CN113896705A - Synthetic method for co-production of 1-fluoro-2-chloroethylene carbonate and 1, 2-difluoroethylene carbonate - Google Patents
Synthetic method for co-production of 1-fluoro-2-chloroethylene carbonate and 1, 2-difluoroethylene carbonate Download PDFInfo
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- CN113896705A CN113896705A CN202111321314.8A CN202111321314A CN113896705A CN 113896705 A CN113896705 A CN 113896705A CN 202111321314 A CN202111321314 A CN 202111321314A CN 113896705 A CN113896705 A CN 113896705A
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- carbonate
- fluoro
- chloroethylene
- dichloroethylene
- difluoroethylene
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- RCUYBENHBFYGDP-UHFFFAOYSA-N 4-chloro-5-fluoro-1,3-dioxolan-2-one Chemical compound FC1OC(=O)OC1Cl RCUYBENHBFYGDP-UHFFFAOYSA-N 0.000 title claims abstract description 39
- DSMUTQTWFHVVGQ-UHFFFAOYSA-N 4,5-difluoro-1,3-dioxolan-2-one Chemical compound FC1OC(=O)OC1F DSMUTQTWFHVVGQ-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000010189 synthetic method Methods 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- BETICXVUVYXEJX-UHFFFAOYSA-N 4,5-Dichloro-1,3-dioxolan-2-one Chemical compound ClC1OC(=O)OC1Cl BETICXVUVYXEJX-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 39
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 238000003682 fluorination reaction Methods 0.000 claims abstract description 19
- 239000000047 product Substances 0.000 claims abstract description 19
- 238000006467 substitution reaction Methods 0.000 claims abstract description 13
- 239000006227 byproduct Substances 0.000 claims abstract description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000005292 vacuum distillation Methods 0.000 claims description 10
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 claims description 8
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 4
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 4
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 4
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 4
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 4
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims 3
- HIGQQEOWQNDHJD-UHFFFAOYSA-N 4,4-dichloro-1,3-dioxolan-2-one Chemical compound ClC1(Cl)COC(=O)O1 HIGQQEOWQNDHJD-UHFFFAOYSA-N 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 239000007795 chemical reaction product Substances 0.000 abstract description 4
- 238000001308 synthesis method Methods 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical class O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 abstract description 3
- 238000004821 distillation Methods 0.000 description 15
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 8
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 239000002920 hazardous waste Substances 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000003828 vacuum filtration Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- -1 lithium carbonate compound Chemical class 0.000 description 3
- 239000011698 potassium fluoride Substances 0.000 description 3
- 235000003270 potassium fluoride Nutrition 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- PMGNOQUKCGLETL-UHFFFAOYSA-N carbonic acid 1,2-difluoroethene Chemical compound C(O)(O)=O.FC=CF PMGNOQUKCGLETL-UHFFFAOYSA-N 0.000 description 2
- ZNNZFUYGJVHLGX-UHFFFAOYSA-N carbonic acid;fluoroethyne Chemical compound FC#C.OC(O)=O ZNNZFUYGJVHLGX-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- OYOKPDLAMOMTEE-UHFFFAOYSA-N 4-chloro-1,3-dioxolan-2-one Chemical compound ClC1COC(=O)O1 OYOKPDLAMOMTEE-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application discloses a synthetic method for co-producing 1-fluoro-2-chloroethylene carbonate and 1, 2-difluoroethylene carbonate. The synthesis method comprises the following steps: mixing 1, 2-dichloroethylene carbonate and fluoride, carrying out fluorination reaction at the fluorination reaction temperature under normal pressure, and filtering to remove chloride as a reaction byproduct after the reaction is finished; 1, 2-dichloroethylene carbonate, 1-fluoro-2-chloroethylene carbonate and 1, 2-difluoroethylene carbonate are separated by three-tower rectification, and the 1, 2-dichloroethylene carbonate is recycled to carry out fluoro-substitution reaction to obtain 1-fluoro-2-chloroethylene carbonate and 1, 2-difluoroethylene carbonate products. 1, 2-dichloroethylene carbonate is the heavy component in the vinylene carbonate synthesis process, and accounts for about 9-15% of chlorinated reaction products, and the method recycles dichloroethylene carbonate byproducts, coproduces 1-fluoro-2-chlorinated ethylene carbonate, and improves the production yield.
Description
Technical Field
The invention relates to the technical field of production methods of fluoroethylene carbonate, in particular to a synthetic method for co-producing 1-fluoro-2-chloroethylene carbonate and 1, 2-difluoroethylene carbonate.
Background
The 1-fluoro-2-chloroethylene carbonate is a tower bottom high boiling point component in the vinylene carbonate VC production process, and if deep processing and utilization cannot be carried out, hazardous waste is formed. Fluoroethylene carbonate is an important additive material of lithium battery electrolyte, and the material can form a compact and stable organic film on the surface of a battery. The organic film generates polyalkyl lithium carbonate compound under the conditions of not losing conductivity and not increasing internal resistance of the battery, the compound can effectively inhibit solvent molecules and solvated lithium ions from being inserted into graphite, decomposition of electrolyte is reduced, stability of a graphite cathode is improved, and further charge and discharge performance of the lithium battery is improved, and high-purity fluoroethylene carbonate is required in the lithium battery industry.
The conventional production process of fluoroethylene carbonate has various processes: one is that fluorine gas reacts with ethylene carbonate directly, because the preparation difficulty of fluorine gas is great, the reaction activity is higher, the reaction is violent, the control difficulty is greater, the resulting product is more complicated (there are monofluoro thing, many fluoro things, etc., even ethylene carbonate decomposes into carbon tetrafluoride directly), the yield of reaction is lower, must achieve the fluoro ethylene carbonate of stable high purity, the cost is higher and the pollution is greater; in addition, the reaction of chloroethylene carbonate and potassium fluoride needs to strictly control the moisture content, the potassium fluoride needs to be correspondingly spray-dried, and meanwhile, the potassium fluoride needs to be dissolved in anhydrous polar solvents such as acetonitrile, sulfolane and the like, so that the problems of high control requirement, low yield and the like are solved.
In addition, the prior method for preparing fluoroethylene carbonate only adopts a single method, lacks a co-production mode, and cannot recycle reactants, so that the yield is low.
Disclosure of Invention
The invention aims to provide a synthetic method for coproducing 1-fluoro-2-chloroethylene carbonate and 1, 2-difluoroethylene carbonate, which is used for solving the technical problems that the existing synthetic method for coproducing 1-fluoro-2-chloroethylene carbonate and 1, 2-difluoroethylene carbonate is complex in process and low in production yield, particularly, the existing method for preparing fluoroethylene carbonate singly is adopted, a coproduction production mode is lacked, reactants cannot be recycled, and the yield is low.
In order to achieve the above object, an embodiment of the present invention provides a synthetic method for co-producing 1-fluoro-2-chloroethylene carbonate and 1, 2-difluoroethylene carbonate, including the steps of: mixing 1, 2-dichloroethylene carbonate and fluoride, carrying out fluorination reaction at the fluorination reaction temperature under normal pressure, and filtering to remove chloride as a reaction byproduct after the reaction is finished; 1, 2-dichloroethylene carbonate, 1-fluoro-2-chloroethylene carbonate and 1, 2-difluoroethylene carbonate are separated by three-tower rectification, and the 1, 2-dichloroethylene carbonate is recycled to carry out fluoro-substitution reaction to obtain 1-fluoro-2-chloroethylene carbonate and 1, 2-difluoroethylene carbonate products.
Further, the 1, 2-dichloroethylene carbonate is obtained by vacuum distillation of the bottom heavy component in the vinylene carbonate process.
Further, the pressure of the tower top for carrying out reduced pressure distillation on the heavy components at the tower bottom in the vinylene carbonate process is 1-2.5 KPa; the operation of the vacuum distillation column is a batch operation.
Further, the fraction at the temperature of 150-180 ℃ of the vacuum distillation tower for collecting the bottom heavy components in the vinylene carbonate process is the 1, 2-dichloroethylene carbonate.
Further, the purity of the 1, 2-dichloroethylene carbonate obtained after the vacuum distillation of the bottom heavy components in the vinylene carbonate process is higher than 95%.
Further, the mixing ratio of the 1, 2-dichloroethylene carbonate and the fluoride is 1 (1.05-1.2).
Further, the fluoride used is one or more of calcium fluoride, magnesium fluoride, zinc fluoride and aluminum fluoride.
Further, the fluorination reaction temperature is 100-180 ℃.
Further, negative pressure rectification is used in the three-tower rectification process of the fluorinated product; the pressure of each rectifying tower is 0.5-2 KPa.
Further, in the three-tower rectification process of the fluorinated product, the operation of the rectification tower is batch operation or continuous operation.
The invention has the beneficial effects that the synthesis method for coproducing 1-fluoro-2-chloroethylene carbonate and 1, 2-difluoroethylene carbonate is provided, 1, 2-dichloroethylene carbonate is heavy components in the synthesis process of vinylene carbonate, accounts for about 9-15% of chlorinated reaction products, and appears in the form of heavy component hazardous waste at the bottom of a tower after the vinylene carbonate is distilled and separated, and the conventional vinylene carbonate enterprises treat the heavy components as hazardous waste, so that the yield of the device is reduced, and the pressure for treating the environmentally-friendly hazardous waste is increased. The application of the method for recycling the dichloroethylene carbonate byproduct is an important way for improving the comprehensive competitiveness of the vinylene carbonate device. The 1, 2-difluoro ethylene carbonate is one of the important additives of the lithium battery, and the qualified 1-fluoro-2-chloro ethylene carbonate can be further processed into fluoro vinylene carbonate products and can also be used as the additive of the lithium battery. And the synthetic method for coproducing the 1-fluoro-2-chloroethylene carbonate and the 1, 2-difluoroethylene carbonate has the advantages of simple reaction conditions, simple operation and high production yield.
Detailed Description
The technical solutions in the embodiments of the present application are clearly and completely described below. It is to be understood that the embodiments described are only a few embodiments of the present application and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The following disclosure provides many different embodiments or examples for implementing different features of the application. In order to simplify the disclosure of the present application, specific example components and arrangements are described below. Of course, they are merely examples and are not intended to limit the present application. In addition, examples of various specific processes and materials are provided herein, but one of ordinary skill in the art may recognize applications of other processes and/or use of other materials.
Specifically, the embodiment of the present application provides a synthetic method for co-producing 1-fluoro-2-chloroethylene carbonate and 1, 2-difluoroethylene carbonate, including the steps of: carrying out reduced pressure distillation on the heavy components at the bottom of the vinylene carbonate process, collecting 1, 2-dichloroethylene carbonate components within a specific temperature range, mixing the 1, 2-dichloroethylene carbonate with fluoride, carrying out a fluorination reaction at a fluorination reaction temperature under normal pressure, and filtering to remove the chloride as a reaction byproduct after the reaction is finished; 1, 2-dichloroethylene carbonate, 1-fluoro-2-chloroethylene carbonate and 1, 2-difluoroethylene carbonate are separated by three-tower rectification, and the 1, 2-dichloroethylene carbonate is recycled to carry out fluoro-substitution reaction to obtain 1-fluoro-2-chloroethylene carbonate and 1, 2-difluoroethylene carbonate products.
In the embodiment of the application, the 1, 2-dichloroethylene carbonate is obtained by carrying out reduced pressure distillation on the bottom heavy component in the vinylene carbonate process, and the pressure of the top of the reduced pressure distillation is 1-2.5 KPa; the operation of the vacuum distillation column is a batch operation.
In the embodiment of the application, the 150-180 ℃ fraction of the reduced pressure distillation tower for collecting the bottom heavy component in the vinylene carbonate process is the 1, 2-dichloroethylene carbonate.
In the examples of the application, the purity of the 1, 2-dichloroethylene carbonate obtained after the reduced pressure distillation of the bottom heavy components in the vinylene carbonate process is higher than 95%. Wherein the purity of the 1, 2-dichloroethylene carbonate obtained after distillation under reduced pressure of the bottom components in the vinylene carbonate process is preferably higher than 99%.
Wherein, 1, 2-dichloroethylene carbonate is the heavy component in the vinylene carbonate synthesis process, and accounts for about 9-15% of the chlorinated reaction product, the method recycles the dichloroethylene carbonate byproduct, coproduces 1-fluoro-2-chloroethylene carbonate, and improves the production yield.
In the examples of the present application, the mixing ratio of the 1, 2-dichloroethylene carbonate and the fluoride is 1 (1.05-1.2). Preferably, the mixing ratio of the 1, 2-dichloroethylene carbonate to the fluoride is 1: 1.
In the embodiment of the application, the fluoride used is one or more of calcium fluoride, magnesium fluoride, zinc fluoride and aluminum fluoride.
In the embodiment of the application, the fluorination reaction temperature is 100-180 ℃.
In the embodiment of the application, negative pressure rectification is used in the three-tower rectification process of the fluorinated product; the pressure of each rectifying tower is 0.5-2 KPa.
In the embodiment of the application, in the three-tower rectification process of the fluorinated product, the operation of the rectification tower is batch operation or continuous operation.
Specifically, the following examples are given to specifically explain the synthesis method for co-producing 1-fluoro-2-chloroethylene carbonate and 1, 2-difluoroethylene carbonate.
Example 1
Weighing 500g of the bottom heavy component of the vinylene carbonate rough distillation tower, carrying out reduced pressure distillation, keeping the vacuum degree at-0.099 MPa, collecting the 1, 2-dichloroethylene carbonate component within the range of 105-plus 110 ℃, transferring the 1, 2-dichloroethylene carbonate component into a fluorination reaction kettle, adding 125g of magnesium fluoride, starting stirring, carrying out nitrogen substitution until the oxygen content is less than 0.3%, heating to 120 ℃ for carrying out fluorination reaction, and carrying out vacuum filtration to remove the magnesium chloride as a reaction byproduct after 15 hours of reaction. 1, 2-dichloroethylene carbonate, 1-fluoro-2-chloroethylene carbonate and 1, 2-difluoroethylene carbonate are separated by three-tower rectification, and the 1, 2-dichloroethylene carbonate is recycled to carry out fluoro-substitution reaction to obtain 1-fluoro-2-chloroethylene carbonate and 1, 2-difluoroethylene carbonate products.
Example 2
Weighing 500g of the bottom component of the vinylene carbonate rough distillation tower, carrying out reduced pressure distillation, keeping the vacuum degree at-0.099 MPa, collecting the 1, 2-dichloroethylene carbonate component within the range of 105-plus 110 ℃, transferring the 1, 2-dichloroethylene carbonate component into a fluorination reaction kettle, adding 145g of calcium fluoride, starting stirring, carrying out nitrogen substitution until the oxygen content is less than 0.3%, heating to 140 ℃ for carrying out fluorination reaction, and carrying out vacuum filtration to remove magnesium chloride as a reaction byproduct after 15 hours of reaction. 1, 2-dichloroethylene carbonate, 1-fluoro-2-chloroethylene carbonate and 1, 2-difluoroethylene carbonate are separated by three-tower rectification, and the 1, 2-dichloroethylene carbonate is recycled to carry out fluoro-substitution reaction to obtain 1-fluoro-2-chloroethylene carbonate and 1, 2-difluoroethylene carbonate products.
Example 3
Weighing 500g of the bottom heavy component of the vinylene carbonate rough distillation tower, carrying out reduced pressure distillation, keeping the vacuum degree at-0.099 MPa, collecting the 1, 2-dichloroethylene carbonate component within the range of 105-plus 110 ℃, transferring the 1, 2-dichloroethylene carbonate component into a fluorination reaction kettle, adding 100g of zinc fluoride, starting stirring, carrying out nitrogen substitution until the oxygen content is less than 0.3%, heating to 130 ℃ for fluorination reaction, and carrying out vacuum filtration to remove the magnesium chloride as a reaction byproduct after 15 hours of reaction. 1, 2-dichloroethylene carbonate, 1-fluoro-2-chloroethylene carbonate and 1, 2-difluoroethylene carbonate are separated by three-tower rectification, and the 1, 2-dichloroethylene carbonate is recycled to carry out fluoro-substitution reaction to obtain 1-fluoro-2-chloroethylene carbonate and 1, 2-difluoroethylene carbonate products.
Example 4
Weighing 500g of the bottom heavy component of the vinylene carbonate rough distillation tower, carrying out reduced pressure distillation, keeping the vacuum degree at-0.099 MPa, collecting the 1, 2-dichloroethylene carbonate component within the range of 105-plus 110 ℃, transferring the 1, 2-dichloroethylene carbonate component into a fluorination reaction kettle, adding 80g of aluminum trifluoride, starting stirring, carrying out nitrogen substitution until the oxygen content is less than 0.3%, heating to 130 ℃ for fluorination reaction, and carrying out vacuum filtration to remove the magnesium chloride as a reaction byproduct after 15 hours of reaction. 1, 2-dichloroethylene carbonate, 1-fluoro-2-chloroethylene carbonate and 1, 2-difluoroethylene carbonate are separated by three-tower rectification, and the 1, 2-dichloroethylene carbonate is recycled to carry out fluoro-substitution reaction to obtain 1-fluoro-2-chloroethylene carbonate and 1, 2-difluoroethylene carbonate products.
The invention has the beneficial effects that the synthesis method for coproducing 1-fluoro-2-chloroethylene carbonate and 1, 2-difluoroethylene carbonate is provided, 1, 2-dichloroethylene carbonate is heavy components in the synthesis process of vinylene carbonate, accounts for about 9-15% of chlorinated reaction products, and appears in the form of heavy component hazardous waste at the bottom of a tower after the vinylene carbonate is distilled and separated, and the conventional vinylene carbonate enterprises treat the heavy components as hazardous waste, so that the yield of the device is reduced, and the pressure for treating the environmentally-friendly hazardous waste is increased. The application of the method for recycling the dichloroethylene carbonate byproduct is an important way for improving the comprehensive competitiveness of the vinylene carbonate device. The 1, 2-difluoro ethylene carbonate is one of the important additives of the lithium battery, and the qualified 1-fluoro-2-chloro ethylene carbonate can be further processed into fluoro vinylene carbonate products and can also be used as the additive of the lithium battery. And the synthetic method for coproducing the 1-fluoro-2-chloroethylene carbonate and the 1, 2-difluoroethylene carbonate has the advantages of simple reaction conditions, simple operation and high production yield.
The above embodiments of the present application are described in detail, and specific examples are applied in the present application to explain the principles and implementations of the present application, and the description of the above embodiments is only used to help understand the technical solutions and core ideas of the present application; those of ordinary skill in the art will understand that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; such modifications or substitutions do not depart from the spirit and scope of the present disclosure as defined by the appended claims.
Claims (10)
1. A synthetic method for co-producing 1-fluoro-2-chloroethylene carbonate and 1, 2-difluoroethylene carbonate is characterized by comprising the following steps: mixing 1, 2-dichloroethylene carbonate and fluoride, carrying out fluorination reaction at the fluorination reaction temperature under normal pressure, and filtering to remove chloride as a reaction byproduct after the reaction is finished; 1, 2-dichloroethylene carbonate, 1-fluoro-2-chloroethylene carbonate and 1, 2-difluoroethylene carbonate are separated by three-tower rectification, and the 1, 2-dichloroethylene carbonate is recycled to carry out fluoro-substitution reaction to obtain 1-fluoro-2-chloroethylene carbonate and 1, 2-difluoroethylene carbonate products.
2. The synthetic method for coproducing 1-fluoro-2-chloroethylene carbonate and 1, 2-difluoroethylene carbonate according to claim 1, characterized in that the 1, 2-dichloroethylene carbonate is obtained by vacuum distillation of the bottom heavy components in the vinylene carbonate process.
3. The synthetic method for coproducing 1-fluoro-2-chloroethylene carbonate and 1, 2-difluoroethylene carbonate according to claim 2, wherein the pressure at the top of the vacuum distillation of the heavy components at the bottom of the vinylene carbonate process is 1-2.5 KPa; the operation of the vacuum distillation column is a batch operation.
4. The method as claimed in claim 2, wherein the 150-180 ℃ fraction of the vacuum distillation tower for collecting the bottom heavy component in the vinylene carbonate process is the 1, 2-dichloroethylene carbonate.
5. The method for synthesizing 1-fluoro-2-chloroethylene carbonate and 1, 2-difluoroethylene carbonate as co-production of claim 1, characterized in that the purity of the 1, 2-dichloroethylene carbonate obtained after vacuum distillation of the bottom heavy components in the vinylene carbonate process is higher than 95%.
6. The synthetic method for co-producing 1-fluoro-2-chloroethylene carbonate and 1, 2-difluoroethylene carbonate according to claim 1, wherein the mixing ratio of the 1, 2-dichloroethylene carbonate and the fluoride is 1 (1.05-1.2).
7. The method for synthesizing 1-fluoro-2-chloroethylene carbonate and 1, 2-difluoroethylene carbonate as co-products according to claim 1, wherein the fluoride used is one or more of calcium fluoride, magnesium fluoride, zinc fluoride and aluminum fluoride.
8. The method as claimed in claim 1, wherein the fluorination reaction temperature is 100-180 ℃.
9. The synthetic method for coproducing 1-fluoro-2-chloroethylene carbonate and 1, 2-difluoroethylene carbonate as claimed in claim 1, wherein negative pressure rectification is used in the three-tower rectification process of the fluorinated product; the pressure of each rectifying tower is 0.5-2 KPa.
10. The method for synthesizing 1-fluoro-2-chloroethylene carbonate and 1, 2-difluoroethylene carbonate as co-products according to claim 1, wherein the operation of the rectification column is a batch operation or a continuous operation in the three-column rectification process of the fluorinated products.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20060067460A (en) * | 2004-12-15 | 2006-06-20 | 주식회사 엘지화학 | Preparation method of fluoroethylene carbonate |
| CN101205226A (en) * | 2006-12-22 | 2008-06-25 | 比亚迪股份有限公司 | Method for preparing monochlorin ethylene carbonate ester and vinylene carbonate |
| CN102766130A (en) * | 2012-07-18 | 2012-11-07 | 太仓华一化工科技有限公司 | Preparation method of difluoroethylene carbonate |
| CN102875521A (en) * | 2012-09-27 | 2013-01-16 | 中国海洋石油总公司 | Method for preparing fluoro-carbonate ester by means of phase-transfer catalysis |
| CN104529992A (en) * | 2014-11-26 | 2015-04-22 | 苏州华一新能源科技有限公司 | Preparation method for 4,5-difluoro-1,3-dioxolan-2-one |
| CN105541783A (en) * | 2015-12-28 | 2016-05-04 | 苏州华一新能源科技有限公司 | Production method of high-purity fluoroethylene carbonate |
| CN110903274A (en) * | 2019-12-18 | 2020-03-24 | 江苏华盛锂电材料股份有限公司 | 4, 5-difluoroethylene carbonate and preparation method thereof |
| CN110981849A (en) * | 2019-12-16 | 2020-04-10 | 苏州华一新能源科技有限公司 | Preparation method and application of fluoroethylene carbonate |
| CN111808064A (en) * | 2020-07-14 | 2020-10-23 | 江苏华盛锂电材料股份有限公司 | Preparation method of vinylene carbonate, vinylene carbonate and application |
-
2021
- 2021-11-09 CN CN202111321314.8A patent/CN113896705A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20060067460A (en) * | 2004-12-15 | 2006-06-20 | 주식회사 엘지화학 | Preparation method of fluoroethylene carbonate |
| CN101205226A (en) * | 2006-12-22 | 2008-06-25 | 比亚迪股份有限公司 | Method for preparing monochlorin ethylene carbonate ester and vinylene carbonate |
| CN102766130A (en) * | 2012-07-18 | 2012-11-07 | 太仓华一化工科技有限公司 | Preparation method of difluoroethylene carbonate |
| CN102875521A (en) * | 2012-09-27 | 2013-01-16 | 中国海洋石油总公司 | Method for preparing fluoro-carbonate ester by means of phase-transfer catalysis |
| CN104529992A (en) * | 2014-11-26 | 2015-04-22 | 苏州华一新能源科技有限公司 | Preparation method for 4,5-difluoro-1,3-dioxolan-2-one |
| CN105541783A (en) * | 2015-12-28 | 2016-05-04 | 苏州华一新能源科技有限公司 | Production method of high-purity fluoroethylene carbonate |
| CN110981849A (en) * | 2019-12-16 | 2020-04-10 | 苏州华一新能源科技有限公司 | Preparation method and application of fluoroethylene carbonate |
| CN110903274A (en) * | 2019-12-18 | 2020-03-24 | 江苏华盛锂电材料股份有限公司 | 4, 5-difluoroethylene carbonate and preparation method thereof |
| CN111808064A (en) * | 2020-07-14 | 2020-10-23 | 江苏华盛锂电材料股份有限公司 | Preparation method of vinylene carbonate, vinylene carbonate and application |
Non-Patent Citations (1)
| Title |
|---|
| 任章顺;等: "氟代碳酸乙烯酯的合成与精制进展", 化学推进剂与高分子材料, no. 06, 28 November 2015 (2015-11-28), pages 39 - 44 * |
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