A catalyst and a process for its preparation, a catalyst composition and the use thereof

Abstract

The application discloses a catalyst and a preparation method thereof, a catalyst composition and application thereof, and a general structural formula of the catalyst is shown as formula (I): wherein R1 and R2 can be the same or different, and are independently selected from an alkyl group or an aryl group; R1 and R2 can also form a cyclic structure with a P atom, such as a three-membered ring, a four-membered ring, a five-membered ring or a six-membered ring. The catalyst composition comprises component A and component B, wherein A is a nitrogen-containing organic base, and a general structural formula of component B is shown as formula (I). The catalyst composition can catalyze a substitution reaction of chloroethylene carbonate to prepare fluoroethylene carbonate, and the reaction yield can be up to 95% or more, which is significantly higher than that of a traditional process.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis, specifically relating to a catalyst and its preparation method, a catalyst composition, and a method for using it to prepare fluoroethylene carbonate. Background Technology

[0002] Fluorinated ethylene carbonate (FEC) is a fluorinated organic compound and a major additive in lithium-ion battery electrolytes. It improves the performance of the SEI film, forming a dense structural layer without increasing impedance, preventing further electrolyte decomposition, and improving the electrolyte's low-temperature performance. Currently, lithium batteries with added FEC are mainly used in hybrid and pure electric vehicles, and are expected to be used in energy storage in the future, particularly in solar and wind power, indicating a promising market prospect.

[0003] In industrial production, there are two main process routes for fluoroethylene carbonate. The first is the fluorine method, which uses 30% F2 / N2 as a fluorinating agent to directly fluorinate ethylene carbonate at 50°C. This reaction is highly reactive, has many side reactions, is difficult to control, and requires sophisticated equipment. The second method uses a fluorinated metal salt as a fluorinating agent, which reacts with chloroethylene carbonate in the presence of a phase transfer catalyst to produce fluoroethylene carbonate. In this reaction, potassium fluoride has low reactivity, a long reaction time, and produces large amounts of mixed potassium chloride and potassium fluoride salts as byproducts, which are difficult to process and costly.

[0004] Both of the above processes have industrial-scale facilities in China, especially the fluorinated metal salt (potassium fluoride) process, which is the mainstream production process domestically. However, the reaction yield is low, only about 80%. Given the current sluggish market for fluoroethylene carbonate, industrial-scale facilities are unprofitable, or even fail to generate revenue. Therefore, the industry urgently needs to develop a simple, efficient, high-yield, and low-cost catalytic system and synthesis method for the preparation of fluoroethylene carbonate. Summary of the Invention

[0005] To overcome the shortcomings of the prior art, this invention provides a catalyst and its preparation method. This catalyst can be used to catalyze fluorination reactions using hydrogen fluoride as a fluorinating agent, significantly improving the selectivity of the fluorination reaction. The catalyst has mild synthesis conditions, simple and easy post-processing, high yield, and is suitable for large-scale synthesis.

[0006] The present invention also provides a catalyst composition and its use in the preparation of fluoroethylene carbonate. When the catalyst composition is used in the preparation of fluoroethylene carbonate, the reaction yield can reach more than 95%, which is significantly higher than that of the traditional process.

[0007] To achieve the above-mentioned objectives, the technical solution adopted by this invention is as follows:

[0008] A catalyst, with the general structural formula shown in formula (I):

[0009]

[0010] R1 and R2 can be the same or different, and can be independently selected from alkyl or aryl groups; R1 and R2 can also form cyclic structures with P atoms, such as three-membered rings, four-membered rings, five-membered rings or six-membered rings.

[0011] Further, in the catalyst structure of formula (I), the alkyl group includes straight-chain alkyl, branched alkyl, and cycloalkyl; the alkyl group has no more than 10 carbon atoms, preferably alkyl with 1-6 carbon atoms; the aryl group in the catalyst structure is a C6-C20 aryl group and a substituted aryl group, preferably phenyl, p-methylphenyl, o-methylphenyl or m-methylphenyl.

[0012] Further, the catalyst described in formula (I) is prepared as follows: (1) a reaction solvent, a phosphine chloride compound, and a metal fluoride are added to a reactor, and the reaction is stirred at the reaction temperature. After the reaction is completed, the mixture is filtered and the solvent is removed under vacuum to obtain a phosphine fluoride compound; (2) the phosphine fluoride compound, the reaction solvent, and triethylamine from step (1) are added to a reactor, and the reaction is stirred at the reaction temperature. After the reaction is completed, the solvent is removed under vacuum to obtain component B. The general structural formula of the phosphine chloride compound is shown in formula (II), and preferably, a phosphine chloride compound with the structural formula af is used.

[0013]

[0014] Further, in step (1) of the preparation method, the reaction solvent is one or more of acetonitrile, ethyl acetate, dimethyl tetrahydrofuran carbonate, and diethyl carbonate, preferably acetonitrile and / or ethyl acetate. The metal fluoride is one or more of lithium fluoride, sodium fluoride, and potassium fluoride. The reaction temperature is 30-90℃, preferably 50-70℃; the reaction time is 1-8h, preferably 3-5h. After the reaction, filtration and vacuum desolvation are performed. During vacuum desolvation, the pressure is 1-10kPa, preferably 2-5kPa, the desolvation temperature is 40-80℃, preferably 50-70℃, and the desolvation time is 0.5-2h, preferably 0.5-1.5h. The molar ratio of phosphine chloride compound to metal fluoride is 1:1-1.5; the concentration of phosphine chloride compound in the solvent is 0.2-0.8mol / L, preferably 0.4-0.6mol / L.

[0015] Furthermore, in step (2) of the preparation method, the reaction solvent is one or more of acetonitrile, ethyl acetate, tetrahydrofuran, dimethyl carbonate, and diethyl carbonate, preferably tetrahydrofuran and / or dimethyl carbonate. The reaction temperature is 20-70℃, preferably 30-50℃; the reaction time is 1-5h, preferably 2-4h. When removing the solvent under vacuum, the pressure is 1-10kPa, preferably 1-3kPa, the removal temperature is 40-80℃, preferably 60-75℃, and the removal time is 0.5-3h, preferably 0.5-2h; the molar ratio of fluorinated phosphine compounds to triethylamine is 1:1-1.3; the concentration of fluorinated phosphine compounds in the solvent is 0.2-0.8mol / L, preferably 0.3-0.5mol / L.

[0016] A catalyst composition comprising component A and component B, wherein A is a nitrogen-containing organic base, and component B has the general structural formula shown in formula (I):

[0017]

[0018] R1 and R2 can be the same or different, and can be independently selected from alkyl or aryl groups; R1 and R2 can also form a cyclic structure with P atoms, such as a three-membered ring, a four-membered ring, a five-membered ring or a six-membered ring. Preferably, the molar ratio of A to B in the composition is 1:0.01%-0.1%.

[0019] Preferably, component A, a nitrogenous organic base, is one or more of trimethylamine, triethylamine, tripropylamine, diisopropylamine, diethylenetriamine, and pyridine, with triethylamine and / or pyridine being the most preferred.

[0020] The present invention also provides the use of the catalyst composition described herein in the preparation of fluoroethylene carbonate.

[0021] A method for preparing fluoroethylene carbonate includes the following steps:

[0022] The organic solvent and catalytic composition were added to the reactor and mixed. After stirring until homogeneous, hydrogen fluoride was introduced, and the mixture was stirred again until homogeneous. Then, ethylene chlorocarbonate was added, and the reaction was carried out under stirring at the reaction temperature. After the reaction was completed, residual hydrogen fluoride in the reaction solution was removed under negative pressure. The conversion rate and selectivity of the reaction were detected by gas chromatography. The catalytic composition includes component A and component B, where A is a nitrogen-containing organic base, and the general structural formula of B is shown in formula (I):

[0023]

[0024] Furthermore, in the preparation method of the fluoroethylene carbonate, the organic solvent is one or more of acetonitrile, ethyl acetate, dimethyl carbonate, diethyl carbonate, and aliphatic ether, preferably aliphatic ether, and more preferably one of tetrahydrofuran, dipropyl ether, dibutyl ether, and methyl tert-butyl ether.

[0025] Further, in the preparation method of the fluoroethylene carbonate, the molar ratio of catalytic composition A to B is 1:0.01%-0.1%; the concentration of B in the system is 0.1 mmol / L-1 mmol / L. The molar ratio of chloroethylene carbonate, nitrogen-containing organic base, and hydrogen fluoride in the system is 1:0.5-2:1-2, more preferably 1:1-1.5:1-1.2.

[0026] Furthermore, in the preparation method of the fluoroethylene carbonate, the reaction temperature is 0-100℃, preferably 30-60℃; and the reaction time is 0.5-5h, preferably 0.5-1.5h.

[0027] Furthermore, in the preparation method of the fluoroethylene carbonate, the negative pressure removal pressure is 1-10 kPa; the negative pressure removal temperature is 20-40℃; and the negative pressure removal time is 5-30 min.

[0028] The positive effects of this invention:

[0029] Fluorine has the highest electronegativity of all elements, so the F in one molecule can form a strong hydrogen bond with the H in another molecule. This hydrogen bond is the strongest among simple hydrides. This formation of hydrogen bonds results in very weak nucleophilicity of the F in the hydrogen fluoride molecule, preventing it from directly undergoing a substitution reaction with chloroethylene carbonate. The catalyst (component B) provided by this invention can effectively weaken the hydrogen bonding between F and H, promote the release of active fluoride ions, significantly improve the nucleophilicity of fluoride ions, efficiently promote the fluorination reaction using hydrogen fluoride as the fluorinating agent, and significantly improve the selectivity of the fluorination reaction. The catalytic composition formed by the catalyst (component B) and the nitrogen-containing organic base (component A) ensures both high selectivity and high conversion rate in the catalytic preparation of chloroethylene carbonate, with a reaction yield exceeding 95%, demonstrating significant advantages and great potential industrial application value. Detailed Implementation

[0030] The technical solution of the present invention will be further described below, but it is not limited thereto. Any modifications or equivalent substitutions to the technical solution of the present invention that do not depart from the scope of the technical solution of the present invention should be covered within the protection scope of the present invention.

[0031] NMR analysis: Bruker / AVANCE NEO 500M.

[0032] Chromatographic analysis:

[0033] Chromatography model: Agilent WAX:1701.42249

[0034] Carrier gas: High-purity nitrogen

[0035] Sample introduction mode: Autosampler

[0036] Nitrogen flow rate: 60 ml / min

[0037] Vaporization chamber temperature: 250℃

[0038] Split injection, split ratio: 1:10

[0039] Injection volume: 0.1 μl

[0040] Column flow rate: 2.0 ml / min

[0041] Column temperature: First-order temperature program, initial temperature 50℃, hold for 2 minutes, then increase to 260℃ at a rate of 15℃ / min.

[0042] Maintain at ℃ for 8 minutes; total running time is 24 minutes.

[0043] Detector temperature 280℃

[0044] Example 1:

[0045] Preparation of component B1

[0046]

[0047] (1) In a 250ml reaction flask, add 100ml acetonitrile, 5.79g dimethylphosphine chloride, and 5.23g anhydrous potassium fluoride. Stir at 50℃ for 4h, then filter. Remove the solvent under negative pressure (2kPa) and 50℃ for 1.5h to obtain 4.77g dimethylphosphine fluoride; (2) In a 250ml reaction flask, add 198ml dimethyl carbonate, 4.77g dimethylphosphine fluoride, and 6.03g triethylamine. Stir at 30℃ for 4h, then remove the solvent under negative pressure (1kPa) and 75℃ for 2h to obtain 10.77g component B1. NMR data 1 H NMR (500MHz, Chloroform-d) δ3.39 (dd, J=100.4, 12.3Hz, 6H), 2.44 (s, 6H), 1.31 (s, 9H).

[0048] 2. Preparation of fluoroethylene carbonate

[0049] 1 L of tetrahydrofuran, 101.19 g (1 mol) of triethylamine, and 0.18 g (1 mmol) of catalytic composition B1 were added to a 2 L stainless steel reactor. The reactor was adjusted to 50 °C, and 24.01 g (1.2 mol) of hydrogen fluoride was introduced. After stirring until homogeneous, 122.51 g (1 mol) of chloroethylene carbonate was added and the mixture was stirred for 0.8 h. The temperature was maintained at 50 °C during the reaction. After the reaction was completed, residual hydrogen fluoride was removed under negative pressure (10 kPa) and temperature of 20 °C for 30 minutes. The product was quantified by gas chromatography, yielding 101.82 g of fluoroethylene carbonate with a conversion rate of 99.8% and a selectivity of 96.2%.

[0050] Example 2:

[0051] 1. Preparation of component B2

[0052]

[0053] (1) In a 250ml reaction flask, add 100ml ethyl acetate, 7.63g diisopropylphosphine chloride, and 1.56g anhydrous lithium fluoride. Stir at 70℃ for 5h, then filter. Remove the solvent under negative pressure (5kPa) and 70℃ for 1h to obtain 6.77g diisopropylphosphine fluoride; (2) In a 250ml reaction flask, add 100ml tetrahydrofuran, 6.77g diisopropylphosphine fluoride, and 6.54g triethylamine. Stir at 50℃ for 2h, then remove the solvent under negative pressure (3kPa) and 65℃ for 0.5h to obtain 11.78g component B2. NMR data 1 H NMR (500MHz, Chloroform-d) δ3.22(s,6H),3.16(s,2H),1.31(s,9H),1.20(s,12H).

[0054] 2. Preparation of fluoroethylene carbonate

[0055] 1 L of dipropyl ether, 189.84 g (2.4 mol) of pyridine, and 0.09 g (0.4 mmol) of catalytic composition B2 were added to a 2 L stainless steel reactor. The reactor was adjusted to 30 °C, and 32.01 g (1.6 mol) of hydrogen fluoride was introduced. After stirring until homogeneous, 196.01 g (1.6 mol) of chloroethylene carbonate was added and the mixture was stirred for 1.5 h. The temperature was maintained at 30 °C during the reaction. After the reaction was completed, residual hydrogen fluoride was removed under negative pressure (1 kPa) and temperature of 40 °C for 5 minutes. The product was quantified by gas chromatography, yielding 161.54 g of fluoroethylene carbonate with a conversion rate of 99.9% and a selectivity of 95.3%.

[0056] Example 3:

[0057] 1. Preparation of component B3

[0058]

[0059] (1) In a 250ml reaction flask, add 100ml acetonitrile, 8.83g diphenylphosphine chloride, and 1.68g anhydrous sodium fluoride. Stir at 60℃ for 3h, then filter. Remove the solvent under negative pressure (3kPa) and 60℃ for 1.2h to obtain 8.12g diphenylphosphine fluoride; (2) In a 250ml reaction flask, add 100ml dimethyl carbonate, 8.12g diphenylphosphine fluoride, and 4.43g triethylamine. Stir at 40℃ for 3h, then remove the solvent under negative pressure (1kPa) and 70℃ for 1.5h to obtain 12.13g component B3. NMR data 1 H NMR (500MHz, Chloroform-d) δ7.54–7.47(m,4H),7.41–7.34(m,2H),7.34–7.27(m,4H),3.43(s,6H),1.36(s,9H).

[0060] 2. Preparation of fluoroethylene carbonate

[0061] 1 L of methyl tert-butyl ether, 101.19 g (1 mol) of triethylamine, and 0.03 g (0.1 mmol) of catalytic composition B3 were added to a 2 L stainless steel reactor. The reactor was adjusted to 60 °C, and 18.47 g (0.92 mol) of hydrogen fluoride was introduced. After stirring until homogeneous, 94.24 g (0.77 mol) of chloroethylene carbonate was added and the mixture was stirred for 0.5 h. The temperature was maintained at 60 °C during the reaction. After the reaction was completed, residual hydrogen fluoride was removed under negative pressure (7 kPa) and temperature of 25 °C for 20 minutes. The product was quantified by gas chromatography, yielding 77.99 g of fluoroethylene carbonate with a conversion rate of 99.8% and a selectivity of 95.8%.

[0062] Example 4:

[0063] 1. Preparation of component B4

[0064]

[0065] (1) In a 250ml reaction flask, add 100ml ethyl acetate, 5.46g cyclopentylphosphine chloride, and 3.14g anhydrous potassium fluoride. Stir at 70℃ for 3h, then filter. Remove the solvent under negative pressure (4kPa) and 60℃ for 1.4h to obtain 4.79g fluorinated cyclopentylphosphine; (2) In a 250ml reaction flask, add 133ml tetrahydrofuran, 4.79g fluorinated cyclopentylphosphine, and 4.84g triethylamine. Stir at 50℃ for 4h, then remove the solvent under negative pressure (2kPa) and 60℃ for 1h to obtain 8.8g component B4. NMR data 1 H NMR (500MHz, Chloroform-d) δ3.47–3.33(m,6H),2.80(s,4H),1.77(s,4H),1.59(s,2H),1.32(s,9H).

[0066] 2. Preparation of fluoroethylene carbonate

[0067] 1 L of dibutyl ether, 166.11 g (2.1 mol) of triethylamine, and 0.15 g (0.7 mmol) of catalytic composition B4 were added to a 2 L stainless steel reactor. The reactor was adjusted to 40 °C, and 42.02 g (2.1 mol) of hydrogen fluoride was introduced. After stirring until homogeneous, 233.88 g (1.91 mol) of chloroethylene carbonate was added and the mixture was stirred for 1.2 h. The temperature was maintained at 40 °C during the reaction. After the reaction was completed, residual hydrogen fluoride was removed under negative pressure (4 kPa) and temperature of 30 °C for 15 minutes. The product was quantified by gas chromatography, yielding 194.77 g of fluoroethylene carbonate with a conversion rate of 99.9% and a selectivity of 96.3%.

[0068] Example 5:

[0069] 1. Preparation of component B5

[0070]

[0071] (1) In a 250ml reaction flask, add 100ml acetonitrile, 11.64g dicyclohexylphosphine chloride, and 3.20g anhydrous potassium fluoride. Stir at 65℃ for 4h, then filter. Remove the solvent at 50℃ under negative pressure (2kPa) for 1.3h to obtain 10.76g dicyclohexylphosphine fluoride. (2) In a 250ml reaction flask, add 166ml tetrahydrofuran, 10.76g dicyclohexylphosphine fluoride, and 5.54g triethylamine. Stir at 35℃ for 3.5h, then remove the solvent at 65℃ under negative pressure (1kPa) for 1.2h to obtain 15.76g component B5. NMR data 1H NMR (500MHz, Chloroform-d) δ3.23–3.08(m,6H),2.80(s,2H),1.71(d,J=2.6Hz,8H),1.59(s,4H),1.58–1.49(m,8H),1.35(s,9H).

[0072] 2. Preparation of fluoroethylene carbonate

[0073] 1 L of tetrahydrofuran, 455.36 g (4.5 mol) of triethylamine, and 0.10 g (0.3 mmol) of catalytic composition B5 were added to a 2 L stainless steel reactor. The reactor was adjusted to 45 °C, and 75.03 g (3.75 mol) of hydrogen fluoride was introduced. After stirring until homogeneous, 459.40 g (3.75 mol) of chloroethylene carbonate was added and the mixture was stirred for 1.3 h. The temperature was maintained at 45 °C during the reaction. After the reaction was completed, residual hydrogen fluoride was removed under negative pressure (2 kPa) and temperature of 30 °C for 15 minutes. The product was quantified by gas chromatography, yielding 379.83 g of fluoroethylene carbonate with a conversion rate of 99.8% and a selectivity of 95.7%.

[0074] Example 6:

[0075] 1. Preparation of component B6

[0076]

[0077] (1) In a 250ml reaction flask, add 100ml ethyl acetate, 14.92g di-p-tolylphosphine chloride, and 4.88g anhydrous potassium fluoride. Stir at 55℃ for 5h, then filter. Remove the solvent under negative pressure (3kPa) and 70℃ for 1.1h to obtain 13.87g di-p-tolylphosphine fluoride. (2) In a 250ml reaction flask, add 171ml dimethyl carbonate, 13.87g di-p-tolylphosphine fluoride, and 7.25g triethylamine. Stir at 45℃ for 2.5h, then remove the solvent under negative pressure (1.5kPa) and 60℃ for 0.8h to obtain 19.86g component B6. NMR data 1 H NMR (500MHz, Chloroform-d) δ7.45–7.39(m,4H),7.25(dq,J=7.5,1.1Hz,4H),3.41(s,6H),2.38(t,J=1.0Hz,6H),1.36(s,9H).

[0078] 2. Preparation of fluoroethylene carbonate

[0079] 1 L of methyl tert-butyl ether, 212.50 g (2.1 mol) of triethylamine, and 0.10 g (0.3 mmol) of catalyst composition B6 were added to a 2 L stainless steel reactor. The reactor was adjusted to 50 °C, and 36.01 g (1.8 mol) of hydrogen fluoride was introduced. After stirring until homogeneous, 183.76 g (1.5 mol) of chloroethylene carbonate was added and the mixture was stirred for 1.0 h. The temperature was maintained at 50 °C during the reaction. After the reaction was completed, residual hydrogen fluoride was removed under negative pressure (8 kPa) and temperature of 40 °C for 25 minutes. The product was quantified by gas chromatography, yielding 152.72 g of fluoroethylene carbonate with a conversion rate of 99.9% and a selectivity of 96.1%.

[0080] Example 7:

[0081] Fluorinated ethylene carbonate was prepared under essentially the same reaction conditions as in Example 1, except that component A (triethylamine) was not added during the reaction. Gas chromatography results showed that the conversion rate of ethylene carbonate was only 78.6%, and the selectivity was 95.2%.

[0082] Comparative Example 1:

[0083] Fluorinated ethylene carbonate was prepared under essentially the same reaction conditions as in Example 1, except that component B1 was not added during the reaction. Gas chromatography results showed that the conversion rate of ethylene carbonate was only 80.7% and the selectivity was 82.3%.

Claims

1. A catalyst having the general structural formula shown in formula (I): ， in, R1 and R2 can be the same or different, and can be independently selected from alkyl or aryl groups. Alkyl groups include straight-chain alkyl, branched alkyl, and cycloalkyl groups, and the number of carbon atoms in the alkyl group is 1-6. The aryl group is phenyl, p-methylphenyl, o-methylphenyl, or m-methylphenyl. R1 and R2 can form a cyclic structure with the P atom, such as a three-membered ring, a four-membered ring, a five-membered ring, or a six-membered ring.

2. The method for preparing the catalyst according to claim 1, characterized in that, The process includes the following steps: (1) adding a reaction solvent, a phosphine chloride compound, and a metal fluoride to a reactor, stirring the reaction, and after the reaction is completed, filtering and removing the solvent under vacuum to obtain a phosphine fluoride compound; (2) adding the phosphine fluoride compound, the reaction solvent, and triethylamine from step (1) to a reactor, stirring the reaction, and after the reaction is completed, removing the solvent under vacuum to obtain the catalyst. The general structural formula of the phosphine chloride compounds is shown in formula (II); Metal fluorides are one or more of lithium fluoride, sodium fluoride, and potassium fluoride.

3. The preparation method according to claim 2, characterized in that, In step (1), the reaction solvent is one or more of acetonitrile, ethyl acetate, tetrahydrofuran, dimethyl carbonate and diethyl carbonate; and / or, in step (1), the reaction temperature is 30-90℃ and the reaction time is 1-8h.

4. The preparation method according to claim 3, characterized in that, In step (1), the reaction temperature is 50-70℃ and the reaction time is 3-5h.

5. The preparation method according to any one of claims 2-4, characterized in that, In step (1), the molar ratio of phosphine chloride compound to metal fluoride is 1:1-1.5; the concentration of phosphine chloride compound in solvent is 0.2-0.8 mol / L.

6. The preparation method according to claim 5, characterized in that, In step (1), the concentration of phosphine chloride compounds in the solvent is 0.4-0.6 mol / L.

7. The preparation method according to claim 2, characterized in that, In step (2), the reaction solvent is one or more of acetonitrile, ethyl acetate, tetrahydrofuran, dimethyl carbonate and diethyl carbonate; and / or, the reaction temperature is 20-70℃ and the reaction time is 1-5h.

8. The preparation method according to claim 7, characterized in that, In step (2), the reaction temperature is 30-50℃ and the reaction time is 2-4h.

9. The preparation method according to any one of claims 7-8, characterized in that, In step (2), the molar ratio of fluorinated phosphine compounds to triethylamine is 1:1-1.3; the concentration of fluorinated phosphine compounds in the solvent is 0.2-0.8 mol / L.

10. The preparation method according to claim 9, characterized in that, In step (2), the concentration of fluorinated phosphine compounds in the solvent is 0.3-0.5 mol / L.

11. A catalyst composition, characterized in that, It contains component A and component B, where A is a nitrogen-containing organic base, and the general structural formula of component B is shown in formula (I): ， R1 and R2 may be the same or different, and are independently selected from alkyl or aryl groups. The alkyl group includes straight-chain alkyl, branched alkyl, and cycloalkyl groups, and the alkyl group has 1-6 carbon atoms. The aryl group is phenyl, p-methylphenyl, o-methylphenyl, or m-methylphenyl. R1 and R2 can form a cyclic structure with the P atom, such as a three-membered ring, a four-membered ring, a five-membered ring, or a six-membered ring.

12. The catalyst composition according to claim 11, characterized in that, Component A contains a nitrogenous organic base, which is one or more of trimethylamine, triethylamine, tripropylamine, diisopropylamine, diethylenetriamine, and pyridine.

13. The catalyst composition according to any one of claims 11 or 12, characterized in that, The molar ratio of A to B in the composition is 1:0.01%-0.1%.

14. Use of the catalyst composition according to any one of claims 11-13 in catalyzing the substitution reaction of chloroethylene carbonate with hydrogen fluoride to prepare fluoroethylene carbonate.

15. The use according to claim 14, characterized in that, The preparation method of fluoroethylene carbonate includes the following steps: adding an organic solvent and a catalytic composition into a reactor and mixing them. After stirring evenly, hydrogen fluoride is introduced, and after stirring evenly again, chloroethylene carbonate is added. The mixture is stirred and reacted. After the reaction is completed, residual hydrogen fluoride in the reaction solution is removed under negative pressure.

16. The use according to claim 15, characterized in that, The concentration of catalyst component B in the reaction system is 0.1 mmol / L-1 mmol / L; and / or, the molar ratio of chloroethylene carbonate, nitrogen-containing organic base and hydrogen fluoride in the system is 1:0.5-2:1-2.

17. The use according to claim 16, characterized in that, The molar ratio of chloroethylene carbonate, nitrogen-containing organic base and hydrogen fluoride in the system is 1:1-1.5:1-1.

2.

18. The use according to claim 15, characterized in that, The reaction temperature in the preparation method of the fluoroethylene carbonate is 0-100℃, and the reaction time is 0.5-5h.

19. The use according to claim 18, characterized in that, The reaction temperature in the preparation method of the fluoroethylene carbonate is 30-60℃, and the reaction time is 0.5-1.5h.

20. The use according to claim 15, characterized in that, The organic solvent is one or more of acetonitrile, ethyl acetate, dimethyl carbonate, diethyl carbonate, and aliphatic ethers.

21. The use according to claim 15, characterized in that, The organic solvent is one of tetrahydrofuran, dipropyl ether, dibutyl ether, and methyl tert-butyl ether.

Images