12 hours, the product was desolvated and distilled to obtain 140.1 g of product with a GC purity of 99.3% and a yield of 91.6%.

[0054] 1 HNMR (100MHz) δ = 1.20 (m, 2H), 1.92 (m, 2H), 2.47 (t, J = 6.5Hz, 2H); 19 FNMR(96MHz)δ=-137.08(s).Found:m / z 153.0217.Calcd for C4H6NF3Si:M,153.0222.

[0055] Example 2

[0056] Example 2 provides a method for preparing 3-cyanoethyltrifluorosilane using triethoxysilane and acrylonitrile as raw materials, octacarbonyldicobalt as catalyst, and hydrofluoric acid aqueous solution as fluorinating agent. The synthesis reaction formula is as follows:

[0057]

[0058] The preparation steps include:

[0059] 164 g of triethoxysilane, 58.3 g of acrylonitrile, and 492 g of chlorobenzene were accurately weighed into a 1000 ml four-necked flask. Under nitrogen protection, 3.42 g of octacarbonyl dicobalt was added, and the mixture was slowly heated to 90 °C and reacted for 18 hours. After cooling to 25 °C, 127 g of 49% hydrofluoric acid aqueous solution was added dropwise while maintaining the temperature. After reacting for 3 hours, the mixture was separated, the organic phase was desolvated, and the product was obtained by distillation, yielding 126.7 g of product with a GC purity of 99.0% and a yield of 91.2%.

[0060] Example 3

[0061] Example 3 provides a method for preparing 3-cyanobutyltrifluorosilane using triisopropoxysilane and pentenonitrile as raw materials, ferrocene as catalyst, and potassium hydrofluoric acid as fluorinating agent. The synthesis reaction formula is as follows:

[0062]

[0063] The preparation steps include:

[0064] Accurately weigh 206 g of triisopropoxysilane, 243 g of acrylonitrile, and 1030 g of acetonitrile into a 2000 ml four-necked flask. Under nitrogen protection, add 18.6 g of ferrocene, and slowly heat to 40 °C and react for 21 hours. Then heat to 70 °C, maintain the temperature, add 468 g of potassium hydrofluoric acid, and react for 10 hours. Filter, remove solvent from the filtrate, and distill to obtain 150.1 g of product with GC purity of 98.7% and yield of 89.9%.

[0065] Example 4

[0066] Example 4 provides a method for preparing 3-cyanopropyltrifluorosilane using tri-n-butoxysilane and butenocyanate as raw materials, iron phthalocyanine as catalyst, and pyridine hydrogen fluoride as fluorinating agent. The synthesis reaction formula is as follows:

[0067]

[0068] The preparation steps include:

[0069] 248 g of tri-n-butoxysilane, 201 g of butenonitrile, and 992 g of tetrahydrofuran were accurately weighed into a 3000 ml four-necked flask. Under nitrogen protection, 28.4 g of ferrophthalocyanine was added, and the mixture was slowly heated to 60 °C and reacted for 20 hours. After cooling to 30 °C, 396 g of pyridine hydrogen fluoride was added dropwise. After reacting for 3 hours, the mixture was filtered to remove the solvent, and the product was obtained by distillation with a purity of 98.3% and a yield of 91.0%.

[0070] In summary, this invention effectively overcomes the various shortcomings of the prior art and has high industrial application value.

[0071] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any form or substance. It should be noted that those skilled in the art can make various improvements and additions without departing from the method of the present invention, and these improvements and additions should also be considered within the scope of protection of the present invention. Any modifications, alterations, and equivalent changes made by those skilled in the art based on the above-disclosed technical content without departing from the spirit and scope of the present invention are equivalent embodiments of the present invention. Furthermore, any modifications, alterations, and evolutions made to the above embodiments based on the essential technology of the present invention still fall within the scope of the technical solution of the present invention.

Claims

1. A method for synthesizing silanes containing polyfluorinated and cyano groups, characterized in that, The synthesis method includes the following steps: After compounds I and II react under the action of a catalyst, a fluorinating agent is added to react and give the silane containing polyfluorinated and cyano groups as shown in formula III; In formulas I and II, R is independently selected from C1-C5 alkyl groups; in formulas I and III, X is a cyano group and n is 0-6.

2. The method for synthesizing silanes containing polyfluorinated and cyano groups according to claim 1, characterized in that, It also includes one or more of the following conditions: A1) The catalyst is a cobalt catalyst or an iron catalyst; A2) The molar ratio of compound I, compound II, and catalyst is 1:(1-3):(0.01-0.1); A3) The reaction of compounds I and II under the action of a catalyst also includes a reaction solvent, wherein the reaction solvent is selected from one or more of toluene, chlorobenzene, xylene, p-chlorotrifluorotoluene, tetrahydrofuran, acetonitrile, and dioxane.

3. The method for synthesizing silanes containing polyfluorinated and cyano groups according to claim 2, characterized in that, Step 1) also includes one or more of the following conditions: A11) In feature A1), the cobalt catalyst is selected from one or more of cobalt octacarbonyl, cobalt acetate, bis(salicylic acid) ethyl cobalt, and cobalt acetylacetonate; A12) In feature A1), the iron catalyst is selected from one or more of tetraphenylporphyrin iron, ferrocene, and phthalocyanine iron; In feature A3), the mass ratio of compound I to the reaction solvent is 1:(2-5).

4. The method for synthesizing silanes containing polyfluorinated and cyano groups according to claim 1, characterized in that, It also includes one or more of the following conditions: B1) In the reaction of compound I and compound II under the action of a catalyst, the reaction temperature is 40-100℃; B2) The reaction of compounds I and II under the action of a catalyst takes 18-25 hours.

5. The method for synthesizing silanes containing polyfluorinated and cyano groups according to claim 1, characterized in that, Compound I is selected from one or more of the following structures:

6. The method for synthesizing silanes containing polyfluorinated and cyano groups according to claim 1, characterized in that, In this context, compound Ⅱ is selected from one or more of the following structures:

7. The method for synthesizing silanes containing polyfluorinated and cyano groups according to claim 1, characterized in that, It also includes one or more of the following conditions: C1) The fluorinating agent is selected from one or more of the following: aqueous hydrofluoric acid, pyridine hydrogen fluoride, triethylamine hydrofluoric acid salt, potassium hydrofluoride, and ammonium fluoride salt of hydrofluoric acid; The molar ratio of compound I to the fluorinating agent in C2) is 1:(1-6).

8. The method for synthesizing silanes containing polyfluorinated and cyano groups according to claim 1, characterized in that, It also includes one or more of the following conditions: D1) Add the fluorinating agent to the reaction, and the reaction temperature is 25℃-100℃; D2) is added to the fluorinating reagent and reacted for 3 to 12 hours.

9. The method for synthesizing silanes containing polyfluorinated and cyano groups according to claim 1, characterized in that, The polyfluorinated and cyano silanes represented by Formula III are selected from one or more of the following structures:

10. A silane containing polyfluorine and cyano groups, prepared by the synthetic method according to any one of claims 1 to 9.

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