CN105566280A - Preparation method of fluoroethylene carbonate - Google Patents
Preparation method of fluoroethylene carbonate Download PDFInfo
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- CN105566280A CN105566280A CN201410617049.1A CN201410617049A CN105566280A CN 105566280 A CN105566280 A CN 105566280A CN 201410617049 A CN201410617049 A CN 201410617049A CN 105566280 A CN105566280 A CN 105566280A
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- fluorinated ethylene
- ethylene carbonate
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- fluoroethylene
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Abstract
The invention discloses a preparation method of fluoroethylene carbonate. The fluoroethylene carbonate is prepared by using a synthetic oxygen carrier or an inorganic salt as a catalyst and using fluoroethylene as a fluorine source, and catalyzing the fluoroethylene to react with carbon dioxide and oxygen at the temperature of 30-400 DEG C and under the pressure of 0.1-10 MPa, and the fluoroethylene carbonate is 4-fluoro-1, 3- dioxolane-2-one. Exchange of halogen atoms is not performed by using chloroethylene carbonate, generation of a lot of solid waste residues as well as acidic gas is avoided, and the utilization ratio of the atoms is high; compared with alkali metal fluoride which has very high requirements (water-free) on the storage environment and the reaction conditions, a pressure container used in the reaction can store gas which can be compressed relatively easily, and is not high in requirements on the storage environment and the material transport, so that requirements of green chemistry are met.
Description
Technical field
The present invention relates to a kind of preparation method of fluorinated ethylene carbonate.
Background technology
Fluorinated ethylene carbonate is main lithium-ion battery electrolytes additive, the performance forming SEI film is better, forms fine structure layer and does not increase impedance, electrolytic solution can be stoped to decompose further, and have fire retardation, the while that battery cycle life being improved, safety performance significantly increases.The method adopted in the industry at present has and chlorocarbonic acid vinyl acetate to be mixed with Potassium monofluoride and to make it react, acquisition fluorinated ethylene carbonate, and yield is 70%; With ketone, nitrile, sulfone compound as solvent, reaction yield is 70%; With phase-transfer catalyst crown ether or polyoxyethylene glycol for catalyzer, with chlorocarbonic acid vinyl acetate and Sodium Fluoride reaction under condition of no solvent, reaction yield 50%.Also have other patents using excess alkali metal fluorochemical as fluorination reagent, in aprotic solvent reacting by heating, then by the aftertreatment such as filtrations, extraction, the research of last rectifying acquisition product, it distinguishes mainly fluorine source, temperature of reaction and reaction solvent aspect.
But such as above synthetic route needs the exchange carrying out halogen atom with chlorocarbonic acid vinyl acetate, a large amount of solid slags (main component is the alkali metal chloride generated, excessive alkaline metal fluoride cpd and organic polymer residue) will be produced, and to produce chlorocarbonic acid vinyl acetate itself be also chlorination by NSC 11801, produce a large amount of sour gas with the difference of chlorination reagent.This technique atom utilization is low, and expensive starting materials is far apart with the requirement of Green Chemistry.
Summary of the invention
The technical problem to be solved in the present invention is to provide one and can avoids producing a large amount of sour gas, solid slag, and has the preparation method of the fluorinated ethylene carbonate of higher atom utilization.
For solving the problems of the technologies described above, the present invention adopts a kind of preparation method of fluorinated ethylene carbonate, use artificial synthetic oxygen carrier or inorganic salt as catalyzer, using vinyl fluoride as fluorine source, at 30 ~ 400 DEG C, under 0.1 ~ 10MPa pressure, catalysis vinyl fluoride and carbon dioxide and oxygen react, and obtain fluorinated ethylene carbonate, its fluorinated ethylene carbonate is 4-fluoro-1,3-dioxolan-2-one.
Preferably, synthetic oxygen carrier is presence of Schiff-base complex.
Preferably, its presence of Schiff-base complex is the presence of Schiff-base complex of period 4 metallic element ion.
Preferably, its inorganic salt are the mixture of mantoquita, molysite or mantoquita and molysite.
Preferably, above-mentioned vinyl fluoride refers to 1-fluorinated ethylene.
Preferably, need to be laid in special stainless steel frame before the reaction of its presence of Schiff-base complex, be placed in closed cabinet, pass into high purity oxygen gas, heating and pressurizing makes it complete adsorption activation.
Beneficial effect of the present invention: the exchange not carrying out halogen atom with chlorocarbonic acid vinyl acetate, avoid producing a large amount of solid slags, avoid producing sour gas, atom utilization is high, compare the high requirement (anhydrous) of alkaline metal fluoride cpd to storage condition and reaction conditions, this reaction uses pressurized vessel to store more squeezable gas, less demanding to storage condition and mass transport, meets the requirement of Green Chemistry.
Embodiment
Below in conjunction with embodiment, the present invention will be further described.
Embodiment 1
The preparation of fluorinated ethylene carbonate
Choose the schiff bases Manganse Dioxide title complex of the drying of brand-new, be laid in special stainless steel frame, be placed in closed cabinet, pass into high purity oxygen gas, heating makes adsorption activation.In 5L stainless steel autoclave, add the presence of Schiff-base complex 400g(oxygen level about 10% of activation), add dry ice 242g, close autoclave.The speed of dividing with 50ML/ from bottom slowly passes into vinyl fluoride gas.Progressively raise temperature of reaction kettle, control temperature 45 ~ 50 DEG C, pressure slowly rises to 0.8MPa.Breather valve is closed after note heavily passes into 46g vinyl fluoride.Control pressure≤1.5MPa, slowly increases the temperature to 80 DEG C, insulation reaction.When pressure durations declines, raise temperature gradually to 100 DEG C, react fully.Then cool to room temperature, get rid of tail gas.Open reactor after abundant pressure release, add 250g methylcarbonate and fully stir, and filter, with 250g methylcarbonate washing leaching cake, filter cake washing can activate use after drying again.Merging filtrate, carries out the aftertreatments such as rectification under vacuum, obtains 73.6g fluorinated ethylene carbonate, GC content 99.91%, yield 69.4%.
Embodiment 2
Choose and to reclaim and the schiff bases Manganse Dioxide title complex 400g activated adds in 5L stainless steel autoclave and adds dry ice 242g, close autoclave.The speed of dividing with 50ML/ from bottom slowly passes into vinyl fluoride gas.Progressively raise temperature of reaction kettle, control temperature 45 ~ 50 DEG C, pressure slowly rises to 0.8MPa.Breather valve is closed after note heavily passes into 46g vinyl fluoride.Control pressure≤1.5MPa, slowly increases the temperature to 80 DEG C, insulation reaction.When pressure durations declines, raise temperature gradually to 100 DEG C, react fully.Then cool to room temperature, get rid of tail gas.Open reactor after abundant pressure release, add 250g methylcarbonate and fully stir, and filter, with 250g methylcarbonate washing leaching cake, filter cake washing can activate use after drying again.Merging filtrate, carries out the aftertreatments such as rectification under vacuum, obtains 68.6g fluorinated ethylene carbonate, GC content 99.90%, yield 64.7%.
Embodiment 3
In 5L stainless steel autoclave, add tetramethylene sulfone 1000g, add 2g ferrous sulfate, add 242g dry ice, close autoclave, pass into 40g pure oxygen, open and stir.The speed of dividing with 50ML/ from bottom slowly passes into vinyl fluoride gas.Progressively raise temperature of reaction kettle, control temperature 45 ~ 50 DEG C, pressure slowly rises≤0.8MPa.Breather valve is closed after note heavily passes into 46g vinyl fluoride.Control pressure≤1.5MPa, slowly increases the temperature to 90 DEG C, insulation reaction.When pressure durations declines, raise temperature gradually to 110 DEG C, react fully.Then cool to room temperature, get rid of tail gas.Open reactor after abundant pressure release, filter, filtrate carries out the aftertreatments such as rectification under vacuum, obtains 79.1g fluorinated ethylene carbonate, GC content 99.88%, yield 74.6%.
Embodiment 4
In 5L stainless steel autoclave, add diethyl carbonate 1000g, add 4g ferrous sulfate, 2g copper carbonate, add 242g dry ice, close autoclave, pass into 80g pure oxygen, open and stir.The speed of dividing with 50ML/ from bottom slowly passes into vinyl fluoride gas.Progressively raise temperature of reaction kettle, control temperature 45 ~ 50 DEG C, pressure slowly rises≤0.8MPa.Breather valve is closed after note heavily passes into 46g vinyl fluoride.Control pressure≤2.0MPa, slowly increases the temperature to 90 DEG C, insulation reaction.When pressure durations declines, raise temperature gradually to 130 DEG C, react fully.Then cool to room temperature, get rid of tail gas.Open reactor after abundant pressure release, filter, filtrate carries out the aftertreatments such as rectification under vacuum, obtains 84.2g fluorinated ethylene carbonate, GC content 99.93%, yield 79.4%.
The foregoing is only embodiments of the invention; only as the description of embodiment; not thereby the scope of the claims of the present invention is limited; under not departing from the present invention and conceiving the prerequisite of thought; the various distortion that this area engineering technical personnel make technical solution of the present invention and improvement; or the conversion of the equivalence utilizing description of the present invention to do, be all in like manner included in scope of patent protection of the present invention.
Claims (6)
1. the preparation method of fluorinated ethylene carbonate, it is characterized in that using artificial synthetic oxygen carrier or inorganic salt as catalyzer, using vinyl fluoride as fluorine source, at 30 ~ 400 DEG C, under 0.1 ~ 10MPa pressure, catalysis vinyl fluoride and carbon dioxide and oxygen react, obtain fluorinated ethylene carbonate, described fluorinated ethylene carbonate is 4-fluoro-1,3-dioxolan-2-one.
2. the preparation method of fluorinated ethylene carbonate according to claim 1, is characterized in that described synthetic oxygen carrier is presence of Schiff-base complex.
3. presence of Schiff-base complex according to claim 2 is the presence of Schiff-base complex of period 4 metallic element ion.
4. the preparation method of fluorinated ethylene carbonate according to claim 1, is characterized in that described inorganic salt are the mixture of mantoquita, molysite or mantoquita and molysite.
5. the preparation method of fluorinated ethylene carbonate according to claim 1, is characterized in that described vinyl fluoride refers to 1-fluorinated ethylene.
6. the preparation method of fluorinated ethylene carbonate according to claim 1, need to be laid on special stainless steel frame before it is characterized in that the reaction of described presence of Schiff-base complex, be placed in closed cabinet, pass into high purity oxygen gas, heating and pressurizing makes it complete adsorption activation.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410617049.1A CN105566280A (en) | 2014-11-06 | 2014-11-06 | Preparation method of fluoroethylene carbonate |
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| CN201410617049.1A CN105566280A (en) | 2014-11-06 | 2014-11-06 | Preparation method of fluoroethylene carbonate |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106632226A (en) * | 2016-12-08 | 2017-05-10 | 江苏理文化工有限公司 | Preparation method of 4,4-difluoroethylene carbonate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4247465A (en) * | 1979-08-23 | 1981-01-27 | Atlantic Richfield Company | Preparation of alkylene carbonates from olefins |
| US20050070724A1 (en) * | 2003-09-29 | 2005-03-31 | Council Of Scientific And Industrial Research | Process for the preparation of cyclic carbonates |
| CN101514195A (en) * | 2009-03-11 | 2009-08-26 | 兰州大学 | Preparation method for cyclic carbonates |
-
2014
- 2014-11-06 CN CN201410617049.1A patent/CN105566280A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4247465A (en) * | 1979-08-23 | 1981-01-27 | Atlantic Richfield Company | Preparation of alkylene carbonates from olefins |
| US20050070724A1 (en) * | 2003-09-29 | 2005-03-31 | Council Of Scientific And Industrial Research | Process for the preparation of cyclic carbonates |
| CN101514195A (en) * | 2009-03-11 | 2009-08-26 | 兰州大学 | Preparation method for cyclic carbonates |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106632226A (en) * | 2016-12-08 | 2017-05-10 | 江苏理文化工有限公司 | Preparation method of 4,4-difluoroethylene carbonate |
| CN106632226B (en) * | 2016-12-08 | 2019-04-23 | 江苏理文化工有限公司 | A kind of preparation method of 4,4- difluorinated ethylene carbonate |
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