CN1958582A - Method for preparing vinylene carbonate - Google Patents
Method for preparing vinylene carbonate Download PDFInfo
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- CN1958582A CN1958582A CN 200510115555 CN200510115555A CN1958582A CN 1958582 A CN1958582 A CN 1958582A CN 200510115555 CN200510115555 CN 200510115555 CN 200510115555 A CN200510115555 A CN 200510115555A CN 1958582 A CN1958582 A CN 1958582A
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Abstract
This invention discloses a method for preparing vinylene carbonate. The method comprises contact-reacting monohalogenated vinyl carbonate and hydrogen-halide-removing agent. The hydrogen-halide-removing agent is alkali metal hydroxide particles with particle sizes smaller than 5 mum. The prepared vinylene carbonate can be easily purified to purity higher than 99.5% (GC) through conventional distillation and crystallization techniques. Besides, the overall yield can reach 85%. The hydrogen-halide-removing agent is easy to obtain, the reaction time is short, and the operation is easy.
Description
Technical field
The invention relates to a kind of preparation method of vinylene carbonate, especially about a kind of method for preparing vinylene carbonate by a halogenated ethylene carbonate.
Background technology
Vinylene carbonate as the additive of high reaction activity, can suppress the electrolytical various reaction that takes place do not wished, the decomposition reaction of resolving into LiF etc. as lithium hexafluoro phosphate in lithium-ion secondary cell.Vinylene carbonate can generate the SEI film of excellent property in the negative terminal surface of lithium-ion secondary cell, and then can improve the efficiency for charge-discharge and the cycle characteristics of lithium-ion secondary cell, is therefore more and more favored.
American chemical will, 77,3789-3793 (1995) discloses a kind of preparation method of vinylene carbonate, this method comprises that at first the chlorination reaction by ethylene carbonate prepares monochloro-Ethylene Carbonate, then monochloro-Ethylene Carbonate is under refluxad spent the night with the triethylamine reaction in ether solvents, obtain vinylene carbonate behind the dehydrochlorination.After removing ether solvents and distillation, the productive rate with 59% obtains thick vinylene carbonate, and then further purifying is carried out in rectifying.The defective of this method is that the yield of long reaction time, target product is low.
CN1139585C discloses a kind of preparation method of vinylene carbonate, this method comprises with NSC 11801 as solvent, and a halogenated ethylene carbonate is obtained vinylene carbonate separating by vacuum distilling after by dehydrohalogenation under the dehydrohalogenating agent effect again.Provide the embodiment that makes dehydrohalogenating agent with triethylamine in this patent the method for preparing vinylene carbonate is described.Obviously, there is following shortcoming in this method: it is low that this patent prepares vinylene carbonate concentration, and described in this patent, generally, the ethylene carbonate ester solvent does not separate with the product vinylene carbonate and is directly used in the electrolyte of lithium-ion secondary battery.Thereby the ethylene carbonate that makes in this way can only be used for some specific end use not high to the ethylene carbonate purity requirement.
Summary of the invention
The objective of the invention is to make in order to overcome in the prior art preparation method of vinylene carbonate that the vinylene carbonate yield is low, the not segregative shortcoming of product, the preparation method of the vinylene carbonate of a kind of vinylene carbonate yield height and the easily separated purification of product is provided.
The inventor notices, used dehydrohalogenating agent is the alkali hydroxide soln that is conventionally used as dehydrohalogenating agent in the CN1139585C patent, and well known to a person skilled in the art and be, alkali metal hydroxide is a kind of mineral alkali, be insoluble to organic solvent, in the described solvents ethylene carbonate of this patent, and generally described alkali hydroxide soln all refers to the aqueous solution of alkali metal hydroxide, because the product vinylene carbonate itself that a halogenated ethylene carbonate contact reacts obtains is very responsive to moisture, therefore, this reaction can not be used the aqueous solution.Therefore, use which type of alkali hydroxide soln and how to use this solution those skilled in the art to learn.In fact, the present inventor is through scrutinizing and a large amount of experiments, and also not obtaining can be as the alkali hydroxide soln of dehydrohalogenating agent.
The invention provides a kind of preparation method of vinylene carbonate, this method comprises carries out contact reacts with a halogenated ethylene carbonate and dehydrohalogenating agent, and wherein, described dehydrohalogenating agent is a granularity less than 5 microns alkali metal hydroxide particle.
Prepare the yield of vinylene carbonate up to 85% with method provided by the invention, the separation and purification of product is very easy to, can make degree of purity of production reach 99.5% (GC) with routine distillation and crystallization technique, used dehydrohalogenating agent raw material is easy to get, and the reaction times is short and simple to operate.The vinylene carbonate that makes with method provided by the invention can be as the carrier of the additive of lithium-ion secondary cell, nonaqueous electrolytic solution solvent, top coat component, immobilized enzyme or the monomer that is used for preparing the polymerized thylene carbonate vinyl acetate be used for various application.And the present invention has also successfully realized the contact reacts between a mineral alkali and the halogenated ethylene carbonate, has broken the traditional method that can only prepare NSC 11801 with organic bases as dehydrohalogenating agent.
Embodiment
Comprise according to the preparation method of vinylene carbonate provided by the invention a halogenated ethylene carbonate and dehydrohalogenating agent are carried out contact reacts, wherein, described dehydrohalogenating agent is that granularity is removed the thing particle less than 5 microns alkali metal hydrogen oxidations.
According to preparation method provided by the invention, although all can realize the present invention with various proportionings between the reactant, under the preferable case, the mol ratio of reactant one halogenated ethylene carbonate and dehydrohalogenating agent is 0.5-4.0, is preferably 1.0-2.0.
Described alkali metal hydroxide can be one or more in sodium hydroxide, potassium hydroxide, the lithium hydroxide.The granularity of described alkaline hydrated oxide particle is less than 5 microns, and preferred size accounts for more than 50% of particle total amount less than 3 microns particle.The granularity of the alkali metal hydroxide particle that makes with ordinary method is bigger, can not satisfy needs of the present invention, thereby need make its granularity be less than 5 microns to directly being purchased or carrying out refinement with the alkali metal hydroxide that ordinary method prepares.Can make the granularity of above-mentioned alkaline hydrated oxide be less than 5 microns in various manners, for example can handle by under drying conditions, using the mode of ball milling and/or vibration mill, the concrete operations of ball milling and/or vibration mill have been conventionally known to one of skill in the art, do not repeat them here.The time of ball milling and/or vibration mill can be 2-24 hour, is preferably 6-15 hour.The granularity that the particle size distribution analysis instrument of the model X100 that can produce with U.S. Honeywell company is tested oxyhydroxide, the dispersion solvent of surveying granularity can be CH
3COCH
3Granularity of the present invention is meant the diameter of spheroidal particle.
Because the particle diameter of conventional basic metal particle is big and be insoluble in a halogenated ethylene carbonate or its organic solution, thereby can not fully contact between basic metal and the halogenated ethylene carbonate, thereby can not realize contact reacts.And among the present invention, because the alkali metal hydroxide solids are carried out abundant refinement, make its granularity less than 5 microns, such particle has the unrivaled character of conventional macroparticle, thereby can unexpectedly carry out contact reacts with a halogenated ethylene carbonate, generate the target product vinylene carbonate.A described halogenated ethylene carbonate can be one or more in a fluorine NSC 11801, monochloro-Ethylene Carbonate, monobromo NSC 11801, the iodine NSC 11801.Consider the preferred monochloro-Ethylene Carbonate that uses in the specific embodiment of the invention from aspects such as the degree that is easy to get of raw material and reactive behavioies.A described halogenated ethylene carbonate can be commercially available, also can in all sorts of ways and prepare, for example can also halogenating reaction take place by sulfuryl chloride and NSC 11801 and make by NSC 11801 and halogen are made by the photochemistry halogenating reaction under initiator such as azo isobutyronitrile effect.
Although in the absence that solvent exists, granularity can directly come in contact reaction with a halogenated ethylene carbonate less than 5 microns alkali metal hydroxide, but because above-mentioned reaction belongs to the neutralization reaction of acid and alkali, react more violent and wayward, thereby the present invention preferably carries out above-mentioned contact reacts in the presence of solvent.
Described solvent can be various organic solvents, if can and a halogenated ethylene carbonate form homogeneous phase and the contact reacts between dehydrohalogenating agent and the halogenated ethylene carbonate do not produced interference, for example can be ether, tetrahydrofuran (THF), benzene, crown ether-like, acetone, ethanol, methyl alcohol, sherwood oil, chlorobenzene, dimethylbenzene, toluene, N, one or more in dinethylformamide, pyridine, the methyl-sulphoxide.Be preferably above-mentioned solvent mid-boiling point and differ solvent more than 20 ℃ than vinylene carbonate boiling point.More preferably boiling point is lower than 110 ℃ low boiling point organic solvent under the normal pressure, for example sherwood oil, ether, tetrahydrofuran (THF), benzene, crown ether-like solvent, described crown ether-like solvent comprise crown ether-like such as 18-hat-6, dibenzo 18-hat-6, two cyclohexanes and 18-hat-6,12-crown-4.More preferably boiling point is lower than 90 ℃ solvent under the normal pressure.Because the crown ether-like solvent costs an arm and a leg, the preferred mixed solvent that uses a spot of crown ether and other solvent in the specific embodiment of the invention, the volume ratio of crown ether and other solvent is preferably 1: 10-20.
The present invention does not have special requirement to the order of addition(of ingredients) of above-mentioned solvent, a halogenated ethylene carbonate, dehydrohalogenating agent, can earlier a halogenated ethylene carbonate and whole solvent be added in the reactor, and then the adding dehydrohalogenating agent reacts; Also can react with a halogenated ethylene carbonate again behind the mixture with dehydrohalogenating agent and solvent formation dehydrohalogenating agent and solvent earlier; A part of solvent can also be mixed forming solution with a halogenated ethylene carbonate, another part solvent mixes the mixture (for example suspension liquid) that forms dehydrohalogenating agent and solvent with dehydrohalogenating agent, and then with the two mixing, reaction.Preferred above-mentioned the third mode of the present invention, be about to a part of solvent and mix the mixture that forms solvent and dehydrohalogenating agent with dehydrohalogenating agent, another part solvent is mixed formation solution with a halogenated ethylene carbonate, the mixture that will contain dehydrohalogenating agent and solvent then mixes, reacts with a halogenated ethylene carbonate solution.This operating method helps controlling the temperature of reaction system.Wherein, the content of dehydrohalogenating agent is preferably the 1.0-6.0 mol in the described mixture that contains dehydrohalogenating agent and solvent, and the concentration of a halogenated ethylene carbonate solution is preferably the 1.0-4.5 mol.Dehydrohalogenating agent can be joined in the halogenated ethylene carbonate, also a halogenated ethylene carbonate can be joined in the dehydrohalogenating agent and react.The mixture that the present invention preferably will contain dehydrohalogenating agent and solvent slowly joins in the halogenated ethylene carbonate solution and carries out contact reacts.The mixture that the mode that preferred employing drips will contain dehydrohalogenating agent and solvent joins in the halo carbon vinyl acetate solution.The speed that drips so that temperature of reaction change and be no more than 5 ℃ and be as the criterion.In order to make reaction evenly, described contact reacts is preferably carried out under agitation condition, and the speed of stirring is preferably 100-300 rev/min.Because alkali metal hydroxide is insoluble in the organic solvent of the present invention, thereby granularity of the present invention can not form the solution of homogeneous in above-mentioned organic solvent less than 5 microns alkali metal hydroxide ultrafine powder, leave standstill inevitable layering of for some time, therefore in order to prevent system layering, the mixture that preferably gained is contained alkali metal hydroxide ultrafine powder and solvent stirs every now and then.
Because vinylene carbonate is very responsive to temperature, decomposes in following a few hours in the temperature that is higher than 60 ℃ usually, even when being higher than 80 ℃, just can decompose fully in the number minute.But usually, temperature of reaction is high more, helps catalytic carrying out more, so preferable reaction temperature of the present invention is 30-60 ℃, and the time of reaction is preferably 2-20 hour.Can come control reaction temperature by variety of way, for example can come control reaction temperature by water-bath.
Because vinylene carbonate is also very responsive to moisture, therefore for decomposition that reduces vinylene carbonate and the generation of avoiding other side reaction that may exist as far as possible, the preferred described solvent of the present invention is an anhydrous solvent.Described anhydrous solvent can for example can carry out drying by add siccative such as molecular sieve, silica gel, aluminum oxide in solvent by carrying out drying and dewater being purchased or ining all sorts of ways with the solvent that ordinary method makes.Decide on moisture content in the solvent time of drying, and moisture content is high more, and time of drying is long more; Moisture content is low more, and time of drying is short more.For the analytical pure benzene solvent that is purchased, be 24-48 hour common time of drying.
The another kind of mode that reduces moisture content in the reaction system is to make to be reflected to carry out above-mentioned reaction under the protection of inert gas.Described rare gas element is meant not one or more in any gas of having an effect with reactant and product, as in nitrogen, the periodic table of elements zero group gas one or more.Preferred rare gas element is nitrogen and/or argon gas.More preferably drying nitrogen and/or argon gas.
Can also come moisture content in the minimizing system by add an amount of siccative in reactor, described siccative can be one or more in molecular sieve, aluminum oxide, the silica gel, is preferably the 5A molecular sieve.Add-on to siccative has no particular limits, and is generally the 10-30 weight % of dehydrohalogenating agent, solvent and a halogenated ethylene carbonate total amount.
Above-mentioned three kinds of methods that reduce the reaction system moisture content can be used separately, also can two or more unite use, and the present invention preferably unites use.
According to preparation method provided by the invention, can also comprise and separate purification contacting reacted product.Those skilled in the art are easy to expect product is separated the method for purification according to above-mentioned description about reaction.For example the mixture that obtains after the reaction can be filtered, remove solid matter, the filtrate distillation, steam solvent at first at a lower temperature, (as under 3 mmhg 46-50 ℃) steams vinylene carbonate under reduced pressure then, remaining is high boiling material, so separately the difficult volatile matter of solid matter, low boiling component and high boiling point, obtain thick product vinylene carbonate, then the gained vinylene carbonate is carried out recrystallization, can obtain the very high target product vinylene carbonate of purity.Described recrystallization solvent can be used ether, toluene, dimethylbenzene equal solvent.
The present invention adopts the mode of gas-matter coupling (GC-MS) to judge the generation and the purity thereof of vinylene carbonate.Used gas chromatograph-mass spectrometer is that the model that U.S. Hewlett Packard produces is the gas chromatograph-mass spectrometer of HP5890, and helium is carrier gas.
The following examples will the invention will be further described.
Embodiment 1
Present embodiment is used to illustrate the preparation method of vinylene carbonate provided by the invention.
The 60 gram particle degree potassium hydroxide ultrafine powder that to be 1-10 micron and granularity account for 58 weight % of total particle less than 3 micron particle joined in 40 milliliters the hexaoxacyclooctadecane-6-6 and mix with 400 milliliters of anhydrous tetrahydro furans then, obtain containing the suspension liquid of hexaoxacyclooctadecane-6-6, tetrahydrofuran (THF) and potassium hydroxide.Under the drying nitrogen protection; under 130 rev/mins of stirring velocitys, 200 gram one chlorocarbonic acid vinyl acetate and 1000 milliliters of anhydrous tetrahydro furan solvents and 50 gram 5A molecular sieves are joined in the reactor; heating simultaneously makes solution temperature remain on 40 ℃; then the above-mentioned suspension liquid that contains crown ether, tetrahydrofuran (THF) and potassium hydroxide is added drop-wise in the reactor; the control temperature of reaction system is no more than 45 ℃, drips complete back and continues to stir 15 hours.Then reaction mixture is filtered, use the oil pump underpressure distillation again, collect the cut of 46-50 ℃ (3 mmhg), get the colourless cut of 142.5 grams.Then above-mentioned cut is carried out recrystallization with 300 milliliters of solvents, obtain GC purity and be 99.8% colorless product 121.4 grams, overall yield of reaction is 86.6%.Occur 86 molecular ion peak on the MS spectrogram and tangible peak do not occur, prove that this colorless product is the target product vinylene carbonate at 122,125 places.
Embodiment 2
Present embodiment is used to illustrate the preparation method of vinylene carbonate provided by the invention.
Join the 83 gram particle degree sodium hydroxide ultrafine powder that to be 1-10 micron and granularity account for 68 weight % of total particle less than 3 micron particle in 400 milliliters of ether and stir, obtain containing the suspension liquid of ether and sodium hydroxide.Under nitrogen protection, 172 gram monobromo NSC 11801 and 500 milliliters of ether and 30 gram silica gel are joined in the reactor; under 300 rev/mins of stirrings; the above-mentioned suspension liquid that contains ether and potassium hydroxide is added drop-wise in the reactor; control reaction temperature is no more than 50 ℃, drips to finish back continuation stirring about 6 hours.Then reaction mixture is used the oil pump underpressure distillation, collected the cut of 46-50 ℃ (3 mmhg), get the colourless cut of 84 grams.Then above-mentioned cut is carried out recrystallization with 300 milliliters of ether solvents, obtain GC purity and be 99.5% colorless product 67.4 grams, overall yield of reaction is 76%.GC-MS identifies that this colorless product is the target product vinylene carbonate.
Embodiment 3
Present embodiment is used to illustrate the preparation method of vinylene carbonate provided by the invention.
With 48 gram particle degree be the lithium hydroxide ultrafine powder of 1-10 micron add in 20 milliliter of 12 hat-4 ether and with 400 milliliters of benzene in and stir, obtain containing the suspension liquid of crown ether, benzene and lithium hydroxide.Under nitrogen protection, 280 gram one iodo NSC 11801 and 400 milliliters of benzene and 60 gram 5A molecular sieves are joined in the reactor; under 200 rev/mins of rotating speeds; system is heated to 60 ℃; then the above-mentioned suspension liquid that contains crown ether, benzene and lithium hydroxide is added drop-wise in the reactor; dripped off at 60 minutes, drip and finish back continuation stirring 5 hours.Then reaction mixture is filtered, remove solid, use the oil pump underpressure distillation again, collect the cut of 46-50 ℃ (3 mmhg), get the colourless cut of 105 grams.Then above-mentioned cut is carried out recrystallization with 350 milliliters of toluene solvants, obtain GC purity and be 99.6% colorless product 89 grams, overall yield of reaction is 79%.GC-MS identifies that this colorless product is the target product vinylene carbonate.
Embodiment 4
Present embodiment is used to illustrate the preparation method of vinylene carbonate provided by the invention.
With 80 gram particle degree is that the potassium hydroxide ultrafine powder of 1-10 micron joins in 20 milliliters of dibenzo, 18 hats six and with 400 milliliters of acetone and stirs, and obtains containing the suspension liquid of acetone, dibenzo 18 hats six and potassium hydroxide.Under nitrogen protection 220 gram monochloro-Ethylene Carbonates being restrained aluminium sesquioxides with 600 milliliters of acetone and 80 joins in the reactor; under 200 rev/mins of stirrings and under 45 ℃; the above-mentioned suspension liquid that contains acetone, dibenzo 18 hats six and potassium hydroxide is added drop-wise in the reactor; the control temperature of reaction system is no more than 50 ℃, drips complete back and continues to stir about 6 hours.Then reaction mixture is filtered, removes solid matter, use the oil pump underpressure distillation again, collect the cut of 46-50 ℃ (3 mmhg), get the colourless cut of 150.0 grams.Then above-mentioned cut is carried out recrystallization with 600 milliliters of toluene solvants, obtain GC purity and be 99.8% colorless product 123.8 grams, overall yield of reaction is 80%.GC-MS identifies that this colorless product is the target product vinylene carbonate.
Embodiment 5
Present embodiment is used to illustrate the preparation of vinylene carbonate provided by the invention.
200 gram monochloro-Ethylene Carbonates are joined in the reactor, and under 100 rev/mins of rotating speeds, dividing 3 times is that the sodium hydroxide of 1-10 micron joins in the reactor with 80 gram particle degree, and control reaction temperature is 40 ℃ and is continuing stirring about 10 hours under this temperature.Then reaction mixture is used the water pump underpressure distillation, collected the colourless cut of 46-50 ℃ (3 mmhg).Then the above-mentioned colourless cut of gained 112 gram is carried out recrystallization with 400 milliliters of toluene solvants, obtain GC purity and be 99.5% colorless product 98.9 and restrain, yield is 70%.GC-MS identifies that this colorless product is the target product vinylene carbonate.
Claims (15)
1, a kind of preparation method of vinylene carbonate, this method comprise a halogenated ethylene carbonate and dehydrohalogenating agent contact reacts, it is characterized in that, described dehydrohalogenating agent is a granularity less than 5 microns alkali metal hydroxide particle.
2, method according to claim 1, wherein, granularity accounts for more than 50% of particle gross weight less than 3 microns particle in the described alkali metal hydroxide particle.
3, method according to claim 1 and 2, wherein, described alkali metal hydroxide is selected from one or more in sodium hydroxide, potassium hydroxide, the lithium hydroxide.
4, method according to claim 1, wherein, a described halogenated ethylene carbonate is selected from one or more in a fluorinated ethylene carbonate, monochloro-Ethylene Carbonate, monobromo NSC 11801, the iodine NSC 11801.
5, method according to claim 1, wherein, described contact reacts is carried out in the presence of solvent, and a halogenated ethylene carbonate is dissolved in described solvent, and alkali metal hydroxide is insoluble or be slightly soluble in described solvent.
6, method according to claim 5, wherein, the mode of described reaction is for to join the form of mixtures of alkali metal hydroxide with alkali metal hydroxide and solvent in the solution of one halogenated ethylene carbonate and solvent.
7, method according to claim 6, wherein, in the mixture of described alkali metal hydroxide and solvent, the content 1.0-6.0 mol of alkali metal hydroxide.
8, method according to claim 6, wherein, in the solution of a described halogenated ethylene carbonate and solvent, the concentration of a halogenated ethylene carbonate is the 1.0-4.5 mol.
9, according to any described method among the claim 5-8, wherein, described solvent is selected from one or more in the organic solvent that boiling point under the normal pressure is lower than 110 ℃.
10, method according to claim 9, wherein, described boiling point is lower than 110 ℃ of organic solvents and is selected from tetrahydrofuran (THF), benzene, ether, crown ether, the acetone one or more.
11, method according to claim 1 or 5, wherein, the mol ratio of a described alkali metal hydroxide and a halogenated ethylene carbonate is 0.6-2.0.
12, method according to claim 11, wherein, the mol ratio of a described alkali metal hydroxide and a halogenated ethylene carbonate is 1.0-2.0.
13, method according to claim 1 or 5, described contact reacts is under agitation carried out, and the temperature of reaction is 30-60 ℃, and the time of reaction is 6-20 hour.
14, method according to claim 1 or 5, wherein, described contact reacts is carried out in inert atmosphere.
15, method according to claim 1 or 5, wherein, described contact reacts is carried out containing under the condition of siccative, and described siccative is selected from one or more in molecular sieve, silica gel, the aluminum oxide.
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| CNB2005101155551A CN100448864C (en) | 2005-11-04 | 2005-11-04 | Method for preparing vinylene carbonate |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532091A (en) * | 2010-12-21 | 2012-07-04 | 湖北德洲科技发展有限公司 | Method for preparing vinylene carbonate |
| CN104402855A (en) * | 2014-10-31 | 2015-03-11 | 中国海洋石油总公司 | Vinylene carbonate dehydration distillation technology |
| CN105384719A (en) * | 2015-12-14 | 2016-03-09 | 苏州华一新能源科技有限公司 | Vinylene carbonate purification method |
| CN109134422A (en) * | 2018-06-08 | 2019-01-04 | 江苏长园华盛新能源材料有限公司 | The preparation method of vinylene carbonate |
| CN111808064A (en) * | 2020-07-14 | 2020-10-23 | 江苏华盛锂电材料股份有限公司 | Preparation method of vinylene carbonate, vinylene carbonate and application |
| CN113527251A (en) * | 2021-09-01 | 2021-10-22 | 上海如鲲新材料有限公司 | Preparation method of vinylene carbonate |
| CN114797957A (en) * | 2022-05-12 | 2022-07-29 | 辽宁浚成科技有限公司 | Solid catalyst for vinylene carbonate liquid phase synthesis, preparation method and application |
| CN115646533A (en) * | 2022-12-29 | 2023-01-31 | 北京探微精细化工科技有限公司 | Solid catalyst for converting deep chlorination product in monochloroethylene carbonate raw material, preparation method and application |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3368832B2 (en) * | 1998-07-10 | 2003-01-20 | 宇部興産株式会社 | Method for producing vinylene carbonate |
| DE19955944A1 (en) * | 1999-11-19 | 2001-07-19 | Merck Patent Gmbh | Process for the production of vinylene carbonate and its use |
-
2005
- 2005-11-04 CN CNB2005101155551A patent/CN100448864C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532091A (en) * | 2010-12-21 | 2012-07-04 | 湖北德洲科技发展有限公司 | Method for preparing vinylene carbonate |
| CN104402855A (en) * | 2014-10-31 | 2015-03-11 | 中国海洋石油总公司 | Vinylene carbonate dehydration distillation technology |
| CN105384719A (en) * | 2015-12-14 | 2016-03-09 | 苏州华一新能源科技有限公司 | Vinylene carbonate purification method |
| CN109134422A (en) * | 2018-06-08 | 2019-01-04 | 江苏长园华盛新能源材料有限公司 | The preparation method of vinylene carbonate |
| CN111808064A (en) * | 2020-07-14 | 2020-10-23 | 江苏华盛锂电材料股份有限公司 | Preparation method of vinylene carbonate, vinylene carbonate and application |
| CN111808064B (en) * | 2020-07-14 | 2022-06-14 | 江苏华盛锂电材料股份有限公司 | Preparation method of vinylene carbonate, vinylene carbonate and application |
| CN113527251A (en) * | 2021-09-01 | 2021-10-22 | 上海如鲲新材料有限公司 | Preparation method of vinylene carbonate |
| CN114797957A (en) * | 2022-05-12 | 2022-07-29 | 辽宁浚成科技有限公司 | Solid catalyst for vinylene carbonate liquid phase synthesis, preparation method and application |
| CN115646533A (en) * | 2022-12-29 | 2023-01-31 | 北京探微精细化工科技有限公司 | Solid catalyst for converting deep chlorination product in monochloroethylene carbonate raw material, preparation method and application |
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| CN100448864C (en) | 2009-01-07 |
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