CN114230549A - Synthetic method of fluoroethylene carbonate - Google Patents
Synthetic method of fluoroethylene carbonate Download PDFInfo
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- CN114230549A CN114230549A CN202111402447.8A CN202111402447A CN114230549A CN 114230549 A CN114230549 A CN 114230549A CN 202111402447 A CN202111402447 A CN 202111402447A CN 114230549 A CN114230549 A CN 114230549A
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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 57
- 238000010189 synthetic method Methods 0.000 title abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 238000004821 distillation Methods 0.000 claims abstract description 38
- 239000012452 mother liquor Substances 0.000 claims abstract description 34
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims abstract description 26
- RCUYBENHBFYGDP-UHFFFAOYSA-N 4-chloro-5-fluoro-1,3-dioxolan-2-one Chemical compound FC1OC(=O)OC1Cl RCUYBENHBFYGDP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 21
- 239000003381 stabilizer Substances 0.000 claims abstract description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 238000012546 transfer Methods 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 28
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 12
- 230000002194 synthesizing effect Effects 0.000 claims description 12
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 7
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 6
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 claims description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 6
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 claims description 6
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 6
- BHRZNVHARXXAHW-UHFFFAOYSA-N sec-butylamine Chemical compound CCC(C)N BHRZNVHARXXAHW-UHFFFAOYSA-N 0.000 claims description 6
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 claims description 6
- -1 2,6, 6-tetramethyl-4-hydroxypiperidine nitroxide free radical Chemical class 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- 229940043279 diisopropylamine Drugs 0.000 claims description 4
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 4
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 4
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 3
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 claims description 3
- 229940044119 2-tert-butylhydroquinone Drugs 0.000 claims description 3
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- HQABUPZFAYXKJW-UHFFFAOYSA-N N-butylamine Natural products CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 3
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229950000688 phenothiazine Drugs 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 3
- 239000002585 base Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 238000001308 synthesis method Methods 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 6
- 238000003828 vacuum filtration Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 239000002920 hazardous waste Substances 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 4
- OYOKPDLAMOMTEE-UHFFFAOYSA-N 4-chloro-1,3-dioxolan-2-one Chemical compound ClC1COC(=O)O1 OYOKPDLAMOMTEE-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 235000003270 potassium fluoride Nutrition 0.000 description 3
- 239000011698 potassium fluoride Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-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
- 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
- 239000002904 solvent Substances 0.000 description 2
- OEWVNDMERGAAKZ-UHFFFAOYSA-N C(O)(=O)F.C#C Chemical compound C(O)(=O)F.C#C OEWVNDMERGAAKZ-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-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
- 239000012320 chlorinating reagent Substances 0.000 description 1
- 238000005660 chlorination reaction 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
- 239000012025 fluorinating agent Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 239000013067 intermediate product Substances 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
- 238000012856 packing Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-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
- C07D317/42—Halogen atoms or nitro radicals
Abstract
The application discloses a synthetic method of fluoroethylene carbonate. The synthetic method of the fluoroethylene carbonate comprises the following steps: mixing dimethyl carbonate and 1-fluoro-2-chloroethylene carbonate, dripping alkali at the synthesis reaction temperature under normal pressure, analyzing the conversion rate of fluoroethylene carbonate after the first time of synthesis reaction, and transferring to a transfer kettle for later use after the conversion rate is qualified; filtering to remove hydrochloride generated by the reaction to form mother liquor, transferring the mother liquor into a mother liquor intermediate tank, adding a stabilizing agent, performing rough distillation to remove dimethyl carbonate, transferring the mother liquor into a rectification intermediate tank for rectification after the rough distillation is qualified, and obtaining a qualified fluoroethylene carbonate finished product. The synthesis method of the fluoroethylene carbonate has the advantages of simple reaction conditions, simple operation, high production yield and high product purity.
Description
Technical Field
The invention relates to the technical field of a production method of fluoroethylene carbonate, in particular to a synthetic method of fluoroethylene 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. For example, patent CN101676282A discloses a method for producing fluoroethylene carbonate, which uses chlorine gas to directly substitute or uses other chlorinating agents such as sulfuryl chloride to perform chlorination to produce chloroethylene carbonate, the chloroethylene carbonate is refined and purified, and then undergoes halogen exchange reaction with fluorinating agents in proper solvents to produce fluoroethylene carbonate, the yield of fluoroethylene carbonate is less than 70%, and the purity is low.
Disclosure of Invention
The invention aims to provide a synthetic method of fluoroethylene carbonate, which is used for solving the technical problems of complex process, low production yield and low purity of the conventional synthetic method of fluoroethylene carbonate.
In order to achieve the above object, an embodiment of the present invention provides a method for synthesizing fluoroethylene carbonate, which comprises the steps of: mixing dimethyl carbonate and 1-fluoro-2-chloroethylene carbonate, dripping alkali at the synthesis reaction temperature under normal pressure, analyzing the conversion rate of fluoroethylene carbonate after the first time of synthesis reaction, and transferring to a transfer kettle for later use after the conversion rate is qualified; filtering to remove hydrochloride generated by the reaction to form mother liquor, transferring the mother liquor into a mother liquor intermediate tank, adding a stabilizing agent, performing rough distillation to remove dimethyl carbonate, transferring the mother liquor into a rectification intermediate tank for rectification after the rough distillation is qualified, and obtaining a qualified fluoroethylene carbonate finished product.
Further, in the mixture of the dimethyl carbonate and the 1-fluoro-2-chloroethylene carbonate, the molar ratio of the dimethyl carbonate to the 1-fluoro-2-chloroethylene carbonate is 1.2-2.5.
Further, the synthesis reaction temperature is 50-100 ℃.
Further, in the synthesis reaction process, the dropwise added alkali is one of ethylenediamine, triethylamine, dipropylamine, tripropylamine, diisopropylamine, butylamine, dibutylamine, tributylamine, isobutylamine and sec-butylamine.
Further, in the synthesis reaction process, the molar ratio of the dropwise added alkali to the 1-fluoro-2-chloroethylene carbonate is 1.05-1.2.
Further, the first time for carrying out the synthesis reaction is 2-12 h.
Further, the added stabilizer is one or more of hydroquinone, p-hydroxyanisole, 2, 6-di-tert-butyl-p-cresol, 2, 5-di-tert-butyl-hydroquinone, 2-tert-butyl-hydroquinone, p-benzoquinone, methyl hydroquinone, 2,6, 6-tetramethyl-4-hydroxypiperidine nitroxide free radical (TMHP0), copper N-di-N-butyl-dithiocarbamate, phenothiazine and p-hydroxyanisole.
Further, the mass of the added stabilizer is 0.001-0.1% of the total mass of the materials.
Further, tower separation is adopted for both rough distillation and rectification, a rough distillation tower is used in the rough distillation process, and a rectification tower is used in the rectification process; the crude distillation tower and the rectifying tower adopt a plate tower or a packed tower.
Furthermore, the crude distillation tower and the rectification tower are controlled by adopting a batch operation mode.
The invention has the beneficial effects that after 1-fluoro-2-chloroethylene carbonate is separated from heavy components at the bottoms of the vinylene carbonate VC rough distillation tower and the rectification tower, the high-boiling-point hazardous waste resource utilization in the vinylene carbonate process can be realized, the amount of hazardous waste is reduced, the comprehensive competitiveness of the vinylene carbonate process is improved, and the formed fluoroethylene carbonate product can also be used as an additive of a lithium battery electrolyte. The synthesis method of the fluoroethylene carbonate has the advantages of simple reaction conditions, simple operation, high production yield and high product purity.
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 method for synthesizing fluoroethylene carbonate, which comprises the steps of: mixing dimethyl carbonate and 1-fluoro-2-chloroethylene carbonate, dripping alkali at the synthesis reaction temperature under normal pressure, analyzing the conversion rate of fluoroethylene carbonate after the first time of synthesis reaction, and transferring to a transfer kettle for later use after the conversion rate is qualified; filtering to remove hydrochloride generated by the reaction to form mother liquor, transferring the mother liquor into a mother liquor intermediate tank, adding a stabilizing agent, performing rough distillation to remove dimethyl carbonate, transferring the mother liquor into a rectification intermediate tank for rectification after the rough distillation is qualified, and obtaining a qualified fluoroethylene carbonate finished product.
In the embodiment of the application, in the mixture of the dimethyl carbonate and the 1-fluoro-2-chloroethylene carbonate, the molar ratio of the dimethyl carbonate to the 1-fluoro-2-chloroethylene carbonate is 1.2-2.5.
In the examples of the present application, the synthesis reaction temperature is 50 to 100 ℃. Wherein the synthesis reaction temperature is optimized to be 60-80 ℃, so that the reaction temperature is not high and controllable.
In the embodiment of the application, in the synthesis reaction process, the dropwise added alkali is one of ethylenediamine, triethylamine, dipropylamine, tripropylamine, diisopropylamine, butylamine, dibutylamine, tributylamine, isobutylamine and sec-butylamine.
In the embodiment of the application, the molar ratio of the dropwise added alkali to the 1-fluoro-2-chloroethylene carbonate in the synthesis reaction process is 1.05-1.2.
In the examples of the present application, the first time for carrying out the synthesis reaction is 2 to 12 hours.
In the embodiment of the application, the added stabilizer is one or more of hydroquinone, p-hydroxyanisole, 2, 6-di-tert-butyl-p-cresol, 2, 5-di-tert-butyl-hydroquinone, 2-tert-butyl-hydroquinone, p-benzoquinone, methyl hydroquinone, 2,6, 6-tetramethyl-4-hydroxypiperidine nitroxide free radical (TMHP0), copper N-di-N-butyl-dithiocarbamate, phenothiazine and p-hydroxyanisole.
In the embodiment of the application, the mass of the added stabilizer is 0.001-0.1% of the total mass of the materials.
In the embodiment of the application, tower separation is adopted for both rough distillation and rectification, a rough distillation tower is used in the rough distillation process, and a rectification tower is used in the rectification process; the crude distillation tower and the rectifying tower adopt a plate tower or a packed tower. The rectification column and the crude distillation column are preferably structured packing.
In this application embodiment, the rough distillation tower and the rectifying column adopt intermittent operation mode to control, can promote energy utilization, avoid the not enough problem of the fractional distillation inefficiency that leads to of intermediate product to promote production efficiency.
Specifically, the method for synthesizing vinylene fluorocarbonate will be specifically described below with reference to the following examples.
Example 1
200g of dimethyl carbonate and 52g of 1-fluoro-2-chloroethylene carbonate are weighed and put into a reactor, nitrogen is replaced until the oxygen content is less than 0.3%, stirring is started, 25g of ethylenediamine is dripped when the temperature is raised to 70 ℃, circulating water is started to keep the reaction temperature at 70 ℃, dripping is carried out for 3 hours, the conversion rate of the fluoroethylene carbonate is analyzed, and the fluoroethylene carbonate is transferred into a transfer kettle with stirring after being qualified. Filtering and removing hydrochloride generated in the reaction by using a vacuum filtration bottle, transferring the mother liquor into a mother liquor intermediate tank, adding a stabilizing agent, performing rough distillation to remove dimethyl carbonate, transferring the mother liquor into a rectification intermediate tank after the rough distillation is qualified, performing rectification, and obtaining a qualified fluoroethylene carbonate finished product at the tower top.
Example 2
200g of dimethyl carbonate and 52g of 1-fluoro-2-chloroethylene carbonate are weighed and put into a reactor, nitrogen is replaced until the oxygen content is less than 0.3%, stirring is started, 42g of triethylamine is dripped when the temperature is raised to 70 ℃, circulating water is started to keep the reaction temperature at 70 ℃, dripping is carried out for 4 hours, the conversion rate of the fluoroethylene carbonate is analyzed, and the fluoroethylene carbonate is transferred into a transfer kettle with stirring after being qualified. Filtering and removing hydrochloride generated in the reaction by using a vacuum filtration bottle, transferring the mother liquor into a mother liquor intermediate tank, adding a stabilizing agent, performing rough distillation to remove dimethyl carbonate, transferring the mother liquor into a rectification intermediate tank after the rough distillation is qualified, performing rectification, and obtaining a qualified fluoroethylene carbonate finished product at the tower top.
Example 3
200g of dimethyl carbonate and 52g of 1-fluoro-2-chloroethylene carbonate are weighed and put into a reactor, nitrogen is replaced until the oxygen content is less than 0.3%, stirring is started, 42g of dipropylamine is dripped when the temperature is raised to 70 ℃, circulating water is started to keep the reaction temperature at 70 ℃, dripping is carried out for 3 hours, the conversion rate of the fluoroethylene carbonate is analyzed, and the fluoroethylene carbonate is transferred into a transfer kettle with stirring after being qualified. Filtering and removing hydrochloride generated in the reaction by using a vacuum filtration bottle, transferring the mother liquor into a mother liquor intermediate tank, adding a stabilizing agent, performing rough distillation to remove dimethyl carbonate, transferring the mother liquor into a rectification intermediate tank after the rough distillation is qualified, performing rectification, and obtaining a qualified fluoroethylene carbonate finished product at the tower top.
Example 4
200g of dimethyl carbonate and 52g of 1-fluoro-2-chloroethylene carbonate are weighed and put into a reactor, nitrogen is replaced until the oxygen content is less than 0.3%, stirring is started, 58g of tripropylamine is dripped when the temperature is raised to 70 ℃, circulating water is started to keep the reaction temperature at 70 ℃, dripping is carried out for 3 hours, the conversion rate of the fluoroethylene carbonate is analyzed, and the fluoroethylene carbonate is transferred into a transfer kettle with stirring after being qualified. Filtering and removing hydrochloride generated in the reaction by using a vacuum filtration bottle, transferring the mother liquor into a mother liquor intermediate tank, adding a stabilizing agent, performing rough distillation to remove dimethyl carbonate, transferring the mother liquor into a rectification intermediate tank after the rough distillation is qualified, performing rectification, and obtaining a qualified fluoroethylene carbonate finished product at the tower top.
Example 5
200g of dimethyl carbonate and 52g of 1-fluoro-2-chloroethylene carbonate are weighed and put into a reactor, nitrogen is replaced until the oxygen content is less than 0.3%, stirring is started, 42g of diisopropylamine is dripped when the temperature is raised to 70 ℃, circulating water is started to keep the reaction temperature at 70 ℃, dripping is carried out for 4 hours, the conversion rate of the fluoroethylene carbonate is analyzed, and the fluoroethylene carbonate is transferred into a transfer kettle with stirring after being qualified. Filtering and removing hydrochloride generated in the reaction by using a vacuum filtration bottle, transferring the mother liquor into a mother liquor intermediate tank, adding a stabilizing agent, performing rough distillation to remove dimethyl carbonate, transferring the mother liquor into a rectification intermediate tank after the rough distillation is qualified, performing rectification, and obtaining a qualified fluoroethylene carbonate finished product at the tower top.
Example 6
200g of dimethyl carbonate and 52g of 1-fluoro-2-chloroethylene carbonate are weighed and put into a reactor, nitrogen is replaced until the oxygen content is less than 0.3%, stirring is started, 42g of triethylamine is dripped when the temperature is raised to 80 ℃, circulating water is started to keep the reaction temperature at 80 ℃, dripping is carried out for 4 hours, the conversion rate of the fluoroethylene carbonate is analyzed, and the fluoroethylene carbonate is transferred into a transfer kettle with stirring after being qualified. Filtering and removing hydrochloride generated in the reaction by using a vacuum filtration bottle, transferring the mother liquor into a mother liquor intermediate tank, adding a stabilizing agent, performing rough distillation to remove dimethyl carbonate, transferring the mother liquor into a rectification intermediate tank after the rough distillation is qualified, performing rectification, and obtaining a qualified fluoroethylene carbonate finished product at the tower top.
The invention has the beneficial effects that after 1-fluoro-2-chloroethylene carbonate is separated from heavy components at the bottoms of the vinylene carbonate VC rough distillation tower and the rectification tower, the high-boiling-point hazardous waste resource utilization in the vinylene carbonate process can be realized, the amount of hazardous waste is reduced, the comprehensive competitiveness of the vinylene carbonate process is improved, and the formed fluoroethylene carbonate product can also be used as an additive of a lithium battery electrolyte. The synthesis method of the fluoroethylene carbonate has the advantages of simple reaction conditions, simple operation, high production yield and high product purity.
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 method for synthesizing fluoroethylene carbonate is characterized by comprising the following steps: mixing dimethyl carbonate and 1-fluoro-2-chloroethylene carbonate, dripping alkali at the synthesis reaction temperature under normal pressure, analyzing the conversion rate of fluoroethylene carbonate after the first time of synthesis reaction, and transferring to a transfer kettle for later use after the conversion rate is qualified; filtering to remove hydrochloride generated by the reaction to form mother liquor, transferring the mother liquor into a mother liquor intermediate tank, adding a stabilizing agent, performing rough distillation to remove dimethyl carbonate, transferring the mother liquor into a rectification intermediate tank for rectification after the rough distillation is qualified, and obtaining a qualified fluoroethylene carbonate finished product.
2. The method of synthesizing fluoroethylene carbonate according to claim 1, wherein the molar ratio of dimethyl carbonate to 1-fluoro-2-chloroethylene carbonate in the mixture of dimethyl carbonate and 1-fluoro-2-chloroethylene carbonate is 1.2 to 2.5.
3. The method for synthesizing fluoroethylene carbonate according to claim 1, wherein the synthesis reaction temperature is 50-100 ℃.
4. The method for synthesizing fluoroethylene carbonate according to claim 1, wherein the dropwise addition of the base during the synthesis reaction is one of ethylenediamine, triethylamine, dipropylamine, tripropylamine, diisopropylamine, butylamine, dibutylamine, tributylamine, isobutylamine and sec-butylamine.
5. The method for synthesizing fluoroethylene carbonate according to claim 1, wherein the molar ratio of the dropwise added alkali to the 1-fluoro-2-chloroethylene carbonate is 1.05 to 1.2 during the synthesis reaction.
6. The method of claim 1, wherein the first time period for the synthesis reaction is 2-12 hours.
7. The method for synthesizing fluoroethylene carbonate according to claim 1, wherein the stabilizer is one or more selected from hydroquinone, p-hydroxyanisole, 2, 6-di-tert-butyl-p-cresol, 2, 5-di-tert-butyl-hydroquinone, 2-tert-butyl-hydroquinone, p-benzoquinone, methyl hydroquinone, 2,6, 6-tetramethyl-4-hydroxypiperidine nitroxide free radical, copper N-di-N-butyl-dithiocarbamate, phenothiazine and p-hydroxyanisole.
8. The method for synthesizing fluoroethylene carbonate according to claim 1, wherein the mass of the stabilizer added is 0.001 to 0.1% of the total mass of the materials.
9. The method for synthesizing fluoroethylene carbonate according to claim 1, wherein the rough distillation and the rectification both adopt tower separation, the rough distillation process adopts a rough distillation tower, and the rectification process adopts a rectification tower; the crude distillation tower and the rectifying tower adopt a plate tower or a packed tower.
10. The method for synthesizing fluoroethylene carbonate according to claim 1, wherein the crude distillation column and the rectification column are controlled in a batch operation.
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