CN105968083B - A kind of preparation method of fluorinated ethylene carbonate - Google Patents
A kind of preparation method of fluorinated ethylene carbonate Download PDFInfo
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- CN105968083B CN105968083B CN201610320898.XA CN201610320898A CN105968083B CN 105968083 B CN105968083 B CN 105968083B CN 201610320898 A CN201610320898 A CN 201610320898A CN 105968083 B CN105968083 B CN 105968083B
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- ethylene carbonate
- fluorinated ethylene
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- hydrogen fluoride
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- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical class O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- 239000007789 gas Substances 0.000 claims abstract description 35
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 34
- 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 abstract description 29
- 239000007788 liquid Substances 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 230000035484 reaction time Effects 0.000 claims abstract description 12
- 239000012467 final product Substances 0.000 claims abstract description 7
- 238000004064 recycling Methods 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000009833 condensation Methods 0.000 claims description 7
- 230000005494 condensation Effects 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- AOGYCOYQMAVAFD-UHFFFAOYSA-N chlorocarbonic acid Chemical compound OC(Cl)=O AOGYCOYQMAVAFD-UHFFFAOYSA-N 0.000 claims description 3
- 229910001120 nichrome Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 7
- 239000000047 product Substances 0.000 abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 5
- 229910000041 hydrogen chloride Inorganic materials 0.000 abstract description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 4
- 229910052731 fluorine Inorganic materials 0.000 abstract description 4
- 239000011737 fluorine Substances 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000003185 calcium uptake Effects 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- AOANMOLKQQXRCC-UHFFFAOYSA-N C(C)(=O)OC=C.C(O)(=O)F Chemical compound C(C)(=O)OC=C.C(O)(=O)F AOANMOLKQQXRCC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical group [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006561 solvent free reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- 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
- C07D317/42—Halogen atoms or nitro radicals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of preparation method of fluorinated ethylene carbonate, comprise the following steps：1) chlorocarbonic acid vinyl acetate raw material and hydrogen fluoride liquid are passed through micro passage reaction, are reacted under the conditions of 20~20 DEG C, obtain mixture；2) by mixture obtained by step 1) be heated to 40~50 DEG C discharge gas after, through rectification under vacuum, to obtain the final product.The preparation method of the fluorinated ethylene carbonate of the present invention, reaction efficiency is high, and the reaction time is short, overcomes labor intensity in Conventional process big, production cycle length, and the three wastes produce the shortcomings that more, gained fluorinated ethylene carbonate product purity height and high income；At the same time, Fluorine source is used as using hydrogen fluoride liquid, greatly reduce the cost of production, and reaction is easy to control, the unreacted post-treated condensing unit of hydrogen fluoride liquid can realize recycling, and the byproduct hydrogen chloride generated realizes zero-emission through Alkali absorption, safety and environmental protection, is particularly suitable for industrialization large-scale production.
Description
Technical field
The invention belongs to be fluorinated synthesis technical field, and in particular to a kind of preparation method of fluorinated ethylene carbonate.
Background technology
Lithium ion battery has become staple product indispensable in people's daily life.But the performance of battery is also much
Cannot meet the needs of people, capacity, security and the cycle performance for improving lithium ion battery have become weight urgently to be resolved hurrily
Want problem.One of the important materials of electrolyte as lithium ion battery, by the preparation such as organic solvent, electrolytic salt and additive
Into being known as the blood of lithium ion battery, its security and chemical property important to battery.
Electrolysis additive fluorinated ethylene carbonate (Fluoroethylene Carbonate, FEC) is as a kind of new
Electrolysis additive, gets most of the attention because being significantly improved to performance of lithium ion battery.Fluorinated ethylene carbonate is because that can improve
Film forming using carbon material as the surface SEI films of anode improves the cycle performance of battery, and because it has surpassing more than 110 DEG C
High-flash and there is good fire resistance.Addition fluorinated ethylene carbonate can significantly improve the specific volume of battery in the electrolytic solution
Measure, cycle performance, and the high-temperature behavior of battery can be improved by compound addition.
At present, the method for synthesizing fluoroethylene carbonate is mainly the following：
In the prior art, CN103113345B discloses a kind of preparation method of fluorinated ethylene carbonate, with chlorocarbonic acid
Vinyl acetate and hydrogen fluoride are raw material, and under nitrogen protection, controlling reaction temperature is 50~120 DEG C, and carbon containing fluoro is obtained after reaction
The mixture of vinyl acetate, required product fluorinated ethylene carbonate is obtained through distilation.This method is although feasible, but phase
For liquid-fluorination hydrogen, using gaseous hydrogen fluoride danger higher, and the reaction temperature of the technical solution is high, the reaction time
It is long, it is unfavorable for operating.
CN101774923B discloses a kind of preparation method of fluorinated ethylene carbonate, and this method makes chlorocarbonic acid vinyl acetate
Substitution reaction generation fluorinated ethylene carbonate, the fluorization agent occurs in organic solvent and in the presence of acid binding agent with fluorization agent
For nitrogenous organic base hydrogen fluoride complex；The substitution reaction is to make reaction system insulation reaction 2~6 at 60~120 DEG C small
When obtain the reaction mixture containing fluorinated ethylene carbonate, to the reaction mixture carry out alkali cleaning, extract organic phase, pass through decompression
Distillation obtains fluorinated ethylene carbonate.This method is due to the use of solvent, so as to add cost, last handling process is cumbersome, and
Yield is not high, and only 85% or so.
The preparation method of above-mentioned fluorinated ethylene carbonate, generally existing reaction rate is low, the reaction time is long and side reaction is more,
The defects of subsequent treatment is cumbersome, is not suitable for large-scale continuous production.
The content of the invention
The object of the present invention is to provide a kind of preparation method of fluorinated ethylene carbonate, reaction rate is high, the reaction time is short,
And gained fluorinated ethylene carbonate has higher yield and purity.
In order to realize the above object the technical solution adopted in the present invention is：
A kind of preparation method of fluorinated ethylene carbonate, comprises the following steps：
1) chlorocarbonic acid vinyl acetate raw material and hydrogen fluoride liquid are passed through micro passage reaction, under the conditions of -20~20 DEG C
Reacted, obtain mixture；
2) by mixture obtained by step 1) be heated to 40~50 DEG C discharge gas after, through rectification under vacuum, to obtain the final product.
In step 1), reaction time of the material in micro passage reaction is 10~300s.Microchannel plate used should
Device is continuous stream micro passage reaction；Chlorocarbonic acid vinyl acetate raw material is continuously to be passed through with hydrogen fluoride liquid.
In step 1), it is 1 to be passed through the chlorocarbonic acid vinyl acetate of micro passage reaction and the molar ratio of hydrogen fluoride:1~10.
The purity of the chlorocarbonic acid vinyl acetate raw material is not less than 70%.The purity is chlorocarbonic acid vinyl acetate in chloro
Mass percentage in ethylene carbonate raw material.Generally, the purity of chlorocarbonic acid vinyl acetate raw material used for 70%~
90%.
In step 1), the micro passage reaction replaces internal gas with protective gas before use.The protective gas
For nitrogen.Nitrogen used is high pure nitrogen.
In step 1), the material of micro passage reaction used is nichrome.
The microchannel of micro passage reaction used is heart-shaped structure.The heart-shaped structure refers to the reaction of micro passage reaction
Passage is composed in series by some heart-shaped structure units with complete mixing flow feature.
In step 1), the material of the pump for being passed through chlorocarbonic acid vinyl acetate raw material is titanium；For being passed through hydrogen fluoride liquid
The material of pump be polytetrafluoroethylene (PTFE).
In step 2), heating the mixture to 40~50 DEG C discharges gas, vaporizes the condensed recycling of gas of discharge, no
Condensing gas is absorbed through alkaline matter.During being somebody's turn to do, this condensation recycling is hydrogen fluoride gas, and non-condensation gas are hydrogen chloride gas.
Specially：The liquid obtained after reaction enters receiving tank, and liquid in receiving tank is heated to 40~50 DEG C, makes hydrogen fluoride and chlorination
Hydrogen vaporizes, and the condensed device recycling of hydrogen fluoride, hydrogen chloride is absorbed through alkaline matter.The alkaline matter for alkali metal oxide,
Alkaline earth oxide, alkali metal hydroxide or alkaline earth metal hydroxide.Preferably, the alkaline matter is calcium oxide.
After gas discharge, remaining liquid carries out follow-up rectification under vacuum.
In step 2), the rectification under vacuum refers to negative pressure more than -0.095MPa, collects 90~100 DEG C of cut.It is described
Negative pressure refer to the range of negative pressure of -0.01~-0.095MPa more than -0.095MPa.
The preparation method of the fluorinated ethylene carbonate of the present invention, is using chlorocarbonic acid vinyl acetate and hydrogen fluoride liquid as original
Material, using the continuous synthesizing fluoroethylene carbonate of micro passage reaction, reaction efficiency is obviously improved, so as to substantially reduce reaction
Time, overcomes labor intensity in Conventional process big, and production cycle length, the three wastes produce the shortcomings that more, gained fluoro carbonic acid
Vinyl acetate product purity height and high income；Meanwhile using hydrogen fluoride liquid as Fluorine source, the cost of production is greatly reduced, and
React easy to control, the unreacted post-treated condensing unit of hydrogen fluoride liquid can realize recycling, the accessory substance generated
Hydrogen chloride realizes zero-emission, safety and environmental protection, is particularly suitable for industrialization large-scale production through Alkali absorption.
The preparation method of the fluorinated ethylene carbonate of the present invention, compared with prior art, has the following advantages that：
1. using micro passage reaction synthesizing fluoroethylene carbonate, reaction efficiency is substantially increased, and can be continuous
Steady production；
2. using hydrogen fluoride liquid, reaction temperature is low, greatly reduces the cost of reaction as Fluorine source；
3. the unreacted condensed recycling reusable edible of hydrogen fluoride, the by-product hydrogen chloride of generation is through Alkali absorption, substantially in fact
Existing zero-emission；
4. the preparation method is solvent-free reaction, reaction process is controlled by being passed through for hydrogen fluoride, and reaction is easy to control
System, it is easy to accomplish large-scale industrial production.
Embodiment
With reference to embodiment, the present invention is further illustrated.
In embodiment, micro passage reaction used is continuous stream micro passage reaction, and material is nichrome,
Microchannel is heart-shaped structure (such as mass transfer enhancement " heart " structure micro passage reaction, G1 types, Corning；Reaction channel is by some
Miniature " heart " construction unit with complete mixing flow feature is composed in series)；For being pumped into the pump (pump of chlorocarbonic acid vinyl acetate raw material
A material) is titanium；The material of pump (pump B) for being pumped into hydrogen fluoride liquid is polytetrafluoroethylene (PTFE).
Embodiment 1
The preparation method of the fluorinated ethylene carbonate of the present embodiment, comprises the following steps：
1) with after the gas inside high pure nitrogen displacement micro passage reaction, the temperature for setting micro passage reaction is 20
DEG C, use pump A, pump B respectively by purity for 70% chlorocarbonic acid vinyl acetate raw material, hydrogen fluoride liquid be continuously pumped into microchannel plate
Device is answered to be reacted, the velocity ratio of chlorocarbonic acid vinyl acetate raw material and hydrogen fluoride liquid is 174:20, make chlorocarbonic acid vinyl acetate
Molar ratio with hydrogen fluoride is 1:1, reaction time of the material in micro passage reaction is 30s；Reaction product is from outlet
Place receives, and obtains mixture；
Analysis is sampled to gained mixture, the mass content of chlorocarbonic acid vinyl acetate is 0.8%, fluoro ethylene carbonate
The mass content of ester is 67.2%；
2) mixture obtained by step 1) is heated to 40 DEG C, discharges gas, the condensed device of gas of discharge is recycled to
Receive kettle, the oxidized calcium uptake of non-condensation gas；Remaining liquid collects 90 through rectification under vacuum more than negative pressure -0.095MPa
~100 DEG C of cut, to obtain the final product.
It will detect, the purity of fluorinated ethylene carbonate obtained by the present embodiment is 98.3%, yield 95.7%.
Embodiment 2
The preparation method of the fluorinated ethylene carbonate of the present embodiment, comprises the following steps：
1) with after the gas inside high pure nitrogen displacement micro passage reaction, the temperature for setting micro passage reaction is 0 DEG C,
Use pump A, pump B respectively by purity be 70% chlorocarbonic acid vinyl acetate raw material, hydrogen fluoride liquid be continuously pumped into microchannel plate answer
Device is reacted, and the velocity ratio of chlorocarbonic acid vinyl acetate raw material and hydrogen fluoride liquid is 153:100, make chlorocarbonic acid vinyl acetate with
The molar ratio of hydrogen fluoride is 1:5, reaction time of the material in micro passage reaction is 150s；Reaction product is from exit
Receive, obtain mixture；
Analysis is sampled to gained mixture, the mass content of chlorocarbonic acid vinyl acetate is 0.6%, fluoro ethylene carbonate
The mass content of ester is 77.5%；
2) mixture obtained by step 1) is heated to 45 DEG C, discharges gas, the condensed device of gas of discharge is recycled to
Receive kettle, the oxidized calcium uptake of non-condensation gas；Remaining liquid collects 90 through rectification under vacuum more than negative pressure -0.095MPa
~100 DEG C of cut, to obtain the final product.
It will detect, the purity of fluorinated ethylene carbonate obtained by the present embodiment is 98.8%, yield 96.2%.
Embodiment 3
The preparation method of the fluorinated ethylene carbonate of the present embodiment, comprises the following steps：
1) with after the gas inside high pure nitrogen displacement micro passage reaction, the temperature for setting micro passage reaction is -20
DEG C, use pump A, pump B respectively by purity for 90% chlorocarbonic acid vinyl acetate raw material, hydrogen fluoride liquid be continuously pumped into microchannel plate
Device is answered to be reacted, the velocity ratio of chlorocarbonic acid vinyl acetate raw material and hydrogen fluoride liquid is 136:200, make chlorocarbonic acid vinyl acetate
Molar ratio with hydrogen fluoride is 1:10, reaction time of the material in micro passage reaction is 300s；Reaction product is from going out
Received at mouthful, obtain mixture；
Analysis is sampled to gained mixture, the mass content of chlorocarbonic acid vinyl acetate is 0.9%, fluoro ethylene carbonate
The mass content of ester is 86.3%；
2) mixture obtained by step 1) is heated to 50 DEG C, discharges gas, the condensed device of gas of discharge is recycled to
Receive kettle, the oxidized calcium uptake of non-condensation gas；Remaining liquid collects 90 through rectification under vacuum more than negative pressure -0.095MPa
~100 DEG C of cut, to obtain the final product.
It will detect, the purity of fluorinated ethylene carbonate obtained by the present embodiment is 98.4%, yield 96.1%.
Embodiment 4
The preparation method of the fluorinated ethylene carbonate of the present embodiment, comprises the following steps：
1) with after the gas inside nitrogen displacement micro passage reaction, the temperature for setting micro passage reaction is 20 DEG C, is adopted
With pump A, pump B respectively by purity be 90% chlorocarbonic acid vinyl acetate raw material, hydrogen fluoride liquid be continuously pumped into micro passage reaction
Reacted, the velocity ratio of chlorocarbonic acid vinyl acetate raw material and hydrogen fluoride liquid is 136:20, make chlorocarbonic acid vinyl acetate and fluorine
The molar ratio for changing hydrogen is 1:1, reaction time of the material in micro passage reaction is 30s；Reaction product connects from exit
Receive, obtain mixture；
Analysis is sampled to gained mixture, the mass content of chlorocarbonic acid vinyl acetate is 0.3%, fluoro ethylene carbonate
The mass content of ester is 89.2%；
2) mixture obtained by step 1) is heated to 45 DEG C, discharges gas, the condensed device of gas of discharge is recycled to
Receive kettle, the oxidized calcium uptake of non-condensation gas；Remaining liquid collects 90 through rectification under vacuum more than negative pressure -0.095MPa
~100 DEG C of cut, to obtain the final product.
It will detect, the purity of fluorinated ethylene carbonate obtained by the present embodiment is 99.1%, yield 96.9%.
The preparation method that can be seen that the fluorinated ethylene carbonate of the present invention from the testing result of above-described embodiment reacts effect
Rate is high, the reaction time is short, and gained fluorinated ethylene carbonate product purity is high, and purity is more than 98.3%, and product yield is high, yield
More than 95.7%.
Claims (10)
- A kind of 1. preparation method of fluorinated ethylene carbonate, it is characterised in that：Comprise the following steps：1）Chlorocarbonic acid vinyl acetate raw material and hydrogen fluoride liquid are passed through micro passage reaction, carried out under the conditions of -20~20 DEG C Reaction, obtains mixture；2）By step 1）Gained mixture be heated to 40~50 DEG C discharge gas after, through rectification under vacuum, to obtain the final product.
- 2. the preparation method of fluorinated ethylene carbonate according to claim 1, it is characterised in that：Step 1）In, material exists Reaction time in micro passage reaction is 10~300s.
- 3. the preparation method of fluorinated ethylene carbonate according to claim 1, it is characterised in that：Step 1）In, it is passed through micro- The chlorocarbonic acid vinyl acetate of channel reactor and the molar ratio of hydrogen fluoride are 1:1~10.
- 4. the preparation method of the fluorinated ethylene carbonate according to claim 1 or 3, it is characterised in that：The chlorocarbonic acid The purity of vinyl acetate raw material is not less than 70%.
- 5. the preparation method of fluorinated ethylene carbonate according to claim 1, it is characterised in that：Step 1）In, it is described micro- Channel reactor replaces internal gas with protective gas before use, and the protective gas is nitrogen.
- 6. the preparation method of fluorinated ethylene carbonate according to claim 1, it is characterised in that：Step 1）In, it is used micro- The material of channel reactor is nichrome.
- 7. the preparation method of the fluorinated ethylene carbonate according to claim 1 or 6, it is characterised in that：Microchannel plate used The microchannel for answering device is heart-shaped structure.
- 8. the preparation method of fluorinated ethylene carbonate according to claim 1, it is characterised in that：Step 1）In, for leading to The material for entering the pump of chlorocarbonic acid vinyl acetate raw material is titanium；The material of pump for being passed through hydrogen fluoride liquid is polytetrafluoroethylene (PTFE).
- 9. the preparation method of fluorinated ethylene carbonate according to claim 1, it is characterised in that：Step 2）In, it will mix Thing, which is heated to 40~50 DEG C, discharges gas, vaporizes the condensed recycling of gas of discharge, and non-condensation gas are absorbed through alkaline matter.
- 10. the preparation method of fluorinated ethylene carbonate according to claim 1, it is characterised in that：Step 2）In, it is described to subtract Pressure rectifying refers to negative pressure more than -0.095MPa, collects 90~100 DEG C of cut.
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Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108250176A (en) * | 2016-12-19 | 2018-07-06 | 上海惠和化德生物科技有限公司 | A kind of quick continuous flow synthesis technology of fluorinated ethylene carbonate |
| WO2018113628A1 (en) * | 2016-12-19 | 2018-06-28 | 上海惠和化德生物科技有限公司 | Rapid continuous-flow synthesis process for fluoroethylene carbonate. |
| CN106749155B (en) * | 2017-01-06 | 2019-04-26 | 淮安瀚康新材料有限公司 | A kind of method that microchannel plate should prepare vinylene carbonate |
| CN106810528A (en) * | 2017-01-06 | 2017-06-09 | 淮安瀚康新材料有限公司 | A kind of method that microchannel plate should prepare chlorocarbonic acid vinyl acetate |
| CN107033119B (en) * | 2017-04-06 | 2019-10-11 | 多氟多化工股份有限公司 | A kind of preparation method of high-purity fluorinated ethylene carbonate |
| CN114213386B (en) * | 2022-01-04 | 2024-06-21 | 山东亘元生物科技有限公司 | Industrial continuous production method of fluoroethylene carbonate |
| CN114632486A (en) * | 2022-03-18 | 2022-06-17 | 山东惟普新能源有限公司 | Device and method capable of continuously synthesizing fluoroethylene carbonate |
| CN114716403B (en) * | 2022-05-11 | 2024-09-03 | 多氟多新材料股份有限公司 | Synthetic method of fluoroethylene carbonate |
| CN115433155A (en) * | 2022-09-25 | 2022-12-06 | 青岛科技大学 | Synthetic method of fluoroethylene carbonate |
| CN115466242B (en) * | 2022-10-03 | 2024-06-21 | 青岛科技大学 | Synthetic method of fluoroethylene carbonate |
| CN115784888A (en) * | 2022-10-25 | 2023-03-14 | 康宁反应器技术有限公司 | Production method of methyl trifluoroethyl carbonate |
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