CN106905290B - A kind of preparation method of difluoroethylene carbonate - Google Patents
A kind of preparation method of difluoroethylene carbonate Download PDFInfo
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- CN106905290B CN106905290B CN201710135755.6A CN201710135755A CN106905290B CN 106905290 B CN106905290 B CN 106905290B CN 201710135755 A CN201710135755 A CN 201710135755A CN 106905290 B CN106905290 B CN 106905290B
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- 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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Abstract
The present invention relates to a kind of preparation method of difluoroethylene carbonate, key step is as follows: (1) being dissolved in the metal fluoride of activation in the polyglycol solution of hydrofluorocarbons sealing end；(2) Lewis Acid metal catalyst SbF is added into reaction system3、SbF5、AlF3One of；(3) dichloro- ethylene carbonate is added in reaction vessel, obtains crude product 4,4- difluorinated ethylene carbonate；(4) the 4,4- difluorinated ethylene carbonate for being greater than 99.95% by obtaining purity after rectifying, recrystallization.It is of the invention the utility model has the advantages that the raw material used is two chloroformate mixtures after EC chlorination, be not necessarily to separating-purifying；The selectivity of reaction, high income are improved using Lewis Acid metal catalyst；Potassium fluoride is dissolved with the polyethylene glycol that fluorine-containing alkane blocks, improves fluorination reaction rate；Process route is simple, yield is 70% or more, and production cost is low, environmentally friendly.
Description
Technical field
The invention belongs to Organic fluoride chemical fields, and in particular to a kind of preparation method of difluoroethylene carbonate.
Background technique
Difluoroethylene carbonate is existed due to the advantages that dielectric constant is high, flash-point is high, the low antioxidative stabilizer of freezing point is good
Lithium battery electrolytes field is concerned.Difluoroethylene carbonate can improve the circulation of electrolyte as lithium battery additive
Performance, cryogenic property and flame retardant property.4,4- difluorinated ethylene carbonate in three kinds of difluoroethylene carbonate structures has
The advantages that fusing point is low, viscosity is low, dielectric constant and conductivity are higher has outstanding excellent in improvement lithium battery electrolytes aspect of performance
Gesture.
The preparation method of 4,4- difluorinated ethylene carbonate is mainly by the preparation of simple substance fluoride and FEC and potassium fluoride and two at present
The two methods of preparation of chlorocarbonic acid vinyl acetate.
Japan Patent JP2000344763 discloses a kind of reacted with simple substance fluoride with FEC and prepares difluorinated ethylene carbonate
Method.What this method obtained is the mixture of three kinds of structures of difluorinated ethylene carbonate, and 4,4- difluorinated ethylene carbonate
Yield only has 5%.United States Patent (USP) US2011048053 discloses a kind of potassium fluoride and dichloro- ethylene carbonate two fluoro of preparation
And the method for more fluorinated ethylene carbonates.This method reaction time is long, yield is low.
Summary of the invention
The purpose of the present invention is overcome the deficiencies of the prior art and provide a kind of high income, purity is high, simple process, raw material
Preparation method of the dichloro- ethylene carbonate without a kind of 4,4- difluorinated ethylene carbonate of purification.
In order to solve the above technical problems, containing the invention adopts the following technical scheme: the metal fluoride of activation is dissolved in
In the polyethylene glycol solvent of fluorohydrocarbon sealing end；Lewis Acid metal catalyst SbF is added into reaction system again3、SbF5、AlF3In
One kind；Then dichloro- ethylene carbonate is added；Under the conditions of anhydrous and oxygen-free, 40 DEG C ~ 80 DEG C of reaction temperature are controlled, reaction
3h ~ 5h obtains 4, the 4- difluorinated ethylene carbonate that purity is greater than 99.95% by rectifying, recrystallization purification after reaction.
To further realize the object of the invention, any one of the metal fluoride in NaF, KF, CsF, gold
The molar ratio for belonging to fluoride and dichloro- ethylene carbonate is 1:1 ~ 3:1.
The activation condition of the metal fluoride is 100 DEG C ~ 150 DEG C, activation time 6h ~ 8h.
The polyethylene glycol of the hydrofluorocarbons sealing end, the hydrocarbon of sealing end are any one in tetrafluoroethene, hexafluoropropene
Kind, and the molecular weight polyethylene glycol of hydrofluorocarbons sealing end is in 400 ~ 1000 ranges.
The quality of the polyethylene glycol of the hydrofluorocarbons sealing end is 1 ~ 3 times of metal pentafluoride amount of substance.
The Lewis Acid metal catalyst is selected from SbF3、SbF5And AlF3In any one, quality be dichloro
For the 5% ~ 10% of ethylene carbonate quality.
The dichloro- ethylene carbonate be by ethylene carbonate and sulfonic acid chloride LED ultraviolet or initiator peroxidating
The lower preparation of bis- (2,4- dichloro-benzoyls) effect, obtains 4,4- dichloro- ethylene carbonate, trans- -4,5- dichloro- ethylene carbonate
Without the mixture of purification composed by ester and cis- -4,5- dichloro- ethylene carbonate, three kinds of structures, structural formula is as follows:
。
The rectification process is rectification under vacuum, and pressure is 20 ~ 25mmHg, and temperature is 47 DEG C ~ 51 DEG C.
The recrystallization solvent is petroleum ether, and petroleum ether quality and the mass ratio of 4,4- difluorinated ethylene carbonate are 1:
1 ~ 5:1, recrystallization temperature are -5 DEG C ~ 0 DEG C.
Compared with prior art, the present invention having the advantage that (1) raw materials used dichloro- ethylene carbonate is by carbonic acid
The lower preparation reaction of ultraviolet or initiator peroxidating bis- (2,4- dichloro-benzoyls) effect of vinyl acetate and sulfonic acid chloride in LED obtains
, by 4,4- dichloro- ethylene carbonate, trans- -4,5- dichloro- ethylene carbonate and cis- -4,5- dichloro- ethylene carbonate
Without the mixture of purification composed by three kinds of structures of ester, simplify
The synthesis technology of 4,4-difluorinated ethylene carbonates；Use Lewis Acid metal catalyst SbF3、SbF5、AlF3In
Any one, obtain 4, the 4- difluorinated ethylene carbonate of highly selective single configuration after reaction；(2) hydrofluorocarbons are used
The polyethylene glycol of sealing end improves reaction rate as solvent；(3) reactivity of the metal fluoride after activating increases, and improves
Reaction yield shortens the reaction time；(4) crude product 4,4-difluorinated ethylene carbonates are recrystallization solvent using petroleum ether, can be with
Obtain the product that purity is greater than 99.95%.
Specific embodiment
The present invention will be described in detail combined with specific embodiments below, but is not limited to these embodiments.
Embodiment 1
Into the four round flask equipped with thermometer, sample tap, condenser pipe and agitating device, 104g sodium fluoride is added
The polyethylene glycol (molecular weight 400) that (100 DEG C, activate 8h) and 104g tetrafluoroethene block is added after stirring and dissolving
7.53gSbF3, the dichloro- ethylene carbonate of 118g is added, reacts 5h at 40 DEG C of temperature；After reaction in 20mmHg,
Collect 47 DEG C of fraction；The mass ratio of 4, the 4- difluorinated ethylene carbonate and petroleum ether that are collected into is 1:1, in -5 DEG C of Shi Chongjie
Crystalline substance obtains 99.96% sample, molar yield 76.6%.
Embodiment 2
Into the four round flask equipped with thermometer, sample tap, condenser pipe and agitating device, 69.6g potassium fluoride is added
The polyethylene glycol (molecular weight 1000) that (150 DEG C, activate 6h) and 139.2g hexafluoropropene block is added after stirring and dissolving
6.3gAlF3, add 87.2g(0.4mol, 72%) dichloro- ethylene carbonate, react 4h under temperature 60 C；Reaction knot
In 25mmHg after beam, 51 DEG C of fraction is collected；The mass ratio of the 4,4- difluorinated ethylene carbonate and petroleum ether that are collected into is 1:
3, it is recrystallized at 0 DEG C, obtains 99.95% sample, molar yield 79.5%.
Embodiment 3
Into the four round flask equipped with thermometer, sample tap, condenser pipe and agitating device, 232g is added
The polyethylene glycol (molecular weight 700) of potassium fluoride (130 DEG C, activate 7h) and 696g hexafluoropropene sealing end), stirring and dissolving
After SbF is added5, the dichloro- ethylene carbonate of 189.2g is added, reacts 3h at 80 DEG C of temperature；Exist after reaction
22mmHg collects 49 DEG C of fraction；The mass ratio of 4, the 4- difluorinated ethylene carbonate and petroleum ether that are collected into is 1:5, -2
DEG C when recrystallize, obtain 99.97% sample, molar yield 81.0%.
Comparative example 1
Into the four round flask equipped with thermometer, sample tap, condenser pipe and agitating device, 104g sodium fluoride is added
The polyethylene glycol (molecular weight 400) of (unactivated) and 104g tetrafluoroethene sealing end, is added 7.53gSbF after stirring and dissolving3, then plus
The dichloro- ethylene carbonate for entering 118g, reacts 4h under temperature 50 C；After reaction in 20mmHg, 47 DEG C of collection evaporates
Point；The mass ratio of 4, the 4- difluorinated ethylene carbonate and petroleum ether that are collected into is 1:1, recrystallizes, obtains at -5 DEG C
99.96% sample, molar yield 56.6%.
Comparative example 2
Into the four round flask equipped with thermometer, sample tap, condenser pipe and agitating device, 232g is added
The polyethylene glycol (molecular weight 700) of potassium fluoride (130 DEG C, activate 7h) and 696g hexafluoropropene sealing end), stirring and dissolving
After SbF is added5, the dichloro- ethylene carbonate of 189.2g is added, reacts 3h at 80 DEG C of temperature；Exist after reaction
22mmHg collects 49 DEG C of fraction；The mass ratio of 4, the 4- difluorinated ethylene carbonate and petroleum ether that are collected into is 1:5, -10
DEG C when recrystallize, obtain 99.2% sample 83.8g, molar yield 65.0%.
Comparative example 3
Into the four round flask equipped with thermometer, sample tap, condenser pipe and agitating device, 232g is added
The polyethylene glycol (molecular weight 700) of potassium fluoride (130 DEG C, activate 7h) and 696g hexafluoropropene sealing end), stirring and dissolving
After SbF is added5, the dichloro- ethylene carbonate of 189.2g is added, reacts 3h at 80 DEG C of temperature；Exist after reaction
22mmHg collects 49 DEG C of fraction；The mass ratio of 4, the 4- difluorinated ethylene carbonate and petroleum ether that are collected into is 1:5, at 5 DEG C
When recrystallize, obtain 99.8% sample, molar yield 63.2%.
Claims (8)
1. a kind of preparation method of difluoroethylene carbonate, it is characterised in that: be dissolved in the metal fluoride of activation fluorine-containing
In the solvent of the polyethylene glycol of hydrocarbon sealing end, then Lewis Acid metal catalyst is added into reaction vessel, then adds dichloro
For ethylene carbonate；Under the conditions of anhydrous and oxygen-free, 40 DEG C~80 DEG C of reaction temperature are controlled, reacts 3h-5h, reaction solution is by essence
Evaporate, recrystallize purification obtain purity be greater than 99.95% 4,4- difluorinated ethylene carbonate；The Lewis Acid metal catalysis
Agent is selected from SbF3、SbF5And AlF3In any one, quality be dichloro- ethylene carbonate quality 5%~10%.
2. a kind of preparation method of difluoroethylene carbonate according to claim 1, which is characterized in that the metal
Any one of fluoride in NaF, KF, CsF, the molar ratio of metal fluoride and dichloro- ethylene carbonate be 1:1~
3:1。
3. a kind of preparation method of difluoroethylene carbonate according to claim 1 or 2, which is characterized in that described
The activation condition of metal fluoride is 100 DEG C~150 DEG C, activation time 6h~8h.
4. a kind of preparation method of difluoroethylene carbonate according to claim 1, which is characterized in that described is fluorine-containing
Hydrocarbon of its sealing end of the polyethylene glycol of hydrocarbon sealing end is tetrafluoroethene, any one in hexafluoropropene, and the poly- second of hydrofluorocarbons sealing end
Glycol molecular weight is in 400~1000 ranges.
5. a kind of preparation method of difluoroethylene carbonate according to claim 1, which is characterized in that described is fluorine-containing
The quality of the polyethylene glycol of hydrocarbon sealing end is 1~3 times of metal pentafluoride amount of substance.
6. a kind of preparation method of difluoroethylene carbonate according to claim 1, which is characterized in that the dichloro
It is that ultraviolet or initiator peroxidating by ethylene carbonate and sulfonic acid chloride in LED is bis- (2,4- dichloro-benzoyl) for ethylene carbonate
The lower preparation of effect, obtains by 4,4- dichloro- ethylene carbonate, trans- -4,5- dichloro- ethylene carbonate and cis- -4,5- bis-
Without the mixture of purification composed by three kinds of structures of chlorocarbonic acid vinyl acetate, structure is as follows:
7. a kind of preparation method of difluoroethylene carbonate according to claim 1, which is characterized in that the rectifying
Technique is rectification under vacuum, and pressure is 20~25mmHg, and temperature is 47 DEG C~51 DEG C.
8. a kind of preparation method of difluoroethylene carbonate according to claim 1, which is characterized in that the knot again
Brilliant solvent is petroleum ether, and the mass ratio of petroleum ether quality and 4,4- difluorinated ethylene carbonate is 1:1~5:1, recrystallization temperature
It is -5~0 DEG C.
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| 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 |
| CN115611846B (en) * | 2022-11-10 | 2024-07-09 | 广州理文科技有限公司 | Preparation method of high-purity fluoroderivatives of ethylene carbonate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101717390A (en) * | 2009-10-29 | 2010-06-02 | 张家港市华盛化学有限公司 | Purifying process of difluoroethylene 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 |
| CN103113346A (en) * | 2013-01-21 | 2013-05-22 | 张家港瀚康化工有限公司 | Preparation method of bis-fluoro-ethylene carbonate |
| CN104529992A (en) * | 2014-11-26 | 2015-04-22 | 苏州华一新能源科技有限公司 | Preparation method for 4,5-difluoro-1,3-dioxolan-2-one |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101717390A (en) * | 2009-10-29 | 2010-06-02 | 张家港市华盛化学有限公司 | Purifying process of difluoroethylene 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 |
| CN103113346A (en) * | 2013-01-21 | 2013-05-22 | 张家港瀚康化工有限公司 | Preparation method of bis-fluoro-ethylene carbonate |
| CN104529992A (en) * | 2014-11-26 | 2015-04-22 | 苏州华一新能源科技有限公司 | Preparation method for 4,5-difluoro-1,3-dioxolan-2-one |
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