CN114716403A - Synthetic method of fluoroethylene carbonate - Google Patents
Synthetic method of fluoroethylene carbonate Download PDFInfo
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- CN114716403A CN114716403A CN202210515208.1A CN202210515208A CN114716403A CN 114716403 A CN114716403 A CN 114716403A CN 202210515208 A CN202210515208 A CN 202210515208A CN 114716403 A CN114716403 A CN 114716403A
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- fluoroethylene carbonate
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- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 238000010189 synthetic method Methods 0.000 title claims abstract description 10
- OYOKPDLAMOMTEE-UHFFFAOYSA-N 4-chloro-1,3-dioxolan-2-one Chemical compound ClC1COC(=O)O1 OYOKPDLAMOMTEE-UHFFFAOYSA-N 0.000 claims abstract description 71
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- 238000003682 fluorination reaction Methods 0.000 claims abstract description 37
- 239000007788 liquid Substances 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 30
- 239000012025 fluorinating agent Substances 0.000 claims abstract description 29
- 238000000926 separation method Methods 0.000 claims abstract description 25
- 230000000536 complexating effect Effects 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 66
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 59
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 59
- 239000011698 potassium fluoride Substances 0.000 claims description 47
- 235000003270 potassium fluoride Nutrition 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 31
- 238000010438 heat treatment Methods 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 18
- 230000002194 synthesizing effect Effects 0.000 claims description 18
- VBKNTGMWIPUCRF-UHFFFAOYSA-M potassium;fluoride;hydrofluoride Chemical compound F.[F-].[K+] VBKNTGMWIPUCRF-UHFFFAOYSA-M 0.000 claims description 16
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 14
- 229910052731 fluorine Inorganic materials 0.000 claims description 14
- 239000011737 fluorine Substances 0.000 claims description 14
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 13
- 238000002425 crystallisation Methods 0.000 claims description 13
- 230000008025 crystallization Effects 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 239000000654 additive Substances 0.000 abstract description 3
- 238000005070 sampling Methods 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- YPDSOAPSWYHANB-UHFFFAOYSA-N [N].[F] Chemical compound [N].[F] YPDSOAPSWYHANB-UHFFFAOYSA-N 0.000 description 8
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- HIGQQEOWQNDHJD-UHFFFAOYSA-N 4,4-dichloro-1,3-dioxolan-2-one Chemical compound ClC1(Cl)COC(=O)O1 HIGQQEOWQNDHJD-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- XJHDWSFEGCYSFP-UHFFFAOYSA-N C=C.ClC(Cl)=O Chemical compound C=C.ClC(Cl)=O XJHDWSFEGCYSFP-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/42—Halogen atoms or nitro radicals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a synthetic method of fluoroethylene carbonate, belonging to the technical field of lithium ion battery additives. The synthetic method of fluoroethylene carbonate comprises the following steps: carrying out fluorination reaction on the chloroethylene carbonate material and a complexing fluorinating agent, carrying out solid-liquid separation after the fluorination reaction is finished, and separating fluoroethylene carbonate from liquid obtained by the solid-liquid separation; the sum of the mass fractions of the chloroethylene carbonate and the fluoroethylene carbonate in the chloroethylene carbonate material is more than or equal to 92 percent; the complex fluorinating agent is HF-KF complex and/or HF-KHF2A complex compound. The invention adopts the complexing fluorinating agent to realize the liquid-liquid fluorination synthesis of the fluoroethylene carbonate under the conditions of low temperature and no catalyst, and improves the fluorination efficiency, the reaction yield and the product purity.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery additives, and particularly relates to a synthetic method of fluoroethylene carbonate.
Background
The fluoroethylene carbonate (FEC) is an important solvent or additive in the electrolyte of the lithium ion battery, can improve the charge-discharge cycle characteristic and the current efficiency of the lithium ion battery, and also has the advantages of reducing the impedance of the battery, improving the low-temperature resistance of the battery, and improving the specific capacity and the cycle stability of the battery.
In the prior art, fluoroethylene carbonate is prepared by nucleophilic substitution of chloroethylene carbonate (CEC) mainly by adopting a fluorination reagent, the commonly used fluorination reagent comprises potassium fluoride, hydrogen fluoride and the like, the method needs to be carried out in a proper solvent and a proper catalyst, and otherwise, the problems of high reaction temperature, long reaction time and low conversion rate can occur. In the prior art, such as yao, chu and the like, potassium fluoride is used as a fluorinating reagent, acetonitrile is used as a solvent, the reaction temperature is 75 ℃, the reaction time is 2h, and n (CEC): n (KF) ═ 1:1.3 is the optimum reaction condition (synthesis of fluoroethylene carbonate, fine chemical industry, 2012, 29 (4): 394-397). The potassium fluoride adopted by the technology is in a solid state, and is easy to generate coating in the solid-liquid reaction process with chlorinated ethylene carbonate liquid, the fluorinating agent needs to be excessive, the reaction temperature is high, side reaction is easy to generate, and the reaction process and the cost are difficult to control. In addition, the prior art needs to perform the reaction in an acetonitrile solvent system, and both potassium chloride and the solvent which are the reaction products are difficult to separate from the fluoroethylene carbonate product, so that the solvent in the fluoroethylene carbonate remains.
For another example, the present invention is a chinese patent application with application publication No. CN102060839A, in which CEC and hydrogen fluoride are catalyzed by an organic base catalyst to perform a fluorination reaction at-20 to 250 ℃. The technology adds the fluorinating agent step by step, and compared with chloroethylene carbonate, the fluorinating agent has low local concentration, slow fluorination speed and incomplete fluorination. The organic base catalyst adopted in the prior art also has the problem of difficult removal, and the post-treatment process is complicated and is not beneficial to the purification of fluoroethylene carbonate.
Disclosure of Invention
The invention aims to provide a method for synthesizing fluoroethylene carbonate, which can synthesize fluoroethylene carbonate under the conditions of no solvent and no catalyst, fluorinates chloroethylene carbonate liquid by using a liquid fluorinating agent, and has the advantages of high local concentration of the fluorinating agent, easy reaction and easy separation of products.
The synthetic method of fluoroethylene carbonate adopts the technical scheme that:
a synthetic method of fluoroethylene carbonate comprises the following steps: carrying out fluorination reaction on the chloroethylene carbonate material and a complexing fluorinating agent, carrying out solid-liquid separation after the fluorination reaction is finished, and separating fluoroethylene carbonate from liquid obtained by the solid-liquid separation;
the sum of the mass fractions of the chloroethylene carbonate and the fluoroethylene carbonate in the chloroethylene carbonate material is more than or equal to 92 percent;
the complex fluorinating agent is HF-KF complex and/or HF-KHF2A complex compound.
The invention adopts HF-KF complex and/or HF-KHF2The complex is used as a complexing fluorinating agent to perform fluorination reaction with chloroethylene carbonate, so that the synthesis of fluoroethylene carbonate under the conditions of no solvent and no catalyst can be realized, the separation difficulty of a product and a system is greatly reduced, the chloroethylene carbonate liquid is fluorinated by using the liquid complexing fluorinating agent, the local concentration of the fluorinating agent is high, the reaction is easy to perform, the reaction temperature is low, the occurrence of side reactions such as CEC carbonization and FEC decomposition caused by high temperature is avoided, and the yield of the reaction and the purity of the product are improved; the chloroethylene carbonate material is adopted as a raw material, the raw material source is wide and easy to obtain, the reaction process is green and environment-friendly, and the industrial popularization and application are facilitated.
Preferably, the sum of the mass fractions of the chloroethylene carbonate and the fluoroethylene carbonate in the chloroethylene carbonate material is 92-98%.
Preferably, the ratio of potassium fluoride to hydrogen fluoride in the HF-KF complex is 1: 1-6; the HF-KHF2The ratio of potassium bifluoride to hydrogen fluoride in the complex is 1: 4-5. The complex fluorinating agent in the proportion exists in a liquid state at a lower temperature, which is beneficial to the reaction.
Preferably, in order to promote the reaction and further improve the yield and the product purity of the reaction, the temperature of the fluorination reaction is 50-80 ℃.
Preferably, the mass fraction of the chloroethylene carbonate in the reaction system at the end of the fluorination reaction is less than 0.8%. The condition can avoid side reactions such as high-temperature oxidation and the like of chloroethylene carbonate and fluoroethylene carbonate in the synthesis process, and is favorable for obtaining fluoroethylene carbonate with high purity and high yield.
Preferably, the complex fluorinating agent is prepared by a method comprising the steps of: introducing hydrogen fluoride into potassium fluoride and/or potassium bifluoride at the temperature of 10-20 ℃, continuing introducing hydrogen fluoride when the molar ratio of the hydrogen fluoride to the potassium fluoride and/or the potassium bifluoride reaches 1: 1-3, then heating to 70-80 ℃ under stirring the system for complex reaction, and stopping introducing the hydrogen fluoride when the ratio of the potassium fluoride and/or the potassium bifluoride to the hydrogen fluoride in the reaction product reaches a set value.
Preferably, the HF-KF complex is prepared using a method comprising the steps of: introducing hydrogen fluoride into potassium fluoride at the temperature of 10-20 ℃, continuing introducing the hydrogen fluoride when the molar ratio of the hydrogen fluoride to the potassium fluoride reaches 1:3, then heating the system to 50-80 ℃ under stirring for carrying out a complex reaction, and stopping introducing the hydrogen fluoride when the ratio of the potassium fluoride to the hydrogen fluoride in the reaction product reaches a set value. The method can obtain HF-KF complex with high activity, and is beneficial to the fluorination reaction.
Preferably, in order to save cost and control the obtaining of a complexing fluorinating agent with a proper proportion, the introduction of the hydrogen fluoride is stopped when the molar ratio of the hydrogen fluoride to the potassium fluoride and/or the potassium bifluoride is 4-6: 1.
Preferably, when the complex fluorinating agent is prepared, the rotating speed of the stirring is 10-60 revolutions per minute.
Preferably, the chloroethylene carbonate material is obtained by fluorination reaction of ethylene carbonate in industrial chloroethylene carbonate. Industrial chloroethylene carbonate is prepared by using vinyl carbonate as a raw material and performing chlorination reaction with chlorine gas or other chlorination reagents, and is limited by reaction conditions, the vinyl carbonate cannot completely react and is difficult to separate from the chloroethylene carbonate, so the purity of the industrial chloroethylene carbonate is usually about 80%, for example, the purity of the chloroethylene carbonate is 80-82%. The method adopts the commercially available industrial chloroethylene carbonate to prepare the chloroethylene carbonate material required by the reaction, and has the advantages of wide source and low cost.
Preferably, the mass fraction of the chloroethylene carbonate in the industrial chloroethylene carbonate is more than or equal to 80%.
Preferably, the fluorination reaction of the ethylene carbonate in the industrial chloroethylene carbonate comprises the following steps: the temperature for the fluorination reaction of the industrial chloroethylene carbonate and the fluorine gas is 10-60 ℃, for example, 50-60 ℃.
Preferably, the fluorination reaction with the fluorine gas is carried out under stirring at a rotation speed of 30 to 50 rpm.
Preferably, the fluorine gas is provided by a fluorine-nitrogen mixed gas, namely a mixed gas of fluorine gas and nitrogen gas, and the mass fraction of the fluorine gas in the fluorine-nitrogen mixed gas is 0.1-1%.
Preferably, the molar amount of the fluorine gas is 1.5 times the molar amount of ethylene carbonate in the industrial chloroethylene carbonate.
Preferably, the solid-liquid separation is centrifugal separation; the rotation speed of the centrifugal separation is 800-1500 rpm; the centrifugal separation is carried out under the protection of nitrogen.
Preferably, the complex fluorinating agent is HF-KF complex and HF-KHF2A complex compound; the synthetic method of the fluoroethylene carbonate further comprises the following steps: and carrying out a complex reaction on the solid obtained by the solid-liquid separation and hydrogen fluoride to prepare the complex fluorinating agent. After the system reaction is finished, solid-liquid separation is carried out to obtain potassium fluoride and potassium bifluoride solid, the potassium fluoride and potassium bifluoride solid can be synthesized into the complexing fluorinating agent again by reacting with hydrogen fluoride, the recycling of raw materials is realized, the reaction efficiency of reactants is fully exerted, no solid waste is generated in the reaction process, and the cost is further saved.
And the step of separating the fluoroethylene carbonate from the liquid obtained by the solid-liquid separation comprises the step of cooling and crystallizing the liquid obtained by the solid-liquid separation. The fluoroethylene carbonate synthesized by the method has low impurity content and is easy to remove, and qualified high-purity fluoroethylene carbonate can be obtained through one-time cooling crystallization.
Preferably, the temperature end point of the temperature reduction crystallization is 0-5 ℃.
Preferably, after cooling and crystallization, the crystal is heated in a step manner to be melted, and when the mass fraction of the fluoroethylene carbonate reaches more than 99.95%, a finished product is collected; the step heating is to heat the mixture to 9-10 ℃ and preserve the mixture for 60-120 min, then heat the mixture to 15-18 ℃ and preserve the mixture for 30-120 min, and the heating rates are all 0.1 ℃/min. Low temperature in the early stage can remove low-melting-point impurities in the crystal, and the content of fluoroethylene carbonate in the later stage is gradually increased until the crystal is qualified.
Preferably, sampling and testing are carried out once every 30 minutes in the material melting process, the temperature is raised to 20-23 ℃ after the FEC purity is qualified, and the materials are completely melted into finished products.
Detailed Description
The following provides a supplementary explanation of the technical effects of the present invention with reference to specific embodiments.
The raw materials in the following examples and comparative examples are all conventional commercial products, wherein the mass fraction of the chloroethylene carbonate in the industrial chloroethylene carbonate is 80-85%, the mass fraction of the ethylene carbonate is 5-10%, the mass fraction of the dichloroethylene carbonate is 5-9%, and the mass fraction of the vinylene carbonate is 0.5-1%.
Example 1
The method for synthesizing fluoroethylene carbonate of the embodiment comprises the following steps:
1) adding potassium fluoride into a reaction kettle with a jacket, introducing hydrogen fluoride, and controlling the introduction temperature to be 10-20 ℃. When the molar ratio of the hydrogen fluoride to the potassium fluoride is 1:1, continuously introducing the hydrogen fluoride, starting stirring the system at the rotating speed of 30 revolutions per minute, heating to 80 ℃ while stirring the system for complex reaction, stopping adding the hydrogen fluoride when the molar ratio of the hydrogen fluoride to the potassium fluoride is 6:1, sampling and analyzing, and measuring that the ratio of the potassium fluoride to the hydrogen fluoride in the HF-KF complex is 1: 6.
2) 600g of industrial chloroethylene carbonate (industrial chloroethylene carbonate purity 82%, ethylene carbonate 9%, ethylene dichlorocarbonate 8%, vinylene carbonate 1%) is added into a jacketed reaction kettle, stirring is carried out at the rotating speed of 40 r/min at 50 ℃, then a fluorine-nitrogen mixed gas with the fluorine mass fraction of 0.5% is introduced into the bottom of the reaction kettle to carry out fluorination reaction, and when the molar ratio of the fluorine gas to the ethylene carbonate in the industrial chloroethylene carbonate is 1.5: and 1, stopping introducing the fluorine-nitrogen mixed gas, obtaining a chloroethylene carbonate material after the reaction is finished, and sampling and analyzing to obtain that the total mass fraction of chloroethylene carbonate and fluoroethylene carbonate in the chloroethylene carbonate material is 93.1%.
3) Adding the chloroethylene carbonate material obtained in the step 2) into the KF-HF complex obtained in the step 1), carrying out fluorination reaction at 50-80 ℃, stopping the reaction after reacting for 2 hours, and carrying out sampling analysis on the reaction system to obtain that the content of chloroethylene carbonate in the reaction system is 0.5%.
4) Adding the reaction system obtained in the step 3) into a totally-enclosed centrifuge protected by nitrogen, and carrying out centrifugal separation at a rotating speed of 1500 rpm, wherein the liquid obtained by centrifugal separation is the fluoroethylene carbonate crude product.
5) Adding the fluoroethylene carbonate crude product obtained in the step 4) into a cooling crystallization kettle, cooling to 3 ℃ for crystallization, and then carrying out step heating until the temperature is respectively raised to 9 ℃ and kept for 120min, and the temperature is kept for 60min at 17 ℃, wherein the heating rate is 0.1 ℃/min. Sampling and testing once every 30 minutes, heating to 21 ℃ after the materials are qualified, and completely dissolving the materials. The early low temperature removes mainly some low melting impurities. And the content of the fluoroethylene carbonate is gradually increased in the later period until the purity is 99.95 percent. The results showed that 180 g of fluoroethylene carbonate with a purity of 90.2% and 245 g of fluoroethylene carbonate with a purity of 99.97% and a yield of 82.99% were obtained.
Example 2
The method for synthesizing fluoroethylene carbonate of the embodiment comprises the following steps:
1) adding potassium fluoride into a reaction kettle with a jacket, introducing hydrogen fluoride, and controlling the introduction temperature to be 10-20 ℃. When the molar ratio of the hydrogen fluoride to the potassium fluoride is 1:3, continuously introducing the hydrogen fluoride, starting stirring the system at the rotating speed of 20 revolutions per minute, and heating to 50 ℃ to perform a complex reaction while stirring the system. When the molar ratio of hydrogen fluoride to potassium fluoride is 6:1, stopping adding the hydrogen fluoride, sampling and analyzing, and determining that the ratio of the potassium fluoride to the hydrogen fluoride in the HF-KF complex is 5.5: 1.
2) Adding 500g of industrial chloroethylene carbonate (the purity of industrial chloroethylene carbonate is 82%, ethylene carbonate is 9%, dichloroethylene carbonate is 8%, vinylene carbonate is 1%) into a jacketed reaction kettle, stirring at the rotating speed of 30 r/min at 10 ℃, then introducing a fluorine-nitrogen mixed gas with the fluorine mass fraction of 0.5% into the bottom of the reaction kettle to perform fluorination reaction, and when the molar ratio of the fluorine gas to the ethylene carbonate in the industrial chloroethylene carbonate is 1.1: and 1, stopping introducing the fluorine-nitrogen mixed gas, obtaining a chloroethylene carbonate material after the reaction is finished, and sampling and analyzing to obtain that the total mass fraction of chloroethylene carbonate and fluoroethylene carbonate in the chloroethylene carbonate material is 94.5%.
3) Adding the chloroethylene carbonate material obtained in the step 2) into the KF-HF complex obtained in the step 1), carrying out fluorination reaction at 55 ℃, stopping the reaction for 2 hours, and carrying out sampling analysis on the reaction system to determine that the content of chloroethylene carbonate in the reaction system is 0.6%.
4) Adding the reaction system obtained in the step 3) into a fully-closed centrifuge protected by nitrogen, and carrying out centrifugal separation at the rotating speed of 800 rpm, wherein the liquid obtained by centrifugal separation is the fluoroethylene carbonate crude product.
5) Adding the fluoroethylene carbonate crude product obtained in the step 4) into a cooling crystallization kettle, cooling to 5 ℃ for crystallization, heating to 10 ℃ at the speed of 0.1 ℃/min, preserving heat for 60min, heating to 15 ℃ at the speed of 0.1 ℃/min, preserving heat for 60min, heating to 20 ℃ at the speed of 0.1 ℃/min, sampling and analyzing once every 30 minutes in the step heating and material dissolving process, collecting a finished product when the mass fraction of fluoroethylene carbonate reaches more than 99.95%, wherein the result shows that 256g of fluoroethylene carbonate is obtained, the purity is 99.96%, and in addition, 100g of unqualified fluoroethylene carbonate is collected in the material dissolving process, the purity is 90%, and the total yield is 84.58%.
Example 3
The method for synthesizing fluoroethylene carbonate of the embodiment comprises the following steps:
1) adding potassium fluoride into a reaction kettle with a jacket, introducing hydrogen fluoride, and controlling the introduction temperature to be 10-20 ℃. When the molar ratio of the hydrogen fluoride to the potassium fluoride is 1:3, continuously introducing the hydrogen fluoride, starting stirring the system at the rotating speed of 10 revolutions per minute, and heating to 60 ℃ to perform a complex reaction while stirring the system. When the molar ratio of hydrogen fluoride to potassium fluoride is 5:1, stopping adding the hydrogen fluoride, sampling and analyzing, and determining that the ratio of the potassium fluoride to the hydrogen fluoride in the HF-KF complex is 4.9: 1.
2) Adding 800g of industrial chloroethylene carbonate (industrial chloroethylene carbonate purity is 82%, ethylene carbonate is 9%, dichloroethylene carbonate is 8%, vinylene carbonate is 1%) into a jacketed reaction kettle, stirring at the rotating speed of 50 rpm at 60 ℃, then introducing a fluorine-nitrogen mixed gas with the fluorine mass fraction of 0.2% into the bottom of the reaction kettle to perform fluorination reaction, and when the molar ratio of the fluorine gas to the ethylene carbonate in the industrial chloroethylene carbonate is 2: and 1, stopping introducing the fluorine-nitrogen mixed gas, obtaining a chloroethylene carbonate material after the reaction is finished, and sampling and analyzing to obtain that the total mass fraction of chloroethylene carbonate and fluoroethylene carbonate in the chloroethylene carbonate material is 93%.
3) Adding the chloroethylene carbonate material obtained in the step 2) into the KF-4.5HF complex obtained in the step 1), carrying out fluorination reaction at 75 ℃, stopping the reaction after reacting for 2 hours, and carrying out sampling analysis on the reaction system to determine that the content of fluoroethylene carbonate in the reaction system is 93% and the content of chloroethylene carbonate is 0.5%.
4) Adding the reaction system obtained in the step 3) into a fully-closed centrifuge protected by nitrogen, and carrying out centrifugal separation at the rotating speed of 1200 rpm, wherein the liquid obtained by centrifugal separation is the fluoroethylene carbonate crude product.
5) Adding the fluoroethylene carbonate crude product obtained in the step 4) into a cooling crystallization kettle, cooling to 0 ℃ for crystallization, heating to 10 ℃ at the speed of 0.2 ℃/min, keeping the temperature for 120min, heating to 18 ℃ at the speed of 0.2 ℃/min, keeping the temperature for 120min, sampling and analyzing once every 30 minutes in the step heating and material dissolving process, collecting a finished product when the mass fraction of fluoroethylene carbonate reaches more than 99.95%, and obtaining 373g of fluoroethylene carbonate with the purity of 99.96%, otherwise, collecting 190g of unqualified fluoroethylene carbonate with the purity of 89.8% and the total yield of 83.05%.
Example 4
The method for synthesizing fluoroethylene carbonate of the present example is different from example 1 only in that: step 1) adding potassium bifluoride into a reaction kettle with a jacket, introducing hydrogen fluoride, and controlling the introduction temperature to be 30 ℃. When the molar ratio of the hydrogen fluoride to the potassium bifluoride is 2: 1, continuously introducing hydrogen fluoride, starting stirring the system at the rotating speed of 10 revolutions per minute, and heating to 60 ℃ while stirring the system to perform a complex reaction. When the molar ratio of the hydrogen fluoride to the potassium bifluoride is 4:1 hour, stopping adding hydrogen fluoride, sampling, analyzing, and measuring HF-KHF2The ratio of potassium bifluoride to hydrogen fluoride in the complex is 4: 1. Then HF-KHF is added2The complex is used as a complexing fluorinating agent for subsequent fluorination reaction, and the result shows that 428g (calculated in percent) of fluoroethylene carbonate is obtained, and the yield is 87.35%.
Example 5
The method for synthesizing fluoroethylene carbonate of the present example is different from example 1 only in that: step 1) adding the solid obtained by centrifugal separation in the example 1 into a reaction kettle with a jacket, introducing hydrogen fluoride, and controlling the introduction temperature to be 10-20 ℃. When the introduction amount of the hydrogen fluoride is 2mol, continuously introducing the hydrogen fluoride, starting stirring the system at the rotating speed of 10 revolutions per minute, and heating to 60 ℃ to perform a complex reaction while stirring the system. When the introduction amount of the hydrogen fluoride is 6mol, stopping adding the hydrogen fluoride, sampling and analyzing, wherein the ratio of the potassium fluoride to the hydrogen fluoride in the HF-KF complex is 1:6, and the HF-KHF2The ratio of potassium bifluoride to hydrogen fluoride in the complex is 1: 5. Then the obtained product is used as a complex fluorinating agent to carry out subsequent fluorination reaction, and the result shows that 430g (calculated in percent) of fluoroethylene carbonate is obtained,the yield thereof was found to be 87.76%.
Comparative example 1
The method for synthesizing fluoroethylene carbonate of the present comparative example, which uses potassium fluoride as a fluorinating agent, differs from example 1 only in that: mixing the chloroethylene carbonate material obtained in the step 2) of the example 1 with 302g of potassium fluoride (the potassium fluoride is excessive by 30%), adding a certain amount of solvent, heating to 110 ℃ for fluorination reaction, and after reacting for 2 hours, carrying out subsequent centrifugation and cooling crystallization steps on the reaction system, wherein the result shows that 300g of fluoroethylene carbonate (calculated in percent) is obtained, and the yield is 70.5%.
Comparative example 2
The method for synthesizing fluoroethylene carbonate of the present comparative example, which uses hydrogen fluoride as a fluorinating agent, differs from example 1 only in that: 105g of hydrogen fluoride gas (excessive by 30%) is introduced into the chloroethylene carbonate material obtained in the step 2) of the example 1 at 100 ℃, after 2 hours of fluorination reaction, the reaction system is subjected to subsequent steps of centrifugation and cooling crystallization, and the result shows that 85g (calculated in percent) of fluoroethylene carbonate is obtained, and the yield is 20%.
Claims (11)
1. A synthetic method of fluoroethylene carbonate is characterized in that: the method comprises the following steps: carrying out fluorination reaction on the chloroethylene carbonate material and a complexing fluorinating agent, carrying out solid-liquid separation after the fluorination reaction is finished, and separating fluoroethylene carbonate from liquid obtained by the solid-liquid separation;
the sum of the mass fractions of the chloroethylene carbonate and the fluoroethylene carbonate in the chloroethylene carbonate material is more than or equal to 92 percent;
the complex fluorinating agent is HF-KF complex and/or HF-KHF2A complex compound.
2. The method for synthesizing fluoroethylene carbonate according to claim 1, wherein: the proportion of potassium fluoride and hydrogen fluoride in the HF-KF complex is 1: 1-6; the HF-KHF2The ratio of potassium bifluoride to hydrogen fluoride in the complex is 1: 4-5.
3. The method for synthesizing fluoroethylene carbonate according to claim 1 or 2, wherein: the temperature of the fluorination reaction is 50-80 ℃.
4. The method for synthesizing fluoroethylene carbonate according to claim 1, wherein: the mass fraction of the chloroethylene carbonate in the reaction system at the end of the fluorination reaction is less than 0.8%.
5. The method for synthesizing fluoroethylene carbonate according to claim 1 or 2, wherein: the complex fluorinating agent is prepared by adopting a method comprising the following steps: introducing hydrogen fluoride into potassium fluoride and/or potassium bifluoride at the temperature of 10-20 ℃, continuing introducing hydrogen fluoride when the molar ratio of the hydrogen fluoride to the potassium fluoride and/or the potassium bifluoride reaches 1: 1-3, then heating to 70-80 ℃ under stirring the system for complex reaction, and stopping introducing the hydrogen fluoride when the ratio of the potassium fluoride and/or the potassium bifluoride to the hydrogen fluoride in the reaction product reaches a set value.
6. The method for synthesizing fluoroethylene carbonate according to claim 1, wherein: the chloroethylene carbonate material is obtained by carrying out fluorination reaction on ethylene carbonate in industrial chloroethylene carbonate; the mass fraction of the chloroethylene carbonate in the industrial chloroethylene carbonate is more than or equal to 80 percent.
7. The method for synthesizing fluoroethylene carbonate according to claim 6, wherein: the fluorination reaction of the ethylene carbonate in the industrial chloroethylene carbonate comprises the following steps: the industrial chloroethylene carbonate and fluorine gas are subjected to a fluorination reaction, and the temperature of the fluorination reaction with the fluorine gas is 10-60 ℃.
8. The method for synthesizing fluoroethylene carbonate according to claim 1, wherein: the complex fluorinating agent is HF-KF complex and HF-KHF2A complex compound; the synthetic method of the fluoroethylene carbonate further comprises the following steps: separating the solid from the liquidAnd carrying out a complex reaction on the obtained solid and hydrogen fluoride to prepare the complex fluorinating agent.
9. The method for synthesizing fluoroethylene carbonate according to claim 1, wherein: and the step of separating the fluoroethylene carbonate from the liquid obtained by the solid-liquid separation comprises the step of cooling and crystallizing the liquid obtained by the solid-liquid separation.
10. The method for synthesizing fluoroethylene carbonate according to claim 9, wherein: and the temperature end point of the cooling crystallization is 0-5 ℃.
11. The method for synthesizing fluoroethylene carbonate according to claim 9, wherein: after cooling and crystallization, carrying out stepped heating on the crystal to carry out material melting, and collecting a finished product when the mass fraction of the fluoroethylene carbonate reaches more than 99.95%; the step heating is to heat the mixture to 9-10 ℃ and preserve the mixture for 60-120 min, then heat the mixture to 15-18 ℃ and preserve the mixture for 30-120 min, and the heating rates are all 0.1 ℃/min.
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