CN104718198A - Preparation of purified fluorosubstituted organic carbonates - Google Patents

Preparation of purified fluorosubstituted organic carbonates Download PDF

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CN104718198A
CN104718198A CN201380052486.7A CN201380052486A CN104718198A CN 104718198 A CN104718198 A CN 104718198A CN 201380052486 A CN201380052486 A CN 201380052486A CN 104718198 A CN104718198 A CN 104718198A
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group
fluorine
prepurification
organic carbonates
reaction mixture
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M.邦坎普
A.兰伯特
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Solvay SA
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Solvay SA
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D317/42—Halogen atoms or nitro radicals

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A process for the preparation of purified fluorosubstituted organic carbonates, especially of fluoroethylene carbonate, difluoroethylene carbonate, fluoromethyl methyl carbonate and difluorinated dimethyl carbonate from ethylene carbonate and dimethyl carbonate and F2 is described. After fluorination, and preferably after performing a step of hydrogen fluoride depletion, the impure fluorosubstituted organic carbonates are subjected to a treatment with an agent of formula (I), R-H, wherein R is a nucleophilic group, and a subsequent step of distillation in at least one distillation column. Alcohols and amines, for example, are suitable as agent of formula (I). Methanol is especially preferred.

Description

The preparation of the organic carbonate of the fluorine replacement of purifying
This application claims the right of priority of the European application numbers 12187801.1 submitted on October 9th, 2012, for all objects, the full content of this application is combined in this by reference.
The present invention relates to the method for the organic carbonate that a kind of fluorine for the preparation of some purifying replaces.
The straight chain fluoridized and the carbonic ether of ring-type, such as, carbonic acid list fluoroethylene, carbonic acid fluorine carboxylic acid methyl ester, carbonic acid two fluoroethylene and difluorizated methylcarbonate, and also have corresponding three-and tetrafluorizated carbonic ether, be especially suitable as the solvent for lithium ion battery or solvent additive.
Usually, the organic carbonate that replaces of fluorine can by do not replaced by F or the reaction with the acyclic straight of at least one commutable H atom or the carbonic ether of ring-type and element fluorine prepare.
Carbonic acid list fluoroethylene such as can by corresponding unsubstituted ethylene carbonate by DOX-2-ketone (ethylene carbonate; " EC ") prepare with the reaction of element fluorine.This is described in such as JP-A2000-309583, and wherein, this reaction carries out with a kind of melts of EC or its solution in anhydrous fluorochemical.Optionally, perflexane can be there is; In this case, a kind of suspension of DOX-2-ketone (parent material) is defined.According to U.S. Patent Application Publication 2006-0036102, ethylene carbonate to be dissolved in F1EC and then to make it contact with the fluorine of dilution.According to US Patent No.-A 7,268,238, this reaction carries out in a kind of reactor of multiple Raschig ring, to provide the suitable Air Bubble Size of dilution fluorine gas.According to prior art, these fluoridations and product separation carry out in a batch process.
WO 2011/036283 describes a kind of method for the preparation of carbonic acid two fluoroethylene, carbonic acid three fluoroethylene and/or carbonic acid four fluoroethylene or the wherein mixture of two or more, the method by the nonfluorinated in liquid phase or the ethylene carbonate with lower degree of fluorination and element fluorine (F 2) react to form carbonic acid four fluoroethylene.
WO 2009/118369 describes, by making rare gas element pass mixture from this mixture stripping HF from comprising organic carbonate (organic carbonate of preferred fluorinated) and the preparation of hydrofluoric mixture has the mixture of poor hydrogen fluoride content.Rare gas or they with nitrogen or the same rare gas element that is suitable as of mixture of the mixture of carbonic acid gas or it and nitrogen for stripping; Air also may be applicable, but it is not preferred.Nitrogen is especially suitable as stripping gas.
WO 2009/118368 provides a kind of method of the organic carbonate for the preparation of fluorine replacement, the organic carbonate that this fluorine replaces is poor HF, the fluorinated organic carbonates wherein making the HF-comprising at least one CH-CF group in a kind of molecule pollute contacts with the inorganic reaction thing of a kind of SiO2 of comprising, thus form the mixture of the fluorinated organic carbonates of a kind of solid and poor HF, and the organic carbonate that the fluorine of obtained poor HF replaces is separated with this solid.Preferred use has the solid of high surface area, especially amorphous phase solid silica or silica containing compound.It is most preferred that silica gel.The high surface area of this gellike (it can be applied with the form of forming solid, such as, the form with bead) provides the reaction of a kind of quick removing HF-.
WO 2011/020830 provides a kind of method for purification reaction mixture, this reaction mixture comprises carbonic acid fluoroethylene, ethylene carbonate, one or more higher ethylene carbonates of fluoridizing and hydrogen fluoride and optionally trace impurity is (such as, carbonic acid three fluoroethylene), distilled at least two distilation steps by this reaction mixture, the reaction mixture be wherein fed in the first distilation steps comprises the HF being not more than 5% by weight.Preferably, the reaction mixture be fed in this first distillation tower comprises the HF being not more than 1% by weight.The carbonic acid fluoroethylene of the purifying obtained is so pure, especially with regard to HF content, so that do not need recrystallization.
But, observe even by absorption, stripping and/or these crude products of distillation process with after removing HF, in the product of this process, HF is released.
The object of this invention is to provide the method for the organic carbonate that a kind of fluorine for the preparation of purifying replaces.Realized from specification sheets and obvious this object of claims and other objects by method of the present invention.
The present invention relates to a kind of method of the fluorinated organic carbonates for the preparation of purifying, the method comprises at least one wherein makes the organic carbonate fluoridized containing impurity and a kind for the treatment of agent (be selected from by having formula (I), R-H, the group of organic compound composition) step that contacts, the compound wherein with formula (I) and the compound with group-C (O) F react thus form-C (O) R, and the step of at least one wherein fluorinated organic carbonates of separation and purification.
This at least one separating step preferably includes at least one distilation steps.
There is the reagent of formula (I) when probably forming C-(O)-R group with during C-(O)-F radical reaction.
Within the framework of the invention, singulative is intended to comprise plural form; And plural form is intended to comprise singulative.Therefore, term " fluorinated organic carbonates of purifying " is not limited to a kind of single carbonate products, but comprises a kind of composition, and said composition comprises two or more carbonic ethers fluoridized (comprising isomeric forms).
Under this reaction, especially in view of at the temperature of carrying out method of the present invention and reaction times, these compounds with formula (I) should be substantially or completely nonreactive for the organic carbonate fluoridized, and make the impurity not forming not desired amount; Especially in this at least one separating step process can not separated or be difficult to be separated impurity.
Water, H 2s or NH 3treatment agent can be used as; But they are not preferred treatment agents, and if they are employed, then this process should be short as far as possible, such as, be shorter than 5 minutes.
The compound preferably with formula (I) is selected from the group that is made up of organic compound and comprises at least one OH group, NH group or SH group.Typical treatment agent is selected from the group of alkane alcohols, alkanediol class, alkane three alcohols, ammonia, monoalkyl amine, dialkyl amine and alkane thiol class.These treatment agents are preferred.Possible is the mixture more than a kind for the treatment of agent of application from this group.
Especially preferred treatment agent is selected from lower group, and this group is made up of the following: there is the alkanol of 1 to 3 carbon atom, have the alkanediol of a C2 or C3 alkylen backbone, wherein term alkyl represent C1 to a C3 group monoalkylamine and wherein these alkyl groups be identical or different and represent the dialkylamine of C1 to C3 alkyl.Methyl alcohol, ethanol, methylamine, dimethylamine, ethamine, diethylamine, thiomethyl alcohol and sulfur alcohol are especially preferred, and are outstanding as treatment agent methyl alcohol.
Preferably, the reagent with formula (I) is alcohol or amine.
Preferably, R is selected from by R ao and R br cthe group of N composition, wherein R athat be selected from the straight chain with 1 to 10 carbon atom with alkyl group that is side chain; By at least one halogen atom, at least one hydroxyl, at least one nitro and/or at least one itrile group replace there is the straight chain of 1 to 10 carbon atom with the alkyl group of side chain; That there is the straight chain of 2 to 10 carbon atoms with alkenyl group that is side chain; By at least one halogen atom, at least one hydroxyl, at least one nitro and/or at least one itrile group replace there is the straight chain of 1 to 10 carbon atom with the alkyl group of side chain; There is the cyclic alkylidene group of 3 to 10 carbon atoms; By at least one, be there is the alkylidene group with the ring-type of 3 to 10 carbon atoms that the alkyl group of 1 to 5 carbon atom, at least one halogen atom, at least one hydroxyl, at least one nitro and/or at least one itrile group replace; And wherein R band R cbe identical and represent C1 to C6 alkyl; C3 to the C6 alkylidene group of ring-type; Have the saturated of 5 to 8 members or undersaturated heterocyclic ring, wherein this N is combined in this ring.Polyvalent alcohol and polyamines are also useful treatment agents.
Such as, alkylamine and dialkylamine are applicable purifying agents, such as methylamine, dimethylamine, ethamine, diethylamine or methyl ethyl-amine.
Especially preferred as purifying agent alcohols.Alkylol cpd can with amine compound Combination application, but preferably only apply the purifying agent that one or more are selected from the group of alcohols.
Can apply and there is one, the alcohol of two or three OH groups.Such as, have the alcohol of the C1 to C5 of an OH group, C2 to C5 dibasic alcohol or C3 to C6 triol are applicable.R apreferably be selected from the group be made up of methoxyl group, oxyethyl group, positive propoxy, isopropoxy, butoxy, hydroxyl methoxyl group and hydroxy ethoxy.
Methyl alcohol, ethanol, n-propyl alcohol and Virahol is preferably applied as purifying agent.
The amount of this purifying agent should be relevant with there being the amount of one or more impurity to be removed approx.This amount can rule of thumb be estimated.Alternately, the terminal adding this purifying agent can be determined by physics or chemical process.Such as, by vapor-phase chromatography, NIR or MIR.Often, adding this purifying agent makes its amount relative to there being pending reaction mixture to be by weight 0.01% to 5%.In addition, if with relative to the gross weight having a carbonic ether to be purified by weight from 0.01% to 5% amount application, water, NH 3or H 2s is applicable purifying agent, although be more not preferred than other mixtures above-mentioned.If with so low amount application, water is not considered to be used as clean-out system, and such as, for removing the HF of existence, but in the context of the present invention, it is used as a kind of purifying agent worked by chemical reaction.However, alcohols as mentioned above is preferred purifying agent.
This purifying agent can be added in this crude reaction mixture or preferably be added in the product of this prepurification.This reagent can be made to contact in a batch reactor with the product of this crude mixture or this prepurification.Preferably, directly it is added into the bottom of a distillation tower.
Method of the present invention is especially suitable for purifying by organic carbonate that the organic carbonate of acyclic straight or side chain replaces as the fluorine that the reaction of initial compounds and element fluorine produces.
This fluoridation can be carried out in batches or continuously; It provide crude reaction mixture.Fluorine (preferably by nitrogen dilution) is dispersed in the carbonic ether of this liquid state in a gaseous form.Therefore, method of the present invention is a kind of 2-phase method.Fluorine is that the form of diluting is introduced, and to improve the security of the method, and is because create a large amount of reaction heat, if this reaction heat of application of pure fluorine will be very high.
These class methods are such as described in the WO 2011/036281 describing a kind of fluorination process carried out continuously or U.S. Patent Application Publication 2006-0036102.In a replacement scheme, may do not replaced by F atom as the acyclic straight of parent material or the organic carbonate of side chain, and after reacting with element fluorine, corresponding reaction product comprise by least one F atom replace until the fluoridized organic carbonate fluoridized.In a further alternative, to be replaced by least one F atom as the acyclic straight of parent material or the organic carbonate of side chain and comprise at least one H atom, and after reacting with element fluorine, corresponding reaction product comprise by least two F atom replace until the fluoridized organic carbonate fluoridized.
Ladies and gentlemen contriver infers that a kind of undesirable impurity is present in this reaction mixture, and it may comprise C (O) F group.So a kind of group tends to divide HF when itself and contact with moisture.There is the reagent of formula (I) when forming C-(O)-R group with during C-(O)-F radical reaction.
Aforesaid is only a kind of experimental explanation, and ladies and gentlemen contriver does not wish by its constraint.
Now, the organic carbonate that can replace according to the fluorine of the inventive method purifying is described.
According to a replacement scheme, can the acyclic straight that replaces of purified fluorine or the organic carbonate of side chain in the method in accordance with the invention.Especially, formula (I) ((R can be had by purifying 1o) (R 2o) C (O)) fluorine replace organic carbonate.In formula (I), R 1and R 2can be identical or different.R 1and R 2be straight chained alkyl or branched-chain alkyl, its condition is R 1and R 2in at least one replaced by least one F atom.C1 to the C5 alkyl group that term " straight chained alkyl " preferably represents C1 to a C5 alkyl group or replaced by least one F atom.C3 to the C5 alkyl group that term " branched-chain alkyl " preferably represents C3 to a C5 alkyl group or replaced by least one F atom.As mentioned above, condition is R 1and R 2in at least one must be replaced by least one F atom.Below will not repeat this condition.
Preferably, R 1methyl, methyl fluoride, difluoromethyl, trifluoromethyl, ethyl, fluoro ethyl, two fluoro ethyls, trifluoroethyl, four fluoro ethyls or pentafluoroethyl group, n-propyl, sec.-propyl, the n-propyl replaced by 1 to 7 F atom or the sec.-propyl replaced by 1 to 7 F atom.Preferably, R 2methyl, methyl fluoride, difluoromethyl, trifluoromethyl, ethyl, fluoro ethyl, two fluoro ethyls, trifluoroethyl, four fluoro ethyls or pentafluoroethyl group, n-propyl, sec.-propyl, the n-propyl replaced by 1 to 7 F atom or the sec.-propyl replaced by 1 to 7 F atom.
According to another replacement scheme, there is formula (II) ((OR 3o) C (O)) fluorine replace aliphatic cyclic organic carbonate according to method purifying of the present invention.R 3preferably one has the aliphatics alkylidene group of 2 to 10 C atoms and is replaced by least 1 F atom.More preferably, R 3it is C2 to a C8 group replaced by least 1 F atom.Especially preferably, R 3it is a C2 group replaced by 1,2,3 or 4 F atom; By the C3 group of the straight or branched that at least 1 F atom replaces; By the methyl propylene group that at least 1 F atom replaces; By the dimethylethylene group that at least 1 F atom replaces; By the ethylethylene residue group that at least 1 F atom replaces; By the diethyl ethylene group that at least 1 F atom replaces; Or by the methylethyl ethylene group of at least 1 F atom replacement.Preferably, in this alternate embodiment, R 3single fluorine ethylidene, difluoro ethylidene, trifluoro ethylidene, tetrafluoro ethylidene, single methyl fluoride ethylidene, difluoromethyl ethylidene, methyl list fluorine ethylidene, methyl difluoro ethylidene, single methyl fluoride list fluorine ethylidene, single methyl fluoride difluoro ethylidene, difluoromethyl list fluorine ethylidene, difluoromethyl difluoro ethylidene, trifluoromethyl difluoro ethylidene, difluoromethyl trifluoro ethylidene or trifluoromethyl trifluoro ethylidene.In this embodiment, R 3preferably single fluorine ethylidene, difluoro ethylidene, trifluoro ethylidene, tetrafluoro ethylidene, and optimum menu fluorine ethylidene or difluoro ethylidene." difluoro ethylidene " can be a CF 2c-CH 2group or the CFH-CFH group in cis or transconfiguration.
This organic carbonate fluoridized can be as providing of such as describing in JP-A 2000-309583, US 2006-0036102, US-A 7,268,238 or WO 2011036281.
Method of the present invention may be used for a kind of fluorinated product also not standing purification process of purifying.Alternately, it may be used for the fluorinated product of a kind of prepurification of purifying, and but the fluorinated product of this prepurification has stood a kind of prepurification process to provide the carbonic ether fluoridized of prepurification to be considered to pure not for the solvent or additive that are used as lithium ion battery; Or it may be used for a kind of product of purifying, although the product of this purifying is considered to enough pure for the solvent or additive that are used as lithium ion battery, when storing or still forming some HF when contacting with moisture content.
Preferably first carry out the earlier step that at least one removes HF from this crude reaction mixture, this crude reaction mixture is included in one and uses the organic carbonate fluoridized obtained in the fluorination process of element fluorine.Expert it is well known that in this fluorination step, for consuming the F of every mole 2, produce the HF of a mole.Some methods are suitable for the preliminary purification of this removal HF.Preferred method comprises at least one stripping step, at least one distilation steps or both steps.A kind of method for stripping HF from crude product is described in WO 2009/118369.Make a kind of rare gas element (such as, N 2) through this crude product to remove the HF that carries secretly.Distilling to remove is a kind of replacement scheme, such as, by the multiple distillation of one such as described in WO2011/020830.These two kinds of methods can be combined with each other or be combined to remove HF with a kind of adsorption treatment, such as, by contacting with silica.
The combination of a kind of stripping and distillation is especially preferred as the earlier step of purifying.
After above-mentioned prepurification step, preferably add the HF that this purifying agent exists to remove major part, and preferably added before a final purification step (as distillation).
Preferably by the crude reaction mixture of stripping, distillation or both this fluoridations of prepurification, the content of the HF in the crude product of this prepurification is reduced to be equal to or less than by weight 1%.Often, the content of HF is reduced to and is less than 100ppm by weight.After prepurification, especially after stripping, by weight from the HF of the scope of 100 to 1000ppm be preferred.
Therefore, a preferred embodiment of the method carries out with some steps the carbonic ether providing purifying.
This embodiment comprises the step that a providing package is contained in the reaction of organic carbonate and element fluorine the crude reaction mixture of the organic carbonate fluoridized obtained, to provide a kind of crude reaction mixture comprising the organic carbonate fluoridized with degree of fluorination higher than this parent material; At least one comprises to remove HF that major part carries secretly to provide a kind of subsequent step of prepurification product from this crude reaction mixture; At least one comprises the subsequent step adding this purifying agent; And at least one is separated the step of the fluorinated organic carbonates of this purifying.
In another embodiment, the method comprises the purification step of silicoorganic compound pack processing containing the mixture of this organic carbonate fluoridized that an other use has at least one-Si-N-key, and preferably these silicoorganic compound are selected from organic silazane hydride compounds, organic disilazane compound and organic three silicon nitrogen silane compounds.More preferably, these silicoorganic compound with at least one-Si-N-key are selected from lower group, and this group is made up of the following: (N, N-diethylin) trimethyl silane, N, O-two (trimethyl silyl (sillyl)) ethanamide, N, N '-bis-(trimethyl silyl)-1,4-butanediamine, 1,1,1,3,3,3-hexamethyldisilazane, 1,1,3,3,5,5-pregnancy basic ring three silazane and its any combination.1,1,1,3,3,3-hexamethyldisilazane is especially preferred.This embodiment allows the pollution reducing such as HF and/or water further.
Comprise carbonic ether that a kind of fluorine replaces and HF crude reaction mixture can as describe in document cited above by optionally in a kind of solvent (such as in the HF as a kind of solvent), in a kind of inert solvent (such as in a kind of per-fluorocarbon) or under a kind of organic carbonate fluoridized as thinner exists the reaction of a kind of carbonic ether parent material and element fluorine provide, this carbonic ether parent material is not substituted with at least one fluorine atom or has lower degree of fluorination.
The removal of carrying HF secretly in this subsequent step can be carried out in a way known, such as, by the stripping of use rare gas element (as nitrogen) such as described in WO 2009/118369.This HF removal can also be carried out by the distillation such as described in WO 2011/020830.The combination of stripping and distillation provides a kind of product of suitably prepurification.
According to the present invention, the mixture comprising HF in a wide scope can be processed.In most preferred embodiment, wherein have pending reaction mixture to result from the preparation of the ethylene carbonate of fluorine replacement or the dialkyl carbonate of fluorine replacement, each hydrogen atom replaced by fluorine forms a HF molecule.Usually, in this type of reaction mixture, the content of HF is equal to or less than by weight 10%.But also can pack processing containing the mixture of the more HF of a large amount.
The content of the HF after the treatment in these mixtures is preferably equal to or less than the weighing scale 5% by this reaction mixture, is more preferably equal to or less than the weighing scale 2% by this reaction mixture.Particularly preferably, it is equal to or less than by weight 1%.Also more preferably, it is equal to or less than by weight 0.5%.Particularly preferably, it is equal to or less than by weight 0.1%.
In the simplest mode of one, in containing a container of reaction mixture, stripping can be carried out by rare gas element is blown over this reaction mixture.This can complete in batches or continuously.
Preferably to provide the mode of enough contact area to carry out stripping between reaction mixture and gas.Such as, reaction mixture spraying can be entered in an inert gas flow, or stripping gas can contact with pending liquid in a bubble tower.A kind of method is very preferably carried out in a stripping tower.In a stripping tower, internals or filler are with every m 3equipment has high specific surface area and assembles, to provide the high contact area between gas and liquid.The filler be applicable to is, such as, and Raschig ring.The cylindrical tube that stripping tower is normally vertically placed.The bottom of rare gas element at this stripping tower is introduced lower than filler; By this reaction mixture in its top feed.The rare gas element comprising HF leaves this tower by a separation pipeline at top.
From higher containing the efficiency removing HF the carbonic ether of HF at higher temperature.If this contact carries out in a vessel, then can heat supply in a way known, such as, by the wall of heating container.Optionally, can heated inert gas and/or pending liquid.
If carry out this reaction in a stripping tower with internals or filler, then preferably heated inert gas, pending liquid or both heat, to improve the efficiency of this vaporizing extract process.
Therefore, by rare gas element, especially nitrogen, is advantageously heated before introducing this reaction mixture.The temperature it be heated to preferably is equal to or higher than 60 DEG C; More preferably, it is equal to or higher than 75 DEG C.Most preferably, it is equal to or higher than 100 DEG C.This temperature can also be higher, such as, is equal to or higher than 120 DEG C.Preferably, it is equal to or less than 150 DEG C.Depend on thermotolerance and the erosion resistance of container used, post, tubing, accessory etc., this temperature can higher than 150 DEG C.
Preferably before carrying out a continuous stripping process, also heat this reaction mixture.If a container is used for carrying out a kind of batch process, then can before this stripping process and/or period heat this reaction mixture.Preferably, it is heated to the temperature being equal to or higher than 60 DEG C.Preferably, it is heated to the temperature being equal to or less than 120 DEG C.
It is very favorable for carrying out this stripping step under ambient pressure.If desired, slight vacuum can be used.Such as, pressure can be decreased to 0.5 bar or even 0.2 bar.Temperature not should too high so that organic compound can along with inert gas flow from wherein taking out of.
In a kind of batch process, carry out stripping until there is the HF of the maximum of wishing.
In a kind of continuous processing, in a stripping tower, select the height of this tower to make, for the flow rate of given HF concentration, rare gas element and a reaction mixture, reach desired remaining HF concentration.
This prepurification can also be carried out by the some distillations such as described in WO 2011/020830.In this approach, at least two distilation steps, distill crude reaction mixture, the reaction mixture be wherein fed in the first distilation steps comprises the HF being no more than 5% by weight.Preferably, the reaction mixture be fed in this first distillation tower comprises the HF being not more than 1% by weight.Before these distilation steps, excessive HF can such as be removed by stripping.
Term " at least two distilation steps " represents makes this mixture at least pass twice through a distillation tower.According to an embodiment, this is a distillation tower, makes mixture to be separated by this distillation tower at least twice.This embodiment may be carried out in a kind of batch distillation mode.
According to another embodiment, these at least two distilation steps carry out at least two distillation towers.This embodiment is particularly suitable for carrying out a kind of continuous distillation method.
In first distilation steps, a kind of mixture with more lower boiling many kinds of substance (such as HF and have the carbonates of higher degree of fluorination) is extracted out from top; The component with higher is extracted out from bottom and is fed into second distilation steps.Often, be equal to or less than 100 millibars (absolute values) at the pressure at the top place of the tower of this first distilation steps.Preferably, be equal to or less than 75 millibars (absolute values) at the pressure at the top place of the tower of this first distilation steps.Preferably, it is equal to or greater than 10 millibars (absolute values).In the scope of pressure at the top place of the tower of this first distilation steps especially preferably between 10 and 50 millibars (absolute value).
If wished, the mixture with the more lower boiling many kinds of substance top of the tower from this first distilation steps can extracted out is separated from one another.Such as, can by washing this mixture with water or passing through to remove HF with a kind of this mixture of rare gas element stripping (this is highly preferred).The remaining carbonic ether fluoridized can pass through fractionation by distillation.Alternately, the mixture from the top of the tower of first distilation steps can be separated into multiple different compound without any other process picture washing or stripping simply by distilling.The carbonic ether with higher degree of fluorination is valuable by product, because they can as additive application in solvent for lithium.If wish, they can be outwelled or burn.The hydrogen fluoride of any recovery itself is also all a kind of valuable product.
In second tower, the bottoms of first tower is distilled.Preferably, the pressure at the top place of the tower of this second distilation steps is equal to or less than 50 millibars (absolute values).More preferably, the pressure at the top place of this second tower is equal to or less than 30 millibars (absolute values).Preferably, the pressure at the top place of the tower of this second distilation steps is equal to or greater than 5 millibars (absolute values).At the top of the tower of this second distilation steps, obtain high-purity carbonic ether fluoridized, such as carbonic acid list fluoroethylene.The content of the HF in the carbonic ether of purifying be equal to or less than by weight 30ppm, be preferably equal to or less than 20ppm by weight.Even can realize lower HF content, such as, be equal to or less than 10ppm.
In a preferred embodiment, the HF content in this crude reaction mixture is reached and is equal to or less than 0.1% (that is, being equal to or less than 1000ppm by weight) by weight, to provide a kind of reaction product of prepurification; Then this purifying agent is added, preferred alcohols, such as Virahol, more preferably ethanol and especially methyl alcohol.Preferably, the amount of this purifying agent is that the reaction product of every 100 weight part prepurifications is from 0.01 to 2 weight part.Unexpectedly, the amount of methyl alcohol can lower than the amount of ethanol or Virahol.Such as, ethanol can be applied with the amount being equal to or less than 1 weight part, and methyl alcohol even can add with the amount being equal to or less than by weight 0.6%.
In the adding procedure of this purifying agent, the temperature of this reaction mixture preferably remains on from 0 DEG C to 100 DEG C, preferably 60 DEG C in the scope of 100 DEG C, and this pressure corresponds to environmental stress.
If wish, this reaction mixture can being remained on a post-reaction period, such as, continuing to be equal to or greater than 1 minute to being equal to or less than 5 hours.For reactive purifying agent such as methyl alcohol, this residence time can lower than the lower reagent such as Virahol of reactivity.
Then this reaction mixture is distilled to provide the fluorinated organic carbonates of purifying.
This distillation preferably has in the tower of enough theoretical plate numbers (such as, 10 to 50) at one to be carried out providing a kind of enough pure product.
The advantage of this purified product is when storing or any impurity that can form HF when contacting with moisture is removed by method of the present invention.In the process determining remaining HF content, this is also favourable, determines to carry out under water in interpolation because this.These impurity and water react and form HF; This causes determining the content than unborn higher Free HF.
Be combined in this patent, patent application and the disclosure content of publication and the afoul degree of the explanation of the application by reference if any to term may be caused unclear, then this explanation should be preferential.
The present invention will make an explanation not to be intended to limiting example of the present invention now.
Abbreviation:
EC: ethylene carbonate
F1EC: carbonic acid fluoroethylene
F2EC: carbonic acid two fluoroethylene
GC: vapor-phase chromatography
Example 1: the preparation of carbonic acid list fluoroethylene and prepurification
1.1. the preparation of the crude reaction mixture of carbonic acid list fluoroethylene (" F1EC ") is comprised
The preparation of this F1EC is the F by ethylene carbonate (" EC ") and the volume ratio in 13: 87 2/ N 2reaction to carry out, by F 2/ N 2pass into continuously in the EC in this reactor.This crude reaction mixture comprises as organic as determined by GC, carbonic acid two fluoroethylene (" F2EC ") (as measured by GC) of the EC of 50 area %, the F1EC of 45 area % and 5 area %; It also comprises the HF of by weight 10%.
1.2. the prepurification of this crude reaction mixture
In a stripping tower at the temperature of about 110 DEG C by making crude reaction mixture and the N of example 1.1 2contact makes this crude mixture stand stripping and the content of HF is reduced to by weight about 0.2%.
1.3. the interpolation of methyl alcohol
To in the reaction mixture of the prepurification of example 1.2, add methyl alcohol with the amount of this mixture of every 100g 0.5g methyl alcohol.This reaction is carried out at 80 DEG C.
1.4. separating step
After interpolation methyl alcohol, distill the reaction mixture that produces under vacuo to provide highly purified F1EC.
Example 2: the purifying using ethanol
Repeat example 1, but the amount of ethanol is set to by weight 0.85%.
Example 3: the preparation of carbonic acid fluorine carboxylic acid methyl ester
Highly purified carbonic acid list fluorine carboxylic acid methyl ester is prepared in one approach, the method comprises the methylcarbonate that is similar to as described at example 1 and a kind of fluorine/noble gas mixtures reacts, subsequently stripping HF, then add the step of methyl alcohol and distillation.

Claims (14)

1. the method for the preparation of the fluorinated organic carbonates of purifying, the method comprises use and has formula (I), R-H, and wherein R is nucleophilic group, the step of the impure fluorinated organic carbonates of agent treated, and the subsequent step distilled at least one distillation tower.
2. the method for claim 1, wherein R-H is selected from the group be made up of the alcohols optionally replaced and amine.
3. method as claimed in claim 2, wherein R is selected from by R ao and R br cthe group of N composition, wherein R athat be selected from the straight chain with 1 to 10 carbon atom with alkyl group that is side chain; By at least one halogen atom, at least one hydroxyl, at least one nitro and/or at least one itrile group replace there is the straight chain of 1 to 10 carbon atom with the alkyl group of side chain; That there is the straight chain of 2 to 10 carbon atoms with alkenyl group that is side chain; By at least one halogen atom, at least one hydroxyl, at least one nitro and/or at least one itrile group replace there is the straight chain of 1 to 10 carbon atom with the alkyl group of side chain; There is the cyclic alkylidene group of 3 to 10 carbon atoms; By at least one, be there is the alkylidene group with the ring-type of 3 to 10 carbon atoms that the alkyl group of 1 to 5 carbon atom, at least one halogen atom, at least one hydroxyl, at least one nitro and/or at least one itrile group replace; And wherein R band R cbe identical and represent C1 to C6 alkyl; C3 to the C6 alkylidene group of ring-type; Have the saturated of 5 to 8 members or undersaturated heterocyclic ring, wherein this N is combined in this ring.
4. method as claimed any one in claims 1 to 3, wherein R-H is alcohol.
5. method, wherein R as claimed in claim 4 abe selected from methoxyl group, oxyethyl group, propoxy-, butoxy, hydroxyl methoxyl group and hydroxy ethoxy.
6. the method according to any one of claim 1 to 5, wherein this impure fluorinated organic carbonates is the product of crude reaction mixture or prepurification, this crude reaction mixture obtains from the reaction comprising the step that at least one makes element fluorine and the organic carbonate with lower fluorine substitution value reacts, and the product of this prepurification is from comprising at least one step making element fluorine and the organic carbonate with lower fluorine substitution value react and reaction that at least one removes hydrofluoric step obtains.
7. method as claimed in claim 6, wherein the fluorinated organic carbonates of prepurification is purified, and the fluorinated organic carbonates of this prepurification is from comprising at least one step making element fluorine and the organic carbonate with lower fluorine substitution value react and reaction that at least one removes hydrofluoric step obtains.
8. method as claimed in claim 7, the process wherein for exhausting hydrogen fluoride content is selected from stripping and distillation.
9. the method according to any one of claim 1 to 8, the hydrogen fluoride content wherein in this impure fluorinated organic carbonates is equal to or less than 1000ppm.
10. method as claimed in any one of claims 1-9 wherein, wherein this organic carbonate fluoridized is selected from lower group, and this group is made up of the following: carbonic acid list fluoroethylene, carbonic acid fluorine carboxylic acid methyl ester, carbonic acid two fluoroethylene and carbonic acid two-(methyl fluoride) ester.
11. methods according to any one of claim 1 to 10, wherein this amount with the reagent of formula (I) is equal to or less than by weight 1%.
12. methods according to any one of claim 1 to 11, comprise the following steps:
A) at least one makes fluorine react the step to obtain the crude reaction mixture comprising the organic carbonate fluoridized with the organic carbonate with lower degree of fluorination, and this organic carbonate fluoridized contains hydrogen fluoride;
B) at least one removes the hydrogen fluoride that is included in this crude reaction mixture to obtain the step of the fluorinated organic carbonates of poor hydrofluoric prepurification;
C) at least one uses this to have the step of the fluorinated organic carbonates of this prepurification of agent treated of formula (I);
D) at least one fluorinated organic carbonates that this passes through this prepurification of distillation after having the agent treated of formula (I) in use reclaims the step of the fluorinated organic carbonates of purifying.
13. methods according to any one of claim 1 to 12, the reagent wherein this with formula (I) is introduced into the bottom of distillation tower.
14. methods according to any one of claim 1 to 13, be included in the silicoorganic compound with at least one-Si-N-key exist under be further purified step.
CN201380052486.7A 2012-10-09 2013-10-08 Preparation of purified fluorosubstituted organic carbonates Pending CN104718198A (en)

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