CN105198855B - A kind of synthetic method of 3,3,3 trifluoro propene carbonic ester - Google Patents
A kind of synthetic method of 3,3,3 trifluoro propene carbonic ester Download PDFInfo
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- CN105198855B CN105198855B CN201510734534.1A CN201510734534A CN105198855B CN 105198855 B CN105198855 B CN 105198855B CN 201510734534 A CN201510734534 A CN 201510734534A CN 105198855 B CN105198855 B CN 105198855B
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- trifluoro
- trifluoro propene
- catalyst
- propene carbonic
- carbon dioxide
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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
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
Abstract
The invention discloses a kind of preparation method of 3,3,3 trifluoro propene carbonic ester.For this method using trifluoro-epoxy propane as raw material, slightly solubility tungsten compound is catalyst, is passed through carbon dioxide, and it is 30 DEG C 70 DEG C to control temperature, and regulation reaction pressure is 0.5MPa 3.0MPa, and 3,3,3 trifluoro propene carbonic esters are prepared by the step of cycloaddition reaction one.This method has the advantages of environment-friendly, easy to operate, the reaction time is short, and yield is high, and catalyst can be reused, and is applicable to industrialized production.
Description
Technical field
The invention belongs to Fine Organic Chemical field, and in particular to one kind is using trifluoro-epoxy propane as raw material, slightly solubility tungsten
Compound is catalyst, the method for synthesizing 3,3,3- trifluoro propene carbonic esters.
Background technology
3,3,3- trifluoro propene carbonic esters can be as the cosolvent or additive of lithium-ion battery electrolytes, lithium ion battery
The addition of middle 3,3,3- trifluoro propenes carbonic ester can lift the security of lithium ion battery and extend its service life.
The primary synthetic methods for the 3,3,3- trifluoro propene carbonic esters reported at present in document and patent are as follows：
A kind of synthesis 3,3,3- is disclosed in Electrochemistry Communications 12 (2010) 386-389
The method of trifluoro propene carbonic ester.Toluene solution and the fluoro- 1,2- propane diols of the 3,3,3- tri- containing triethylamine using phosgene
Anhydrous tetrahydrofuran solution reacts, and obtains 3,3,3- trifluoro propene carbonic esters, yield is up to 83%.But play is used in production process
The phosgene of poison and severe corrosive, made troubles to production and dangerous.
US6010806 discloses one kind using Anhydrous potassium carbonate as catalyst, passes through 3,3,3-1,2- propane diols and carbonic acid two
The method that ester exchange reaction synthesis 3,3,3- trifluoro propene carbonic esters occur for methyl esters.The synthesising method reacting condition is more gentle,
But yield is relatively low, only 57%, and the reaction time be up to 24h.
The content of the invention
In order to solve shortcomings and deficiencies of the prior art, the present invention provides a kind of environment-friendly, safe operation, and yield is high,
The synthetic method of the 3,3,3- trifluoro propene carbonic esters of catalyst recoverable.
The synthetic route of the 3,3,3- trifluoro propene carbonic esters of the present invention is as follows：
The synthetic method of provided by the present invention 3,3,3- trifluoro propene carbonic esters is difficult using trifluoro-epoxy propane as raw material
Dissolubility tungsten compound is catalyst, is passed through carbon dioxide, and it is 30 DEG C -70 DEG C to control temperature, regulation reaction pressure 0.5MPa-
The trifluoro propene carbonic ester of 3.0MPa, reaction 1h-6h one-step synthesis 3,3,3-, wherein, tungsten compound catalyst dosage is trifluoro ring
The 1%-10% of Ethylene Oxide quality.
The slightly solubility tungsten compound, including tungstic acid, aqua oxidation tungsten or artificial schellite.
The separation of catalyst can use centrifugation to carry out in the present invention.
Beneficial effects of the present invention：Compared with prior art, the present invention has advantages below：
(1) extremely toxic substance phosgene is used in the prior art, operation is made troubles and dangerous, the present invention is environment-friendly,
Any noxious material is not used, it is easy to operation.
(2) reaction time is up to 24h in the prior art, and product yield is low, and the reaction time of the invention is short, less than 6h, institute
Product yield high is obtained, up to more than 85%.
(3) the use of inorganic salts is in the prior art catalyst, it is difficult to reclaim, catalyst used herein can reclaim,
It can reuse.
Embodiment
The invention will be further described by the following examples, but the present invention is not limited by the following example.
Embodiment 1
In 100mL stainless steel autoclaves, 0.4g tungstic acids and 40g trifluoro-epoxy propanes, confined reaction are sequentially added
Kettle, the carbon dioxide of appropriate pressure is filled with, rises to 30 DEG C by temperature controller control temperature, then control the pressure carbon dioxide to be
0.5MPa, 6h is reacted, room temperature is cooled to, unloads kettle, after excess carbon dioxide is absorbed with saturated sodium carbonate solution, centrifugation hypsokinesis takes
Clear liquid obtains 3,3,3- trifluoro propene carbonic esters, weighs, and calculates yield.By application of gas chromatorgraphy/mass, nmr analysis, selectively it is
99.2%, yield 90.5%.
Embodiment 2
In 100mL stainless steel autoclaves, 2g aqua oxidations tungsten and 40g trifluoro-epoxy propanes, confined reaction are sequentially added
Kettle, the carbon dioxide of appropriate pressure is filled with, rises to 50 DEG C by temperature controller control temperature, then control the pressure carbon dioxide to be
1.5MPa, 3h is reacted, room temperature is cooled to, unloads kettle, after excess carbon dioxide is absorbed with saturated sodium carbonate solution, centrifugation hypsokinesis takes
Clear liquid obtains 3,3,3- trifluoro propene carbonic esters, weighs, and calculates yield.By application of gas chromatorgraphy/mass, nmr analysis, selectively it is
98.6%, yield 89.4%.
Embodiment 3
In 100mL stainless steel autoclaves, 4g artificial schellites and 40g trifluoro-epoxy propanes are sequentially added, closed reactor, is filled
Enter the carbon dioxide of appropriate pressure, rise to 70 DEG C by temperature controller control temperature, it is 3.0MPa then to control pressure carbon dioxide, instead
1h is answered, is cooled to room temperature, unloads kettle, after excess carbon dioxide is absorbed with saturated sodium carbonate solution, centrifugation hypsokinesis takes clear liquid to obtain
3,3,3- trifluoro propene carbonic esters, weigh, and calculate yield.By application of gas chromatorgraphy/mass, nmr analysis, selectivity is 98.2%, yield
For 86.4%.
Embodiment 4
In 100mL stainless steel autoclaves, 1.6g tungstic acids and 40g trifluoro-epoxy propanes, confined reaction are sequentially added
Kettle, the carbon dioxide of appropriate pressure is filled with, rises to 50 DEG C by temperature controller control temperature, then control the pressure carbon dioxide to be
1.8MPa, 4h is reacted, room temperature is cooled to, unloads kettle, after excess carbon dioxide is absorbed with saturated sodium carbonate solution, centrifugation hypsokinesis takes
Clear liquid obtains 3,3,3- trifluoro propene carbonic esters, weighs, and calculates yield.By application of gas chromatorgraphy/mass, nmr analysis, selectively it is
99.5%, yield 92.7%.
Embodiment 5
By the catalyst that embodiment 4 is isolated after methanol is washed, dried, after being calcined 4 hours in 500 DEG C of air atmospheres
Use.3,3,3- trifluoro propene carbonic esters are selectively 98.1%, yield 89.3%, active not obviously lowered, catalyst
It is reusable.
Claims (1)
1. one kind 3,3, the synthetic method of 3- trifluoro propene carbonic esters, it is characterised in that using trifluoro-epoxy propane as raw material, indissoluble
Property tungsten compound be catalyst, be passed through carbon dioxide, control temperature be 30 DEG C -70 DEG C, regulation reaction pressure is 0.5MPa-
The trifluoro propene carbonic ester of 3.0MPa, reaction 1h-6h one-step synthesis 3,3,3-；Wherein, slightly solubility tungsten compound is tungstic acid, water
Tungsten oxide or artificial schellite are closed, catalyst amount is the 1%-10% of trifluoro-epoxy propane quality.
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| CN201510734534.1A CN105198855B (en) | 2015-11-02 | 2015-11-02 | A kind of synthetic method of 3,3,3 trifluoro propene carbonic ester |
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| CN201510734534.1A CN105198855B (en) | 2015-11-02 | 2015-11-02 | A kind of synthetic method of 3,3,3 trifluoro propene carbonic ester |
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| CN105198855A CN105198855A (en) | 2015-12-30 |
| CN105198855B true CN105198855B (en) | 2018-03-13 |
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| CN106967040B (en) * | 2017-03-09 | 2019-05-17 | 南阳师范学院 | A kind of preparation method of cyclic carbonate ester |
| CN113321570A (en) * | 2021-07-14 | 2021-08-31 | 山东华安新材料有限公司 | Preparation method of 3,3, 3-trifluoro-1, 2-propanediol |
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| JP3568225B2 (en) * | 1994-01-19 | 2004-09-22 | 三井化学株式会社 | Method for producing alkylene carbonate |
| JPH07291959A (en) * | 1994-04-27 | 1995-11-07 | Asahi Chem Ind Co Ltd | Fluorine-containing cyclic carbonate |
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