CN103113346A - Preparation method of bis-fluoro-ethylene carbonate - Google Patents
Preparation method of bis-fluoro-ethylene carbonate Download PDFInfo
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- CN103113346A CN103113346A CN2013100195700A CN201310019570A CN103113346A CN 103113346 A CN103113346 A CN 103113346A CN 2013100195700 A CN2013100195700 A CN 2013100195700A CN 201310019570 A CN201310019570 A CN 201310019570A CN 103113346 A CN103113346 A CN 103113346A
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- preparation
- difluoroethylene carbonate
- hydrogen fluoride
- reaction
- reactor
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- DSMUTQTWFHVVGQ-UHFFFAOYSA-N 4,5-difluoro-1,3-dioxolan-2-one Chemical compound FC1OC(=O)OC1F DSMUTQTWFHVVGQ-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007789 gas Substances 0.000 claims abstract description 18
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 239000002912 waste gas Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 238000004821 distillation Methods 0.000 claims abstract description 3
- AGQKYUPKNZGEQS-UHFFFAOYSA-N C(C)(=O)OC=C.C(O)(=O)Cl Chemical compound C(C)(=O)OC=C.C(O)(=O)Cl AGQKYUPKNZGEQS-UHFFFAOYSA-N 0.000 claims description 18
- 238000010521 absorption reaction Methods 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 abstract description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 abstract description 6
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 239000002910 solid waste Substances 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- BETICXVUVYXEJX-UHFFFAOYSA-N 4,5-Dichloro-1,3-dioxolan-2-one Chemical compound ClC1OC(=O)OC1Cl BETICXVUVYXEJX-UHFFFAOYSA-N 0.000 abstract 1
- 239000002000 Electrolyte additive Substances 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 238000009413 insulation Methods 0.000 description 6
- 238000005070 sampling Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Abstract
The invention discloses a preparation method of bis-fluoro-ethylene carbonate as an electrolyte additive. The preparation method comprises the following steps of: with bis-chloro-ethylene carbonate and hydrogen fluoride as raw materials, under the protection of nitrogen, carrying out reaction to obtain a mixture containing the bis-fluoro-ethylene carbonate by controlling the reaction temperature at 40-120 DEG C; and then carrying out distillation and purification on the mixture to obtain the bis-fluoro-ethylene carbonate as a needed product. The preparation method has the beneficial effects that the raw materials are cheap and easy to obtain, a process route is simple, no solid waste is generated, the yield is above 90 percent, and hydrogen fluoride as waste gas and hydrogen chloride gas are absorbed through alkali liquor without environmental pollution basically.
Description
Technical field
The present invention relates to a kind of preparation method of electrolysis additive difluoroethylene carbonate.
Background technology
Difluoroethylene carbonate is mainly used in the lithium-ion electrolyte of lithium cell, and difluoroethylene carbonate can effectively improve the high and low temperature resistance of lithium-ion electrolyte, and can improve the flame retardant properties of lithium-ion electrolyte.Difluoroethylene carbonate has two kinds of structural formulas---cis and trans, and its structural formula is as follows:
Or
At present, the preparation difluoroethylene carbonate mainly adopts following method: two chlorocarbonic acid vinyl acetate and fluorochemical react under organic solvent produces the solution that contains difluoroethylene carbonate, carry out again filtering separation, the modes such as precipitation rectifying obtain high-purity difluoroethylene carbonate, there is following shortcoming in aforesaid method: reaction solution need carry out solid-liquid separation, because solid waste is more, need to adopt a large amount of solvents.
Summary of the invention
The preparation method who the purpose of this invention is to provide the difluoroethylene carbonate that a kind of technique is simple, yield is high.
For achieving the above object, the present invention has adopted following technical scheme.
The preparation method of described difluoroethylene carbonate is characterized in: take two chlorocarbonic acid vinyl acetate and hydrogen fluoride as raw material, under nitrogen protection, controlling temperature of reaction is 40～120 ℃, obtains containing the mixture of difluoroethylene carbonate after reaction; Carry out again distilation and obtain required product difluoroethylene carbonate.
Further, the preparation method of aforesaid difluoroethylene carbonate, wherein, described pair of chlorocarbonic acid vinyl acetate has cis and trans two kinds of structural formulas, and its structural formula is as follows:
In actual use, preferably selecting purity is two chlorocarbonic acid vinyl acetate of 70%～99%.
Further, the preparation method of aforesaid difluoroethylene carbonate, wherein, two chlorocarbonic acid vinyl acetate and hydrofluoric mol ratio are 1: 1～1: 10.
Further, the preparation method of aforesaid difluoroethylene carbonate, wherein, in reaction process, hydrogen fluoride gas and nitrogen are passed in reactor continuously and react, the speed that the control hydrogen fluoride gas passes in reactor is 0.1～0.3L/min, and the speed that control nitrogen passes in reactor is 0.5～1.5L/min.
Further, the preparation method of aforesaid difluoroethylene carbonate, wherein, controlling temperature of reaction is 40～60 ℃.
Further, the preparation method of aforesaid difluoroethylene carbonate, wherein, the waste gas hydrogenchloride that produces in reaction process and hydrogen fluoride gas guarantee not cause environmental pollution by alkali liquor absorption.
Further, the preparation method of aforesaid difluoroethylene carbonate, wherein, the process of distilation is: be underpressure distillation under 100mmHg at pressure, collect 60～90 ℃ of cuts.
In above-mentioned reaction process, usually controlling the reaction times is 4-24 hour, till the two chlorocarbonic acid vinyl acetate reactions of main basis are complete.
Beneficial effect of the present invention: raw material is cheap and easy to get, and operational path is simple, does not have solid waste to produce, and yield is more than 90%, and waste gas hydrogen fluoride and hydrogen chloride gas pass through alkali liquor absorption, basic non-environmental-pollution.
Embodiment
Preparation method to difluoroethylene carbonate of the present invention is further described below by specific embodiment.But the present invention is not limited in these embodiment.
Embodiment 1.
(1) in the there-necked flask with stirring, thermometer, prolong and device for absorbing tail gas, adding two chlorocarbonic acid vinyl acetate 209g(purity is 75%, 1mol); ⑵ stir and to be warming up to 40 ℃, passes into continuously hydrogen fluoride gas with the speed of 0.1L/min, and the speed with 0.5L/min passes into nitrogen, the waste gas hydrogen fluoride that produces in reaction and hydrogen chloride gas alkali liquor absorption continuously simultaneously.After insulation reaction 6 hours, sampling analysis, two chlorocarbonic acid vinyl acetate are 12.3%, difluoroethylene carbonate is 60.1%; After insulation reaction 12 hours, sampling analysis, two chlorocarbonic acid vinyl acetate are 0.9%, and difluoroethylene carbonate is 74.7%, and reaction finishes; ⑶ rectification under vacuum, collecting 60～90 ℃/100mmHg cut 120g(content is 96.7%), yield is 93.6%.
Embodiment 2
(1) in the there-necked flask with stirring, thermometer, prolong and device for absorbing tail gas, adding two chlorocarbonic acid vinyl acetate 184.7g(purity is 85%, 1mol), ⑵ stir and be warming up to 60 ℃, speed with 0.2L/min passes into hydrogen fluoride gas continuously, speed with 1L/min passes into nitrogen, the waste gas hydrogen fluoride that produces in reaction and hydrogen chloride gas alkali liquor absorption continuously simultaneously.After insulation reaction 4 hours, sampling analysis, two chlorocarbonic acid vinyl acetate are 7.6%, difluoroethylene carbonate is 70.5%; After insulation reaction 9 hours, sampling analysis, two chlorocarbonic acid vinyl acetate are 0.5%, and difluoroethylene carbonate is 88.5%, and reaction finishes; ⑶ rectification under vacuum, collecting 60～90 ℃/100mmHg cut 118(content is 97.8%), yield is 93.1%.
Embodiment 3
(1) in the there-necked flask with stirring, thermometer, prolong and device for absorbing tail gas, adding two chlorocarbonic acid vinyl acetate 165.3g(purity is 95%, 1mol), ⑵ stir and be warming up to 60 ℃, speed with 0.3L/min passes into hydrogen fluoride gas continuously, speed with 1L/min passes into nitrogen, the waste gas hydrogen fluoride that produces in reaction and hydrogen chloride gas alkali liquor absorption continuously simultaneously.After insulation reaction 3 hours, sampling analysis, two chlorocarbonic acid vinyl acetate are 10.6%, difluoroethylene carbonate is 83.3%; After insulation reaction 6 hours, sampling analysis, two chlorocarbonic acid vinyl acetate are 0.8%, and difluoroethylene carbonate is 93.2%, and reaction finishes; ⑶ rectification under vacuum, collecting 60～90 ℃/100mmHg cut 118(content is 98.9%), yield is 94.1%.
Claims (8)
1. the preparation method of difluoroethylene carbonate is characterized in that: take two chlorocarbonic acid vinyl acetate and hydrogen fluoride as raw material, under nitrogen protection, controlling temperature of reaction is 40～120 ℃, obtains containing the mixture of difluoroethylene carbonate after reaction; Carry out again distilation and obtain required product difluoroethylene carbonate.
2. the preparation method of difluoroethylene carbonate according to claim 1, it is characterized in that: described pair of chlorocarbonic acid vinyl acetate has cis and trans two kinds of structural formulas, and its structural formula is as follows:
3. the preparation method of difluoroethylene carbonate according to claim 1 and 2, it is characterized in that: two chlorocarbonic acid vinyl acetate and hydrofluoric mol ratio are 1: 1～1: 10.
4. the preparation method of difluoroethylene carbonate according to claim 1 and 2, it is characterized in that: in reaction process, hydrogen fluoride gas and nitrogen are passed in reactor continuously and react, the speed that the control hydrogen fluoride gas passes in reactor is 0.1～0.3L/min, and the speed that control nitrogen passes in reactor is 0.5～1.5L/min.
5. the preparation method of difluoroethylene carbonate according to claim 1 and 2 is characterized in that: controlling temperature of reaction is 40～60 ℃.
6. the preparation method of difluoroethylene carbonate according to claim 1 and 2, it is characterized in that: the waste gas that produces in reaction process passes through alkali liquor absorption.
7. the preparation method of difluoroethylene carbonate according to claim 1 and 2, it is characterized in that: the process of distilation is: be underpressure distillation under 100mmHg at pressure, collect 60～90 ℃ of cuts.
8. the preparation method of difluoroethylene carbonate according to claim 3, it is characterized in that: in reaction process, hydrogen fluoride gas and nitrogen are passed in reactor continuously and react, the speed that the control hydrogen fluoride gas passes in reactor is 0.1～0.3L/min, and the speed that control nitrogen passes in reactor is 0.5～1.5L/min.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310019570.0A CN103113346B (en) | 2013-01-21 | 2013-01-21 | Preparation method of bis-fluoro-ethylene carbonate |
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| CN201310019570.0A CN103113346B (en) | 2013-01-21 | 2013-01-21 | Preparation method of bis-fluoro-ethylene carbonate |
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| CN103113346A true CN103113346A (en) | 2013-05-22 |
| CN103113346B CN103113346B (en) | 2014-11-05 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106905290A (en) * | 2017-03-08 | 2017-06-30 | 江苏理文化工有限公司 | A kind of preparation method of difluoroethylene carbonate |
| CN107903240A (en) * | 2017-11-13 | 2018-04-13 | 张家港瀚康化工有限公司 | The preparation method of difluoroethylene carbonate |
| CN110684006A (en) * | 2019-10-27 | 2020-01-14 | 淮安瀚康新材料有限公司 | Preparation method of high-purity difluoroethylene carbonate |
| CN110903274A (en) * | 2019-12-18 | 2020-03-24 | 江苏华盛锂电材料股份有限公司 | 4, 5-difluoroethylene carbonate and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102060839A (en) * | 2010-12-31 | 2011-05-18 | 上海康鹏化学有限公司 | Preparation method of fluoro-ethylene carbonate |
| CN102766130A (en) * | 2012-07-18 | 2012-11-07 | 太仓华一化工科技有限公司 | Preparation method of difluoroethylene carbonate |
-
2013
- 2013-01-21 CN CN201310019570.0A patent/CN103113346B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102060839A (en) * | 2010-12-31 | 2011-05-18 | 上海康鹏化学有限公司 | Preparation method of fluoro-ethylene carbonate |
| CN102766130A (en) * | 2012-07-18 | 2012-11-07 | 太仓华一化工科技有限公司 | Preparation method of difluoroethylene carbonate |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106905290A (en) * | 2017-03-08 | 2017-06-30 | 江苏理文化工有限公司 | A kind of preparation method of difluoroethylene carbonate |
| CN106905290B (en) * | 2017-03-08 | 2019-06-07 | 江苏理文化工有限公司 | A kind of preparation method of difluoroethylene carbonate |
| CN107903240A (en) * | 2017-11-13 | 2018-04-13 | 张家港瀚康化工有限公司 | The preparation method of difluoroethylene carbonate |
| CN110684006A (en) * | 2019-10-27 | 2020-01-14 | 淮安瀚康新材料有限公司 | Preparation method of high-purity difluoroethylene carbonate |
| CN110903274A (en) * | 2019-12-18 | 2020-03-24 | 江苏华盛锂电材料股份有限公司 | 4, 5-difluoroethylene carbonate and preparation method thereof |
| CN110903274B (en) * | 2019-12-18 | 2022-12-16 | 江苏华盛锂电材料股份有限公司 | 4, 5-difluoroethylene carbonate and preparation method thereof |
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| CN103113346B (en) | 2014-11-05 |
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Effective date of registration: 20231207 Address after: No. 160 Fuxing Road, Hongze Economic Development Zone, Huai'an City, Jiangsu Province, 223100 Patentee after: Jiangsu hankang New Material Co.,Ltd. Address before: Zhangjiagang hankang Chemical Co., Ltd., No.11, Beijing Road, Yangzijiang International Chemical Industrial Park, Zhangjiagang, Suzhou, Jiangsu, 215634 Patentee before: ZHANGJIAGANG HICOMER CHEMICALS CO.,LTD. |