CN105541782A - Vinylene carbonate purifying method - Google Patents
Vinylene carbonate purifying method Download PDFInfo
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- CN105541782A CN105541782A CN201510957380.2A CN201510957380A CN105541782A CN 105541782 A CN105541782 A CN 105541782A CN 201510957380 A CN201510957380 A CN 201510957380A CN 105541782 A CN105541782 A CN 105541782A
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- vinylene carbonate
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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
- C07D317/34—Oxygen atoms
- C07D317/40—Vinylene carbonate; Substituted vinylene carbonates
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- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a vinylene carbonate purifying method, most of impurities and water are removed by adsorption filtration, and high purity vinylene carbonate can be obtained by vacuum distillation and cooling crystallization. The vinylene carbonate purifying method is short in processing time, low in reaction temperature and high in yield, and the resulting product is high in purity.
Description
Technical field
The present invention relates to a kind of purification process of carbonic ether, especially a kind of purification process of vinylene carbonate.
Background technology
Vinylene carbonate (VC, VinyleneCarbonate) is colourless transparent liquid under room temperature (20-25 DEG C).The application of vinylene carbonate widely; it can as a kind of component of top coat; also be production of chemicals, medicine, crop protection agents and the special important intermediate for polymkeric substance, coating and battery electrolyte; it can form the polymerized thylene carbonate vinyl acetate of higher molecular weight as polymer monomer under free radical initiation; vinylene carbonate can react with many organic compound in addition, synthesizes many fine-chemical intermediates.
It has good high temperature performance and anti-inflatable function; can as the additive of lithium-ion battery electrolytes; be at present research relatively deeply and organic film for additive of lithium-ion battery electrolytes satisfactory for result, and it or additives for overcharge protection additive.Raolical polymerizable can be there is in vinylene carbonate on lithium ion batteries anodes surface, generate poly-alkylcarbonic acid lithium compound, occur because this polyreaction is better than EC, therefore can effectively suppress electrolyte solvent molecule at the last decomposition of electrode surface, thus improve the performance of Carbon anode.The close structure formed by above polyreaction but do not increase solid electrolyte interface (Solidelectrolyteinterphase, the SEI) film of impedance, thus improves the electrode capacity of lithium ion battery, cyclical stability and work-ing life.
In order to obtain the vinylene carbonate of higher degree, the method that generally employ direct rectifying is purified.The method has following shortcoming: one is that vinylene carbonate easily decomposes and coking, and the loss of raw material is comparatively large, and transformation efficiency is not high, and this is determined by the heat sensitivity of vinylene carbonate itself.Two is the organochlorines that cannot remove in product.Three is the residual of moisture.
And vinylene carbonate is as important lithium-ion battery electrolytes additive, its product to moisture and purity requirement high, a small amount of water will cause the reduction of circulation of elecrolyte degradation, capacity even to damage battery, therefore has higher requirement to the production technique of vinylene carbonate.
Summary of the invention
For solving above-described problem, the invention provides a kind of impurity and the moisture content that reduce product, improving the purification process of the vinylene carbonate of product purity.
For achieving the above object, the technical solution used in the present invention is to provide a kind of purification process of vinylene carbonate, and the method comprises:
A) in nitrogen atmosphere, vinylene carbonate crude product is mixed 1:0.5 ~ 1 in mass ratio with organic solvent, mixed solution is warming up to 25 ~ 35 DEG C, stir add appropriate dewatering agent and sorbent material in mixed solution after, filter elimination solids component, and with a small amount of organic solvent washing filter cake, collect filtrate and washing lotion pending;
B) filtrate of collection is carried out rectification under vacuum under 10mmHg vacuum condition in rectifying tower, the cut collecting 25 ~ 40 DEG C is pending;
C) when the cut temperature of collecting is down to below 20 DEG C, add in cut with its weight ratio is that the organic solvent of 1 ~ 2:1 mixes, appropriate crystal seed is added after temperature is down to 18 DEG C, then carry out cooling precipitation and crystallization, filtration, vacuum lyophilization, obtain vinylene carbonate high purity goods.
Preferably, organic solvent described in step a and step c is one or more the combination be selected from benzene,toluene,xylene, ethylbenzene, trimethylbenzene, isopropyl benzene.
Further preferably, described organic solvent is toluene.
Preferably, dewatering agent described in step a is molecular sieve, anhydrous magnesium sulfate or Calcium Chloride Powder Anhydrous.
Preferably, sorbent material described in step a is molecular sieve, polymeric adsorbent, activated alumina or silica gel.
Preferably, porous adsorption layer is provided with in the rectifying tower described in step b.
Compared with the prior art, by using technical scheme of the present invention, the present invention has the following advantages: the purification process of vinylene carbonate of the present invention, most of organochlorine impurity in crude product and moisture is first removed by using water-retaining agent and sorbent material, and then carry out rectification under vacuum and the cooling further removal of impurities of precipitation and crystallization and anhydrate, organic solvent usage quantity in purge process can be reduced, shorten rectifying; By adding crystal seed, reduce crystallization time; Carry out at a lower temperature in whole purge process, the rotten of vinylene carbonate can be avoided, improve yield.Adopt the high purity vinylene carbonate after method purifying of the present invention can as the additive of lithium-ion battery electrolytes.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described in detail, but the present invention is not limited to following examples.The reaction conditions adopted in embodiment can require to make further adjustment according to the concrete difference used.
Embodiment 1
Nitrogen is passed in 1L tetra-mouthfuls of round-bottomed flasks, maintain nitrogen atmosphere add the crude product (vinylene carbonate mass percentage content is 90%) of 100g vinylene carbonate and 80g toluene and open stirring, 3g anhydrous magnesium sulfate and 3g activated alumina is added after mixture being warming up to 30 DEG C, stir and filter elimination solids component after 30 minutes, and with 5g toluene wash filter cake, collect filtrate and washing lotion.Collected filtrate and washing lotion rectifying tower are carried out rectification under vacuum under the vacuum tightness of 10mmHg, collects the cut of 25 ~ 40 DEG C.Collected cut temperature is added in crystallizer, when cut temperature is down to 19 DEG C, add 100g toluene wherein and open stirring, when temperature is reduced to 18 DEG C, add the solid-state vinylene carbonate sterling of 2g (purity 99.99%) as crystal seed, be cooled to about 5 DEG C and stir precipitation and crystallization 2 hours.After crystallization terminates, leach solid carbonic acid vinylene, and carry out vacuum lyophilization at 0 DEG C, obtain the vinylene carbonate 90.2g that purity is 99.6%, yield 98.0%.
Embodiment 2
Nitrogen is passed in 1L tetra-mouthfuls of round-bottomed flasks, maintain nitrogen atmosphere add the crude product (vinylene carbonate mass percentage content is 90%) of 100g vinylene carbonate and 50g toluene and open stirring, 3g Calcium Chloride Powder Anhydrous and 3g molecular sieve is added after mixture being warming up to 28 DEG C, stir and filter elimination solids component after 30 minutes, and with 5g toluene wash filter cake, collect filtrate and washing lotion.By collected filtrate and washing lotion, the rectifying tower containing porous adsorption layer carries out rectification under vacuum under the vacuum tightness of 10mmHg, collects the cut of 25 ~ 40 DEG C.Collected cut temperature is added in crystallizer, when cut temperature is down to 19 DEG C, add 120g toluene wherein and open stirring, when temperature is reduced to 18 DEG C, add the solid-state vinylene carbonate sterling of 3g (purity 99.99%) as crystal seed, be cooled to about 2 DEG C and stir precipitation and crystallization 3 hours.After crystallization terminates, leach solid carbonic acid vinylene, and carry out vacuum lyophilization at-6 DEG C, obtain the vinylene carbonate 91.6g that purity is 99.8%, yield 98.4%.
Embodiment 3
Nitrogen is passed in 1L tetra-mouthfuls of round-bottomed flasks, maintain nitrogen atmosphere add the crude product (vinylene carbonate mass percentage content is 90%) of 100g vinylene carbonate and 100g toluene and open stirring, 3g Calcium Chloride Powder Anhydrous and 3g activated alumina is added after mixture being warming up to 34 DEG C, stir and filter elimination solids component after 30 minutes, and with 5g toluene wash filter cake, collect filtrate and washing lotion.Collected filtrate and washing lotion rectifying tower are carried out rectification under vacuum under the vacuum tightness of 10mmHg, collects the cut of 25 ~ 40 DEG C.Collected cut temperature is added in crystallizer, when cut temperature is down to 19 DEG C, add 180g toluene wherein and open stirring, when temperature is reduced to 18 DEG C, add the solid-state vinylene carbonate sterling of 3g (purity 99.99%) as crystal seed, be cooled to about 0 DEG C and stir precipitation and crystallization 2.5 hours.After crystallization terminates, leach solid carbonic acid vinylene, and carry out vacuum lyophilization at-6 DEG C, obtain the vinylene carbonate 90.7g that purity is 99.8%, yield 97.4%.
Above-described embodiment is only for illustrating technical conceive of the present invention and feature; its object is to person skilled in the art can be understood content of the present invention and be implemented; can not limit the scope of the invention with this; all equivalences done according to spirit of the present invention change or modify, and all should be encompassed in protection scope of the present invention.
Claims (6)
1. a purification process for vinylene carbonate, comprising:
A) in nitrogen atmosphere, vinylene carbonate crude product is mixed by weight 1:0.5 ~ 1 with organic solvent, mixed solution is warming up to 25 ~ 35 DEG C, stir add appropriate dewatering agent and sorbent material in mixed solution after, filter elimination solids component, and with a small amount of organic solvent washing filter cake, collect filtrate and washing lotion pending;
B) filtrate of collection and washing lotion are carried out rectification under vacuum under 10mmHg vacuum condition in rectifying tower, collect the cut of 25 ~ 40 DEG C;
C) when the cut temperature of collecting is down to below 20 DEG C, add in cut with its weight ratio is that the organic solvent of 1 ~ 2:1 mixes, appropriate crystal seed is added after temperature is down to 18 DEG C, then carry out cooling precipitation and crystallization, filtration, vacuum lyophilization, obtain vinylene carbonate high purity goods.
2., according to the purification process described in claim 1, wherein organic solvent described in step a and step c is one or more the combination be selected from benzene,toluene,xylene, ethylbenzene, trimethylbenzene, isopropyl benzene.
3., according to the purification process described in claim 2, wherein said organic solvent is toluene.
4., according to the purification process described in claim 1, wherein dewatering agent described in step a is molecular sieve, anhydrous magnesium sulfate or Calcium Chloride Powder Anhydrous.
5., according to the purification process described in claim 1, wherein sorbent material described in step a is molecular sieve, polymeric adsorbent, activated alumina or silica gel.
6., according to the purification process described in claim 1, in the rectifying tower wherein described in step b, be provided with porous adsorption layer.
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| CN201510957380.2A CN105541782A (en) | 2015-12-18 | 2015-12-18 | Vinylene carbonate purifying method |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107501231A (en) * | 2017-07-25 | 2017-12-22 | 苏州华新能源科技有限公司 | A kind of preparation method of vinylene carbonate |
| CN110655499A (en) * | 2018-06-29 | 2020-01-07 | 东营市海科新源化工有限责任公司 | Method and system for purifying battery-grade vinylene carbonate by adopting falling film crystallization coupled rectification |
| CN112375062A (en) * | 2020-11-20 | 2021-02-19 | 泰兴华盛精细化工有限公司 | Method for recovering vinylene carbonate from vinylene carbonate tar |
| CN113636999A (en) * | 2021-07-26 | 2021-11-12 | 珠海理文新材料有限公司 | Water removal and crystallization method of vinylene carbonate |
| CN114507207A (en) * | 2022-01-13 | 2022-05-17 | 北京天弘天达医药科技股份有限公司 | Method for purifying vinylene carbonate by rectification-melt crystallization coupling technology |
| CN115232100A (en) * | 2022-09-21 | 2022-10-25 | 湖南省正源储能材料与器件研究所 | Method for recovering solvent in vinylene carbonate rectification process |
| WO2023098188A1 (en) * | 2021-11-30 | 2023-06-08 | 苏州华一新能源科技股份有限公司 | Vinylene carbonate, preparation method, and lithium battery electrolyte using same |
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| CN104402855A (en) * | 2014-10-31 | 2015-03-11 | 中国海洋石油总公司 | Vinylene carbonate dehydration distillation technology |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107501231A (en) * | 2017-07-25 | 2017-12-22 | 苏州华新能源科技有限公司 | A kind of preparation method of vinylene carbonate |
| CN107501231B (en) * | 2017-07-25 | 2018-08-14 | 苏州华一新能源科技有限公司 | A kind of preparation method of vinylene carbonate |
| CN110655499A (en) * | 2018-06-29 | 2020-01-07 | 东营市海科新源化工有限责任公司 | Method and system for purifying battery-grade vinylene carbonate by adopting falling film crystallization coupled rectification |
| CN110655499B (en) * | 2018-06-29 | 2021-08-24 | 东营市海科新源化工有限责任公司 | Method and system for purifying battery-grade vinylene carbonate by adopting falling film crystallization coupled rectification |
| CN112375062A (en) * | 2020-11-20 | 2021-02-19 | 泰兴华盛精细化工有限公司 | Method for recovering vinylene carbonate from vinylene carbonate tar |
| CN113636999A (en) * | 2021-07-26 | 2021-11-12 | 珠海理文新材料有限公司 | Water removal and crystallization method of vinylene carbonate |
| WO2023098188A1 (en) * | 2021-11-30 | 2023-06-08 | 苏州华一新能源科技股份有限公司 | Vinylene carbonate, preparation method, and lithium battery electrolyte using same |
| CN114507207A (en) * | 2022-01-13 | 2022-05-17 | 北京天弘天达医药科技股份有限公司 | Method for purifying vinylene carbonate by rectification-melt crystallization coupling technology |
| CN115232100A (en) * | 2022-09-21 | 2022-10-25 | 湖南省正源储能材料与器件研究所 | Method for recovering solvent in vinylene carbonate rectification process |
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Application publication date: 20160504 |