CN101519398A - Preparation of 4-fluoro-1,3-dioxolane-2-one - Google Patents
Preparation of 4-fluoro-1,3-dioxolane-2-one Download PDFInfo
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- CN101519398A CN101519398A CN 200910118346 CN200910118346A CN101519398A CN 101519398 A CN101519398 A CN 101519398A CN 200910118346 CN200910118346 CN 200910118346 CN 200910118346 A CN200910118346 A CN 200910118346A CN 101519398 A CN101519398 A CN 101519398A
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Abstract
The present invention provides a method for preparing 4-fluoro-1,3-dioxolane-2-one with reduced halide content at high yield. The preparation of 4-fluoro-1,3-dioxolane-2-one is characterized in that the preparation comprises: the process (A) of fluorizating 4-chloro-1,3-dioxolane-2-one by fluridizer in organic solvent; the process (B) of distilling reaction form solution 4-chloro-1,3-dioxolane-2-one; and the process (C) of treating by antacid.
Description
Technical field
The present invention relates to reduce the 4-fluoro-1 of halogen radical content, the method for 3-dioxolane-2-ketone with high yield manufacturing.
Background technology
4-fluoro-1,3-dioxolane-2-ketone (below be also referred to as " F-EC ") utilizes its high-k and as the solvent of the electrolytic solution of various batteries.
Manufacture method as this F-EC, except with 1,3-dioxolane-2-ketone is parent material, directly carries out beyond the fluorizated method with fluorine gas, also known use roughly the metal fluoride of equivalent as fluorizating agent, replace 4-chloro-1 with fluorine atom, the method (patent documentation 1～3) of 4 chlorine atom of 3-dioxolane-2-ketone (below be also referred to as " Cl-EC ").
In patent documentation 1, to have put down in writing and Cl-EC mixed with Potassium monofluoride and made its reaction, the yield with 70% obtains the technology of F-EC, but primary conditions such as unexposed reaction solvent, temperature of reaction and reaction times.
In patent documentation 2 and 3, use 1.2 normal Potassium monofluorides, make Cl-EC and Potassium monofluoride in acetonitrile, 80～85 ℃ the reaction 11 hours, yield with 87.5% obtains containing the thick resultant of F-EC (if carry out recrystallization, then can collect F-EC with 85% of thick resultant) of parent material Cl-EC.But, because in the method, with Cl-EC is initial feed, replace the chlorine atom with fluorine atom, so, among the thick F-EC after reaction finishes, residual have by-product generates in unreacted Cl-EC, the fluoridation hydrogenchloride (HCl) and be present in chlorine (Cl among the initial feed Cl-EC as impurity
2) wait the chlorine root.In fact, after the fluoridation resultant was filtered, the concentration of carrying out the chlorine root among the F-EC that rectifying obtains was up to 189ppm.
If residually have the F-EC of chlorine root to be used for purposes such as secondary cell with this, because cycle characteristics can reduce, the concentration of the chlorine root among the F-EC after therefore needing to make with extra care is controlled at chlorion and is scaled below the 100ppm, be preferably below the 50ppm, more preferably below the 20ppm, but because the specific inductivity height of F-EC, and the Cl in these chlorine roots
-, HCl, Cl
2Can't remove by distilling fully, so these chlorine roots remain in the solvent easily or in the refining thing.
In order to remove these chlorine roots, in patent documentation 2, adopt by the method for specific organic solvent the F-EC recrystallization, adopt in the patent documentation 3 with specific low polar solvent to contact, make F-EC form sedimentary method.
[patent documentation 1] international brochure that discloses No. 98/15024
[patent documentation 2] TOHKEMY 2007-8825 communique
[patent documentation 3] TOHKEMY 2007-8826 communique
Summary of the invention
The object of the present invention is to provide the manufacture method of a kind of F-EC, this method is parent material with Cl-EC, with fluorizating agent it is fluoridized, and can keep high yield and high purity, and reduces the halogen radical content.
4-fluoro-1 of the present invention, the manufacture method of 3-dioxolane-2-ketone is characterised in that, comprising: utilize fluorizating agent to 4-chloro-1 in organic solvent, 3-dioxolane-2-ketone carries out fluorizated operation (A); To gained contain 4-fluoro-1, the 3-dioxolane-reaction solution of 2-ketone carries out the operation (B) of rectifying; With the operation of handling with antacid (C).
In manufacture method of the present invention, preferably, comprise the operation (D) of removing organic solvent fluoridizing operation (A) afterwards and before at rectification working process (B).
Antacid is preferably the oxide compound of alkaline-earth metal, the supercarbonate of alkaline-earth metal, the phosphoric acid salt of alkaline-earth metal, the carboxylate salt of alkaline-earth metal, alkali-metal supercarbonate, alkali-metal phosphoric acid salt, alkali-metal carboxylate salt, Si oxide, aluminum oxide, sial composite oxides or wherein two or more.
Antacid is preferably antacid porous mass, more preferably Si oxide, aluminum oxide, sial composite oxides or two or more porous mass wherein.
Fluorizating agent is preferably the compound shown in the formula MF (in the formula, M is alkali metal atom or quaternary ammonium cation).
And,, be 6～7 preferably, and under this condition, carry out rectification working process (B) pH regulator from suppressing the viewpoint that carbonate decomposes.
In the present invention, so-called " halogen root " refers to hydrogenchloride (HCl) and the chlorine (Cl that by-product generates in fluoridation
2), and be present in chlorion (Cl among the initial feed Cl-EC as impurity
-) wait the chlorine root; Fluorion (F from fluorizating agent
-) or fluorine (F
2), hydrogen fluoride fluorine roots such as (HF); Come the fluorion (F of the impurity of by-product in the autoreaction
-) etc.Wherein, do not comprise unreacted Cl-EC and in the halogen root as the F-EC of purpose product.
The invention effect
Adopt manufacture method of the present invention, can produce the F-EC that keeps high purity and reduced the halogen radical content.
Embodiment
The manufacture method of F-EC of the present invention comprises following operation (A), rectification working process (B) and the antacid treatment process (C) of fluoridizing.
Fluoridize operation (A) for to utilize fluorizating agent to 4-chloro-1 in organic solvent, 3-dioxolane-2-ketone carries out the fluorizated operation.
Rectification working process (B) for to gained contain 4-fluoro-1, the 3-dioxolane-reaction solution of 2-ketone carries out the operation of rectifying.
The operation of antacid treatment process (C) for handling with antacid.This antacid treatment process in operation (A), operation (A) before, operation (A) afterwards, in the operation (B), operation (B) before and operation (B) carry out once at least afterwards.
Below each operation is described.
Fluoridize operation (A)
Fluoridizing by utilizing fluorizating agent that Cl-EC is fluoridized in organic solvent of Cl-EC implemented.
The reaction formula of fluoridizing operation (A) among the present invention is as follows.
Wherein, parent material Cl-EC and desired substance F-EC are liquid.
As fluorizating agent, except hydrofluoric acid, fluorine gas, the compound shown in the formula MF (in the formula, M is alkali metal atom or quaternary ammonium cation) is preferred owing to obtain easily with the excellent in efficiency of fluoridation.
As the compound shown in the MF, for example can enumerate alkaline metal fluoride cpds such as KF, NaF, CsF, LiF, the compound of quaternary ammonium cation and fluorine anion etc.Wherein, alkaline metal fluoride cpd is owing to be easy to handle with reactive high and preferred, and particularly KF is preferred especially because reactivity is high.
Fluoridizing operation (A) carries out in organic solvent.Owing to exist water will cause reactive the reduction, so carry out under the preferably substantially anhydrous state.
As organic solvent, be preferably non-proton organic solvent, further from improving the viewpoint of speed of response, more preferably polar organic solvent.Specifically can illustration acetonitrile (AN), tetrahydrofuran (THF) (THF), N-Methyl pyrrolidone (NMP), methylene dichloride, trichloromethane, Nitromethane 99Min., N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, 1,3-dimethyl-2-imidazolone, glycol diether (glyme) series solvent, acetone, toluene, ethyl acetate etc.Wherein, from specific inductivity height, viewpoint that viscosity is low, preferred acetonitrile; And from specific inductivity height, the suitable viewpoint of boiling point, preferred N-Methyl pyrrolidone.
From the good viewpoint of transformation efficiency (yield), fluorizating agent is preferably with respect to the usage quantity of Cl-EC, and with respect to chlorine atom 1 equivalent among the Cl-EC, fluorizating agent is more than 1 equivalent, is preferably more than 1.5 equivalents, is preferably especially more than 2 equivalents.The upper limit is not particularly limited, but is easy to viewpoint from aftertreatment, till 3 equivalents.
From easy-to-handle viewpoint, temperature of reaction is preferably more than 30 ℃, more preferably more than 50 ℃.And on be limited to the boiling point of used organic solvent.
In addition, as catalyzer, can use quaternary ammonium cation shown in the formula (1) and the anionic compound of halogen.
R
4N
+X
- (1)
In the formula, R is alkyl, phenyl, benzyl or the cycloalkyl of carbonatoms 1～7; X is a halogen atom.When using this catalyzer, can obtain F-EC with high yield at short notice.
As catalyzer, from easy-to-handle viewpoint, R is the compound of the alkyl of carbonatoms 1～7 in the preferred formula (1).
In addition, the halogen atom as constituting catalyzer from the high viewpoint of initial reaction, is preferably fluorine atom.
As the quaternary ammonium cation of catalyzer and the concrete example of the anionic compound of halogen (1), for example can enumerate Methanaminium, N,N,N-trimethyl-, fluoride, tetraethyl ammonium fluoride, tetrapropyl Neutral ammonium fluoride, tetrabutyl ammonium fluoride etc.
From the high viewpoint of reactivity, preferred catalyst uses with 0.01～0.5 equivalent of fluorizating agent.
The reaction of parent material Cl-EC and fluorizating agent with etc. mol ratio carry out, but,, preferably use 1～2 mole of fluorizating agent with respect to 1 mole of Cl-EC from reactive viewpoint, more preferably use 1～1.5 mole.
Concentration as the parent material Cl-EC in the organic solvent can adopt scope widely, but from being easy to control the viewpoint of reaction, is preferably more than the 5 quality %, more preferably more than the 20 quality %.The upper limit is preferably 60 quality %, more preferably 50 quality %.
When using catalyzer (compound 1), react faster, under yield on an equal basis, finish reaction with the time below 1/2 in existing reaction times than the reaction of existing manufacture method.Yield also is 80～85%, and is equal or on it with existing method.
Rectification working process (B)
Rectification working process is to use rectifying tower to handling by fluoridizing the F-EC reaction solution that operation (A) obtains, and obtains the operation of F-EC with high purity.F-EC obtains with the cut of 74 ℃ (1mmHg).In addition, the boiling point of Cl-EC is 100 ℃ (1mmHg), can pass through rectifying separation.
In addition, for before, can insert that following organic solvent is removed operation (D) or solid state component is removed operation (E) in rectification working process (B).
And, owing to be acid (for example pH1～2) by fluoridizing the F-EC reaction solution that operation (A) obtains sometimes, so in this case, from suppressing F-EC or a small amount of remaining Cl-EC and the viewpoint of NSC 11801 (EC) generation decomposition, be 6～7 preferably, under this condition, carry out rectification working process (B) pH regulator.
The adjusting of pH can be adopted to adding antacid by fluoridizing in the F-EC reaction solution that operation (A) obtains, absorption removes disacidify (HF, HCl etc.) method (identical with following antacid treatment process (C)) is carried out, in addition, can also adopt the temperature (for example 50～130 ℃) that is heated to unlikely decomposition such as F-EC to make the method for acid evaporation, decompression makes the method for acid evaporation, add pH regulator agent or basic cpd (sodium bicarbonate for example, saleratus, yellow soda ash, salt of wormwood, lime carbonate, cesium carbonate, sodium hydroxide, 1 kind of method in the method for potassium hydroxide etc.) regulating etc. is carried out or the method that makes up more than 2 kinds is carried out.
Antacid treatment process (C)
This operation is the operation of the halogen root that utilizes antacid to remove to exist in the reaction system.
Handle by antacid, can remove the halogen root expeditiously, can make that remaining halogen root reduces to below the 10ppm in the end article (refining F-EC), further reduce to below the 1ppm, further reduce to below the 0.1ppm.
As antacid, have absorption and with the compound of the performance of halogen root reaction etc. be effective.
As the compound of performance, for example can metallic compound, inorganic porous material etc. be shown example with absorbing halogen root.As metallic compound, the oxide compound of preferred use basic metal or alkaline-earth metal, oxyhydroxide, carboxylate salt, carbonate, supercarbonate, silicate, phosphoric acid salt, phosphite, borate etc., the oxide compound of periodictable group vib metal (for example Cr, Mo, W etc.), alkali formula carboxylate salt, subcarbonate, subsulphate, three subsulphates, alkali formula phosphite etc.As the concrete example of such metallic compound, can magnesium oxide, calcium oxide, magnesium hydroxide, calcium hydroxide, hydrated barta, Quilonum Retard, yellow soda ash, salt of wormwood, lithium bicarbonate, sodium bicarbonate, saleratus, magnesiumcarbonate, lime carbonate, barium carbonate, Calucium Silicate powder, potassium acetate, lime acetate, calcium stearate, Zinic stearas, phosphorous acid calcium, ferric oxide, stannic oxide, red lead, white lead, dibasic lead phthalate (two salt base Off Le be shown example
), two white lead carbonates, aluminium hydroxide etc.In addition, as inorganic porous material, for example, can use Si oxides such as silicon-dioxide, aluminum oxides such as aluminum oxide, in addition sial composite oxides such as natural zeolite, synthetic zeolite, molecular sieve (3A, 4A, 5A, 13X etc.), various hydrotalcites etc. also can use commercially available various porous antacids etc.As commercially available porous antacid, can the inorganic porous body (the product river changes into the system secado of Co., Ltd., trade(brand)name) that be formed by amorphous silica-alumina gel, hydrate porous insert (the system ア of the marshy land KCC Le Off that contains aluminium and iron be shown example
エマ イ ト, trade(brand)name) etc.
These antacids may be used alone, two or more kinds can also be used in combination.
In the present invention, particularly can suppress aspect the F-EC decomposition, the phosphoric acid salt of the oxide compound of preferred bases earth metals, the supercarbonate of alkaline-earth metal, alkaline-earth metal, the carboxylate salt of alkaline-earth metal, alkali-metal supercarbonate, alkali-metal phosphoric acid salt, alkali-metal carboxylate salt, Si oxide, aluminum oxide, sial composite oxides, or two or more etc. the low antacid of nucleophilicity wherein.
Particularly preferred antacid except tertiary sodium phosphate, sodium acetate, potassium acetate, saleratus, also preferred antacid porous mass, further preferred Si oxide, aluminum oxide, sial composite oxides or the porous mass more than 2 kinds wherein.
Antacid treatment process (C) was carried out in following (1)～(6) stage, particularly operation (A) before, in the operation (A), operation (A) afterwards, operation (B) before, in the operation (B) and operation (B) at least one stage in afterwards carry out.
(1) fluoridize operation (A) before:
That is, the Cl-EC as initial feed is handled with antacid.Owing in initial feed Cl-EC, exist the chlorine root (Cl that in building-up process, produces
-, HCl, Cl
2Deng), so remove these halogen roots.
(2) fluoridize in the operation (A):
In fluoridizing operation (A), except the chlorine root in the initial feed, from the fluorine (F of fluorizating agent (fluorine gas, hydrofluoric acid, MF etc.)
2), hydrogen fluoride (HF), fluorion (F
-) wait beyond, also exist fluorion (F from the impurity of the by product of fluoridation
-) etc., so remove these halogen roots.
(3) fluoridize operation (A) afterwards:
By fluoridizing in the resultant of reaction that operation (A) obtains, exist and above-mentioned (2) same halogen root, so remove these halogen roots.
(4) rectification working process (B) is before:
At rectification working process (B) before, sometimes to carrying out the removing of organic solvent (distillation) or remove (filtrations) processing what carry out carrying out when at least antacid is handled antacid by fluoridizing resultant of reaction that operation (A) obtains.
At rectification working process (B) before, whether organic solvent described later is removed operation (D) and solid state component is removed operation (E) according to carrying out, and concentration is slightly different, but owing to exist and above-mentioned (3) same halogen root, so remove these halogen roots.And, as mentioned above, in distillation (rectifying), be difficult to remove dechlorination root (Cl
-, HCl, Cl
2Deng) and fluorine root (F
-, HF, F
2Deng).
(5) in the rectification working process (B):
In rectification working process (B), owing to exist the halogen root that decomposes from impurity, so remove these halogen roots.
(6) rectification working process (B) is afterwards:
At rectification working process (B) afterwards, the heating or the decompression that exist owing to rectifying are evaporated or are distilled the halogen root halogen root of removing in addition, so remove these halogen roots.
The invention is characterized in that at least one stage in the stage of these (1)～(6) implements antacid and handles.Handle if only implement antacid afterwards, then might sneak into impurity, therefore preferably carry out antacid in the stage of (1)～(5) as far as possible and handle at rectification working process (B).
Antacid is handled for example can enumerate following method: (I) add antacid and well-mixed method in the residue after initial feed, reaction solution, organic solvent are removed, the cut after the rectifying; (II) make the method for residue after initial feed, reaction solution, organic solvent are removed, the cut after the rectifying post by being filled with antacid; And (III) before or when carrying out in the rectifying, in distillation and/or rectifying column, fill the method for antacid etc. in operation (B).Treatment temp under these situations is generally about room temperature～130 ℃, is preferably about room temperature～100 ℃.In addition, for example, when using amorphous silica-alumina gel, be preferably about 40～100 ℃ as antacid.If treatment temp is too high, may cause the decomposition of parent material Cl-EC or object F-EC.Treatment time was generally about 3～5 hours.From being easy to the viewpoint of the scale that enlarges, special preferred method is the method for (III).
The usage quantity of antacid is according to as each conditions such as the kind of the antacid of the kind of the Cl-EC of process object or F-EC, use, the remaining quantity of halogen root, the content of multi-fluorinated compounds and different, can not decide without exception, usually, with respect to Cl-EC or F-EC100 mass parts, be preferably about 1～50 mass parts, consider the advantage of cost face, more preferably about 1～10 mass parts.
The viewpoint of the speed of response when fluoridizing operation from seeking to improve, antacid treatment process (C) are preferably being fluoridized operation (A) before, promptly in advance initial feed (Cl-EC) are handled.
In addition, fluoridize operation (A) afterwards and rectification working process (B) carry out antacid treatment process (C) before since the halogen root is controlled at aspect minimum favourable and preferred.
In addition, (simultaneously promptly) carries out antacid treatment process (C) owing to be easy to the expansion scale preferably in rectification working process (B).
Organic solvent is removed operation (D)
From suppressing the viewpoint that F-EC decomposes, distillation temperature is below 100 ℃, preferably under reduced pressure carries out.
Solid state component is removed operation (E)
Antacid can be after antacid treatment process (C) immediately or in operation subsequently, adopt the method for removing such as solid state component such as filtrations grade to remove.
The F-EC that obtains like this is high purity (more than 99%, further being more than 99.5%), makes the content of impurity such as halogen root be reduced to not enough 1ppm.As a result, painted through also not taking place for a long time, be to have eliminated the solvent that hinders key element as the solvent of electrolytic solution.
In addition, when the degree of the removing miss the mark of impurity such as halogen root (painted etc.), can implement antacid treatment process (C) and rectification working process (B) repeatedly.
Embodiment
Enumerate embodiment below manufacture method of the present invention is described, but the invention is not restricted to these embodiment.
The analytical procedure that following embodiment uses is as described below.
(1)NMR
Device: BRUKER makes AC-300
Condition determination:
19F-NMR:282MHz (phenylfluoroform=-62.3ppm)
1H-NMR:300MHz (phenylfluoroform=7.51ppm)
(2) vapor-phase chromatography (GC)
Device: the system GC-17A of Shimadzu Seisakusho Ltd.
Post: DB624 (J﹠amp; W scientific corporate system)
Condition determination: 100 ℃ → keep 5 minutes → heat up → 230 ℃ with 10 ℃/minute
Embodiment 1 (operation (A) antacid is before handled)
Antacid treatment process (C)
In 500g (4.08mol, pH1～2) Cl-EC (Aldrich corporate system), add 100g amorphous silica-alumina gel (the product river changes into the secado KW of Co., Ltd.'s system, neutral silica gel, trade(brand)name), at room temperature stirred 2 hours.
Solid state component is removed operation (E)
After stirring end, by removing by filter amorphous silica-alumina gel, the Cl-EC (pH6～7) that modulation is handled through antacid.
Fluoridize operation (A)
Return line is installed on top at the 3L glass there-necked flask that is equipped with whipping appts, adds the spray-dired Potassium monofluoride of 355g (6.12mol), under vacuum stir on one side, adopt the flame desiccating method to remove moisture on one side.Use syringe to add the Cl-EC of 1.3L acetonitrile, the processing of 500g (4.08mol) process antacid then, stir.React for 85 ℃ in temperature of reaction, with vapor-phase chromatography (GC) analysis process.Reacted 6 hours, and confirmed that the raw material peak disappeared, reaction finishes.After reaction finished, the salt in the filtering reaction resultant (Potassium monofluoride, Repone K etc.) obtained reaction solution (pH2～3).
Organic solvent is removed operation (D)
Use vaporizer from the gained reaction solution, to distill and remove acetonitrile.At this moment, the small amount of acid that generates at the fluoridation by-product is also volatilized.
Rectification working process (B)
Use thorn shape to separate (vigreux, リ グ リ
ユ-) pipe in rectifying, obtains the water white F-EC as 74 ℃ of (1mmHg) cuts with residue (pH3～4), yield is 63%, GC purity is 99.8%.
Carry out
19F-NMR,
1H-NMR analyzes, and identifies gained F-EC.
19F-NMR (deuterated acetone) :-122.6～-122.3ppm (1F)
1H-NMR (deuterated acetone): 4.54～4.91ppm (2H), 6.42～6.68ppm (1H)
Then, the refining F-EC of gained is carried out following test.The result is as shown in table 1.
(non-coloring is arranged)
At room temperature preserved one day, range estimation is judged non-coloring.
Zero: do not see painted.
*: see painted.
(anion analysis)
As device, use the system ion chromatograph HIC-20ASUPER of Shimadzu Scisakusho Ltd (limit of detection: 1ppm), measure negatively charged ion (Cl
-, F
-, I
-, NO
2, NO
3, PO
4, SO
4) concentration.
(metal ion analysis)
As device, use the system Emission Spectrophotometer device SPS3000ICP of Seiko Instrument Co., Ltd. (limit of detection: 10ppm), measure the concentration of metal ion (Al, Fe, Ca, K, Mg, Na, Ni, Zn).
(pH mensuration)
Utilize the pH (alkalescence or acid) of the F-EC after the colour developing research rectifying of litmus paper.And, use low conductivity water-non-aqueous solvent to measure pH in addition with pH electrode (the system 6377-10D of Horiba Ltd).
Embodiment 2 (operation (A) antacid is afterwards handled)
Fluoridize operation (A)
Return line is installed on top at the 3L glass there-necked flask that is equipped with whipping appts, adds the spray-dired Potassium monofluoride of 355g (6.12mol), under vacuum stir on one side, adopt the flame desiccating method to remove moisture on one side.Use syringe to add 1.3L acetonitrile, the untreated Cl-EC of 500g (4.08mol) then, stir.React for 85 ℃ in temperature of reaction, with vapor-phase chromatography (GC) analysis process.Reacted 6 hours, and confirmed that the raw material peak disappeared, reaction finishes.After reaction finished, the salt in the filtering reaction resultant obtained reaction solution (pH1～2).
Antacid treatment process (C)
(particle diameter 0.063～0.200mm) at room temperature stirred 2 hours for merck corporate system silica gel 60, trade(brand)name to add 100g silica gel in gained filtrate.
Solid state component is removed operation (E)
Then, antacid (silica gel) etc. is filtered.
Organic solvent is removed operation (D)
Use vaporizer from gained filtrate (pH6～7), to distill and remove acetonitrile.
Rectification working process (B)
Use thorn shape separator tube that residue (pH6～7) is supplied to obtain the water white F-EC as 74 ℃ of (1mmHg) cuts in rectifying, yield is 60%, and GC purity is 99.5%.
To this refining F-EC, operation similarly to Example 1 has non-coloring, anion analysis, metal ion analysis and pH to measure.The results are shown in table 1.
Embodiment 3 (operation (A) antacid is afterwards handled)
(the product river changes into the system secado KW of Co., Ltd. to use amorphous silica-alumina gel, neutral silica gel, trade(brand)name) silica gel that uses in the antacid treatment process (C) of replacement embodiment 2, in addition, operation similarly to Example 2, obtain the water white F-EC as 74 ℃ of (1mmHg) cuts, yield is 65%, and GC purity is 99.6%.
To this refining F-EC, operation similarly to Example 1 has non-coloring, anion analysis, metal ion analysis and pH to measure.The results are shown in table 1.
Embodiment 4 (operation (A) antacid is before handled)
Use aluminum oxide (merck corporate system aluminum oxide 90, trade(brand)name, the silica gel that uses in the antacid treatment process of particle diameter 0.063～0.200mm) replacement embodiment 1, in addition, operation similarly to Example 1, obtain the water white F-EC as 74 ℃ of (1mmHg) cuts, yield is 68%, and GC purity is 99.8%.
To this refining F-EC, operation similarly to Example 1 has non-coloring, anion analysis, metal ion analysis and pH to measure.The results are shown in table 1.
Embodiment 5 (antacid in the operation (B) is handled)
Fluoridize operation (A)
Return line is installed on top at the 3L glass there-necked flask that is equipped with whipping appts, adds the spray-dired Potassium monofluoride of 355g (6.12mol), under vacuum stir on one side, adopt the flame desiccating method to remove moisture on one side.Use syringe to add 1.3L acetonitrile, the untreated Cl-EC of 500g (4.08mol) then, stir.React for 85 ℃ in temperature of reaction, use vapor-phase chromatography (GC) analysis process.Reacted 6 hours, and confirmed that the raw material peak disappeared, reaction finishes.After reaction finished, the salt in the filtering reaction resultant (Potassium monofluoride, Repone K etc.) obtained reaction solution (pH1～2).
Organic solvent is removed operation (D)
Use vaporizer from the reaction solution that obtains, to distill and remove acetonitrile.At this moment, the acid in the filtrate is also volatilized.
Rectification working process (B)+antacid treatment process (C)
Use is filled with the distillation tower of amorphous silica-alumina gel (the product river changes into the secado KW of Co., Ltd.'s system, neutral silica gel, trade(brand)name), and residue (pH3～4) in rectifying, is obtained the water white F-EC as 74 ℃ of (1mmHg) cuts.
To this refining F-EC, operation similarly to Example 1 has non-coloring, anion analysis, metal ion analysis and pH to measure.The results are shown in table 1.
Embodiment 6 (antacid after the operation (B) is handled)
Fluoridize operation (A)
Return line is installed on top at the 3L glass there-necked flask that is equipped with whipping appts, adds the spray-dired Potassium monofluoride of 355g (6.12mol), under vacuum stir on one side, adopt the flame desiccating method to remove moisture on one side.Use syringe to add 1.3L acetonitrile, the untreated Cl-EC of 500g (4.08mol) then, stir.React for 85 ℃ in temperature of reaction, with vapor-phase chromatography (GC) analysis process.Reacted 6 hours, and confirmed that the raw material peak disappeared, reaction finishes.After reaction finished, the salt in the filtering reaction resultant (Potassium monofluoride, Repone K etc.) obtained reaction solution (pH1～2).
Organic solvent is removed operation (D)
Use vaporizer from the gained reaction solution, to distill and remove acetonitrile.At this moment, the acid in the filtrate is also volatilized.
Rectification working process (B)
Use thorn shape separator tube that residue (pH3～4) is supplied to obtain the water white F-EC as 74 ℃ of (1mmHg) cuts in rectifying.
Antacid treatment process (C)
In gained F-EC cut, add 100g amorphous silica-alumina gel (the product river changes into the secado KW of Co., Ltd.'s system, neutral silica gel, trade(brand)name), at room temperature stirred 2 hours.
Solid state component is removed operation (E)
Remove amorphous silica-alumina gel by filtering from gained antacid processing F-EC, obtain refining F-EC, yield is 61%, and GC purity is 99.6%.
To this refining F-EC, operation similarly to Example 1 has non-coloring, anion analysis, metal ion analysis and pH to measure.The results are shown in table 1.
Comparative example 1
Except that the antacid treatment process of not carrying out embodiment 1, operation obtains the flaxen F-EC as 74 ℃ of (1mmHg) cuts similarly to Example 1, and yield is 62%, and GC purity is 99.5%.
To this refining F-EC, operation similarly to Example 1 has non-coloring, anion analysis, metal ion analysis and pH to measure.The results are shown in table 1.
By table 1 result as can be known, handle by carrying out antacid, do not take place paintedly, halogen root (chlorine and fluorion etc.) reduces, and the content of metal ion is also few.
Embodiment 7～12
All as the acetonitrile of organic solvent, refining F-EC is made in addition operation equally in each example of use N-Methyl pyrrolidone replacement embodiment 1～6.
To the refining F-EC of gained, operation similarly to Example 1 has non-coloring, anion analysis, metal ion analysis and pH to measure.The results are shown in table 2.
As shown in Table 2, when using N-Methyl pyrrolidone as organic solvent, also can not take place paintedly, halogen root (chlorine and fluorion etc.) reduces, and the content of metal ion is also few.
Embodiment 13～18
Respectively fluoridizing in the operation (A) of embodiment 1～6, all add with respect to 355g (6.12mol) Potassium monofluoride be the tetrabutyl ammonium fluoride (TBAF) of 10 moles of % as catalyzer, refining F-EC is made in addition operation equally.
To the refining F-EC of gained, operation similarly to Example 1 has non-coloring, anion analysis, metal ion analysis and pH to measure.The results are shown in table 3.
By table 3 result as can be known, when TBAF is fluoridized as catalyzer, also can not take place paintedly, halogen root (chlorine and fluorion etc.) reduces, and the content of metal ion is also few.
Claims (11)
1. 4-fluoro-1, the manufacture method of 3-dioxolane-2-ketone is characterized in that, comprising:
Utilize fluorizating agent to 4-chloro-1 in organic solvent, 3-dioxolane-2-ketone carries out fluorizated operation (A);
To gained contain 4-fluoro-1, the 3-dioxolane-reaction solution of 2-ketone carries out the operation (B) of rectifying; With
The operation of handling with antacid (C).
2. manufacture method as claimed in claim 1 is characterized in that:
Carry out antacid treatment process (C) before fluoridizing operation (A).
3. manufacture method as claimed in claim 1 is characterized in that:
Carry out antacid treatment process (C) before afterwards and at rectification working process (B) fluoridizing operation (A).
4. manufacture method as claimed in claim 1 is characterized in that:
In rectification working process (B), carry out antacid treatment process (C).
5. manufacture method as claimed in claim 1 is characterized in that:
Carry out antacid treatment process (C) afterwards at rectification working process (B).
6. manufacture method as claimed in claim 1 is characterized in that:
Fluoridizing operation (A) afterwards and before, comprise the operation (D) of removing organic solvent at rectification working process (B).
7. as each described manufacture method in the claim 1～6, it is characterized in that:
Described antacid is the oxide compound of alkaline-earth metal, the supercarbonate of alkaline-earth metal, the phosphoric acid salt of alkaline-earth metal, the carboxylate salt of alkaline-earth metal, alkali-metal supercarbonate, alkali-metal phosphoric acid salt, alkali-metal carboxylate salt, Si oxide, aluminum oxide, sial composite oxides or wherein two or more.
8. as each described manufacture method in the claim 1～6, it is characterized in that:
Described antacid is antacid porous mass.
9. as each described manufacture method in the claim 1～6, it is characterized in that:
Described antacid is Si oxide, aluminum oxide, sial composite oxides or two or more porous mass wherein.
10. as each described manufacture method in the claim 1～6, it is characterized in that:
Described fluorizating agent is the compound shown in the formula MF, and wherein, M is alkali metal atom or quaternary ammonium cation.
11., it is characterized in that as each described manufacture method in the claim 1～6:
With pH regulator is 6～7, and carries out rectification working process (B) under this condition.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2008-048609 | 2008-02-28 | ||
| JP2008048609 | 2008-02-28 | ||
| JP2008048609 | 2008-02-28 | ||
| JP2008-292412 | 2008-11-14 | ||
| JP2008292412 | 2008-11-14 | ||
| JP2008292412 | 2008-11-14 |
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| CN101519398A true CN101519398A (en) | 2009-09-02 |
| CN101519398B CN101519398B (en) | 2013-07-03 |
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| CN 200910118346 Expired - Fee Related CN101519398B (en) | 2008-02-28 | 2009-02-27 | Preparation of 4-fluoro-1,3-dioxolane-2-one |
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| JP (1) | JP5600876B2 (en) |
| CN (1) | CN101519398B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102060838A (en) * | 2010-12-31 | 2011-05-18 | 浙江华晶氟化学科技有限公司 | Method for preparing fluoroethylene carbonate |
| CN102134227A (en) * | 2010-12-31 | 2011-07-27 | 上海康鹏化学有限公司 | Preparation method of fluoroethylene carbonate |
| CN101717389B (en) * | 2009-10-29 | 2013-01-09 | 江苏华盛精化工股份有限公司 | Disacidifying and dewatering method of fluoroethylene carbonate |
| CN102887883A (en) * | 2012-09-26 | 2013-01-23 | 中国海洋石油总公司 | Continuous purifying method of crude product of fluoroethylene carbonate |
| JP2013505921A (en) * | 2009-09-28 | 2013-02-21 | ソルヴェイ（ソシエテ アノニム） | Composition of fluorinated organic carbonate and Lewis acid |
| CN106916137A (en) * | 2017-03-01 | 2017-07-04 | 山东瀛寰化工有限公司 | A kind of industrial process of electron level fluorinated ethylene carbonate |
| CN107033119A (en) * | 2017-04-06 | 2017-08-11 | 多氟多化工股份有限公司 | A kind of preparation method of high-purity fluorinated ethylene carbonate |
| CN110156743A (en) * | 2019-05-24 | 2019-08-23 | 泰兴华盛精细化工有限公司 | A kind of synthetic method of fluorinated ethylene carbonate |
| CN116396264A (en) * | 2023-03-03 | 2023-07-07 | 山东惟普新能源有限公司 | Method for preparing fluoroethylene carbonate by solvent-free one-pot method |
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| PL3595072T3 (en) | 2017-03-08 | 2024-03-11 | Sumitomo Seika Chemicals Co., Ltd. | Additive for non-aqueous electrolytic solutions, non-aqueous electrolytic solution, and electrical storage device |
| WO2022025002A1 (en) | 2020-07-31 | 2022-02-03 | 住友精化株式会社 | Additive for non-aqueous electrolyte, non-aqueous electrolyte, and power storage device |
| KR20230067597A (en) | 2020-09-14 | 2023-05-16 | 스미토모 세이카 가부시키가이샤 | Additives for non-aqueous electrolytes, non-aqueous electrolytes and electrical storage devices |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| PL143528B1 (en) * | 1984-07-02 | 1988-02-29 | Wojskowa Akad Tech | Method of obtaining novel liquid crystal derivatives of dioxane |
| JPH09131836A (en) * | 1995-11-09 | 1997-05-20 | Daikin Ind Ltd | Bag structure for packaging fluororesin material |
| JP4848684B2 (en) * | 2005-06-28 | 2011-12-28 | セントラル硝子株式会社 | Method for producing high-purity 4-fluoro-1,3-dioxolan-2-one |
| JP4848683B2 (en) * | 2005-06-28 | 2011-12-28 | セントラル硝子株式会社 | Method for producing high-purity 4-fluoro-1,3-dioxolan-2-one |
-
2009
- 2009-01-30 JP JP2009019330A patent/JP5600876B2/en not_active Expired - Fee Related
- 2009-02-27 CN CN 200910118346 patent/CN101519398B/en not_active Expired - Fee Related
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| JP2013505921A (en) * | 2009-09-28 | 2013-02-21 | ソルヴェイ（ソシエテ アノニム） | Composition of fluorinated organic carbonate and Lewis acid |
| CN101717389B (en) * | 2009-10-29 | 2013-01-09 | 江苏华盛精化工股份有限公司 | Disacidifying and dewatering method of fluoroethylene carbonate |
| CN102060838A (en) * | 2010-12-31 | 2011-05-18 | 浙江华晶氟化学科技有限公司 | Method for preparing fluoroethylene carbonate |
| CN102134227A (en) * | 2010-12-31 | 2011-07-27 | 上海康鹏化学有限公司 | Preparation method of fluoroethylene carbonate |
| CN102887883A (en) * | 2012-09-26 | 2013-01-23 | 中国海洋石油总公司 | Continuous purifying method of crude product of fluoroethylene carbonate |
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| WO2018184379A1 (en) * | 2017-04-06 | 2018-10-11 | 多氟多化工股份有限公司 | Preparation method for high purity fluoroethylene carbonate |
| CN107033119B (en) * | 2017-04-06 | 2019-10-11 | 多氟多化工股份有限公司 | A kind of preparation method of high-purity fluorinated ethylene carbonate |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP5600876B2 (en) | 2014-10-08 |
| JP2010138157A (en) | 2010-06-24 |
| CN101519398B (en) | 2013-07-03 |
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