CN115626907B - Preparation method of 4-trifluoro methyl ethylene carbonate - Google Patents
Preparation method of 4-trifluoro methyl ethylene carbonate Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title abstract description 15
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000000460 chlorine Substances 0.000 claims abstract description 52
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- WSFUNGLMDQHNLJ-UHFFFAOYSA-N carbonic acid;3,3,3-trichloroprop-1-ene Chemical compound OC(O)=O.ClC(Cl)(Cl)C=C WSFUNGLMDQHNLJ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000003682 fluorination reaction Methods 0.000 claims abstract description 27
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 18
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 18
- 239000012025 fluorinating agent Substances 0.000 claims abstract description 18
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 14
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000746 purification Methods 0.000 claims abstract description 10
- 230000035484 reaction time Effects 0.000 claims abstract description 7
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 50
- 235000003270 potassium fluoride Nutrition 0.000 claims description 25
- 239000011698 potassium fluoride Substances 0.000 claims description 25
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 19
- 239000012295 chemical reaction liquid Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 6
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 4
- 238000010926 purge Methods 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- LAYPMCGIWDGYKX-UHFFFAOYSA-N trichloromethyl hydrogen carbonate Chemical compound OC(=O)OC(Cl)(Cl)Cl LAYPMCGIWDGYKX-UHFFFAOYSA-N 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 8
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 abstract description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 5
- 239000003792 electrolyte Substances 0.000 abstract description 2
- 239000011259 mixed solution Substances 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- 239000000706 filtrate Substances 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 238000005070 sampling Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- JPLNAQJTXYXDAV-UHFFFAOYSA-N 4,4,5-trichloro-1,3-dioxolan-2-one Chemical compound ClC1OC(=O)OC1(Cl)Cl JPLNAQJTXYXDAV-UHFFFAOYSA-N 0.000 description 5
- 238000004321 preservation Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 4
- 229960004063 propylene glycol Drugs 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- LFEAJBLOEPTINE-UHFFFAOYSA-N 4-(chloromethyl)-1,3-dioxolan-2-one Chemical compound ClCC1COC(=O)O1 LFEAJBLOEPTINE-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of lithium ion battery electrolyte, and particularly relates to a preparation method of 4-trifluoro methyl ethylene carbonate. The preparation method of the 4-trifluoro methyl ethylene carbonate comprises the following steps: (1) Carrying out chlorination reaction on propylene carbonate and chlorine at the temperature of 60-100 ℃ under ultraviolet light, and obtaining trichloromethyl ethylene carbonate after the reaction; (2) The trichloromethyl ethylene carbonate and alkali metal fluorinating agent are subject to fluorination reaction in solvent at 80-115 ℃, and then 4-trifluoro methyl ethylene carbonate is obtained after separation and purification. The whole process does not comprise virulent phosgene, and the method has the advantages of economical and environment-friendly raw materials, mild reaction conditions, short reaction time, high productivity, simple process and the like.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery electrolyte, and particularly relates to a preparation method of 4-trifluoro methyl ethylene carbonate.
Background
The 4-trifluoro methyl ethylene carbonate can be used as a solvent or an additive of nonaqueous electrolyte used in chemical devices such as secondary batteries, capacitors and the like, has the advantages of wide use temperature range, good physical and chemical stability, excellent pressure resistance and the like, and the addition of the 4-trifluoro methyl ethylene carbonate in the lithium ion battery can improve the safety of the lithium ion battery and prolong the service life of the lithium ion battery.
The synthesis method of 4-trifluoro methyl ethylene carbonate mainly comprises a preparation method of reacting 3, 3-trifluoro-1, 2-propanediol with phosgene and a synthesis method of exchanging ester of 3, 3-trifluoro-1, 2-propanediol and dimethyl carbonate.
A method for synthesizing 4-trifluoromethyl ethylene carbonate is disclosed in foreign journal Electrochemistry Communications (2010) 386-389. The toluene solution of phosgene is added into anhydrous THF solution of 3, 3-trifluoro-1, 2-propanediol and triethylamine cooled by ice bath in a dropwise manner, and the mixture is stirred for 1h at room temperature to obtain 4-trifluoro methyl ethylene carbonate with the yield as high as 83 percent. And because of the extremely toxic and strong corrosiveness of phosgene, the phosgene has extremely high danger in the processes of use, transportation and storage, and causes a plurality of inconveniences for production and use.
U.S. patent No. 3,182 discloses a process for preparing K in the absence of water 2 CO 3 The method for synthesizing 4-trifluoro methyl ethylene carbonate by utilizing transesterification reaction of 3, 3-trifluoro-1, 2-propylene glycol and dimethyl carbonate has a yield of 57 percent. The method has mild reaction conditions, but takes a long time to reach 24 hours.
Disclosure of Invention
The invention aims to provide a preparation method of 4-trifluoro methyl ethylene carbonate, which aims to solve the problems of danger, long reaction time consumption and the like in the preparation of 4-trifluoro methyl ethylene carbonate in the prior art.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a method for preparing 4-trifluoro methyl ethylene carbonate, comprising the following steps:
(1) Carrying out chlorination reaction on propylene carbonate and chlorine at the temperature of 60-100 ℃ under ultraviolet light, and obtaining trichloromethyl ethylene carbonate after the reaction;
(2) The trichloromethyl ethylene carbonate and alkali metal fluorinating agent are subject to fluorination reaction in solvent at 80-115 ℃, and then 4-trifluoro methyl ethylene carbonate is obtained after separation and purification.
According to the invention, propylene carbonate and chlorine are adopted as raw materials, trichloromethyl ethylene carbonate is generated through photocatalytic chlorination reaction, and then the trichloromethyl ethylene carbonate and an alkali metal fluorinating agent are subjected to fluorination reaction to generate 4-trifluoro methyl ethylene carbonate; the whole process does not comprise virulent phosgene, the raw materials are economical and environment-friendly, the reaction conditions are mild, the reaction time is short, the productivity is high, the process is simple, and the yield and purity of the 4-trifluoro methyl ethylene carbonate prepared by the whole process are high and reach 99.5%.
In order to ensure a higher reaction yield of the chlorination reaction, preferably, in the step (1), the molar ratio of the propylene carbonate to the chlorine is 1:3-1:4.
In order to further improve the chlorination reaction efficiency, it is preferable that the chlorination reaction temperature in step (1) is 60 to 80 ℃.
Preferably, in the step (1), the chlorination reaction time is 8 to 10 hours.
Preferably, in the step (1) and the step (2), the method further comprises rectifying and purifying the trichloromethyl ethylene carbonate, and purging the reaction liquid with nitrogen before rectifying to carry out chlorine and hydrogen chloride in the reaction liquid. The rectification adopts a laboratory rectification column, and the important technical parameters of rectification are as follows: the bottom temperature is 110-115 ℃, the top temperature is 75 ℃, the top pressure is-99.5 KPa, the bottom pressure is-98.6 KPa, the theoretical plate number is 30, and the reflux ratio is 1:4. The purity of trichloromethyl ethylene carbonate generated by the chlorination reaction can be improved by rectification and purification, so that the fluorination reaction efficiency is improved.
In order to improve the yield and purity of the 4-trifluoromethyl ethylene carbonate, preferably, in the step (2), the separation and purification comprise the steps of cooling the system to 40-60 ℃, and then carrying out solid-liquid separation and purification; the purification is rectification. The system temperature is reduced to 40-60 ℃ and then the subsequent separation and purification are carried out, the temperature is too high, part of potassium chloride and potassium fluoride are dissolved in the reaction liquid, and after the filtrate obtained by solid-liquid separation is placed for a period of time and the temperature is reduced, salt is separated out. The rectification adopts a laboratory rectification column, and the important technical parameters of rectification are as follows: the bottom temperature is 100-105 ℃, the top temperature is 70 ℃, the top pressure is-99.5 KPa, the bottom pressure is-98.6 KPa, the theoretical plate number is 30, and the reflux ratio is 1:4.
Preferably, in the step (2), the fluorination reaction is carried out by dropping trichloromethyl ethylene carbonate into a solvent containing an alkali metal fluorinating agent; the fluorination reaction time is 4-6 h.
In order to ensure a higher reaction yield of the fluorination reaction, preferably, in the step (2), the mass of the solvent is 2-3 times that of the alkali metal fluorinating agent, and the molar ratio of the trichloromethyl ethylene carbonate to the alkali metal fluorinating agent is 1:3-5.
Preferably, in the step (2), the solvent is any one of diethyl carbonate, dimethyl carbonate and acetonitrile.
Preferably, in the step (2), the alkali metal fluorinating agent is any one of potassium fluoride, sodium fluoride and calcium fluoride.
Detailed Description
The preparation method of the 4-trifluoro methyl ethylene carbonate comprises the steps of firstly, carrying out chlorination reaction on propylene carbonate and chlorine to generate trichloromethyl ethylene carbonate, and then carrying out fluorination reaction on the trichloromethyl ethylene carbonate and an alkali metal fluorinating agent to generate the 4-trifluoro methyl ethylene carbonate, wherein the reaction process is shown as a formula (1).
The technical scheme of the invention is further described below with reference to specific embodiments.
1. Specific examples of the preparation method of the 4-trifluoromethyl ethylene carbonate of the invention are as follows:
example 1
The preparation method of the 4-trifluoromethyl ethylene carbonate comprises the following steps:
(1) Chlorination reaction: 204g (2 mol) of propylene carbonate is added into a 1L chlorinator, the temperature is raised to 65 ℃, nitrogen is used for half an hour of gas replacement before chlorine is introduced, after the replacement, an ultraviolet lamp is started to light (the ultraviolet lamp penetrates into the liquid level through a jacket), the partial pressure is controlled to be 0.1MPa through a chlorine pressure reducing meter, the introduced quality of the chlorine is represented by the poor quality of a chlorine steel bottle before and after the chlorine is introduced through a chlorine flow meter, the chlorine enters a system through an inward extending introducing pipe, 224mL/min of the chlorine flow meter is controlled, and the reaction is started. Monitoring the reaction progress through gas chromatography, reacting for 10 hours, wherein the purity of trichloromethyl ethylene carbonate in the synthetic liquid is 82.47%, stopping introducing chlorine, wherein the mass difference of a chlorine steel bottle before and after introducing the chlorine is 425.67g, then introducing nitrogen into the reaction liquid, taking out excessive chlorine and hydrogen chloride in the reaction liquid, rectifying and purifying the reaction liquid, and rectifying by using a laboratory rectifying column, wherein the bottom temperature is 110 ℃, the top temperature is 75 ℃, the top pressure is-99.5 KPa, the bottom pressure is-98.6 KPa, the theoretical plate number is 30, and the reflux ratio is 1:4; after rectification 258g of trichloromethyl ethylene carbonate with a purity of 91.03% are obtained, with a yield of 57.19%.
(2) Fluorination reaction: adding 436g of diethyl carbonate serving as a solvent into a fluorination reaction kettle, then starting stirring, adding 218g of potassium fluoride serving as an alkali metal fluorinating agent into the fluorination reaction kettle, wherein the mass of the added diethyl carbonate is 2 times that of the potassium fluoride, then heating the mixed solution of the diethyl carbonate and the potassium fluoride to 85 ℃, slowly dropwise adding the purified trichloromethyl ethylene carbonate into the mixed solution of the diethyl carbonate and the potassium fluoride, controlling the reaction temperature to be not more than 115 ℃ (110 ℃ in the embodiment), carrying out heat preservation reaction for 6h, sampling detection, obtaining the raw material trichloroethylene carbonate with the purity of 0.4%, stopping the reaction, then cooling the reaction kettle to 40 ℃, carrying out centrifugal separation to obtain filtrate, rectifying the filtrate, wherein the tower bottom temperature is 100 ℃, the tower top temperature is 70 ℃, the tower top pressure is-99.5 KPa, the tower bottom pressure is-98.6 KPa, the theoretical plate number is 30, and the reflux ratio is 1:4. The solvent and the pre-distillation are respectively recovered, when the purity of the fraction reaches 99.95%, the product is received, and 160.27g of 4-trifluoromethyl ethylene carbonate with the purity of 99.95% is obtained, the yield is 89.89%, and the total yield is 51.41%.
Example 2
The preparation method of the 4-trifluoromethyl ethylene carbonate comprises the following steps:
(1) Chlorination reaction: 400g (3.92 mol) of propylene carbonate is added into a 1L chlorinator, the temperature is raised to 70 ℃, nitrogen is used for half an hour of gas replacement before chlorine is introduced, after the replacement, an ultraviolet lamp is started to illuminate (the ultraviolet lamp penetrates into the liquid level through a jacket), the partial pressure is controlled to be 0.1MPa through a chlorine pressure reducing meter, the quality of the introduced chlorine is represented by the poor quality of a chlorine steel bottle before and after the introduced chlorine, the chlorine enters the system through an inward extending introducing pipe, the chlorine flow meter is controlled to 480mL/min, and the reaction is started. Monitoring the reaction progress through gas chromatography, reacting for 10 hours, wherein the purity of trichloromethyl ethylene carbonate in the synthetic liquid is 81.59%, stopping introducing chlorine, wherein the mass difference of chlorine cylinders before and after introducing the chlorine is 834.64g, then introducing nitrogen into the reaction liquid, taking out excessive chlorine and hydrogen chloride in the reaction liquid, rectifying and purifying the reaction liquid, and rectifying by using a laboratory rectifying column, wherein the bottom temperature is 115 ℃, the top temperature is 75 ℃, the top pressure is-99.5 KPa, the bottom pressure is-98.6 KPa, the theoretical plate number is 30, and the reflux ratio is 1:4; after rectification 495.53g of trichloromethyl ethylene carbonate with a purity of 91.84% are obtained, with a yield of 56.52%.
(2) Fluorination reaction: adding 1272g of diethyl carbonate serving as a solvent into a fluorination reaction kettle, then starting stirring, adding 424g of potassium fluoride serving as an alkali metal fluorinating agent into the fluorination reaction kettle, wherein the mass of the added diethyl carbonate is 3 times that of the potassium fluoride, then heating the mixed solution of the diethyl carbonate and the potassium fluoride to 85 ℃, slowly dropwise adding the purified trichloromethyl ethylene carbonate into the mixed solution of the diethyl carbonate and the potassium fluoride, controlling the reaction temperature to be not more than 115 ℃ (105 ℃ in the embodiment), carrying out heat preservation reaction for 6 hours, sampling detection, obtaining the raw material trichloroethylene carbonate with the purity of 0.5%, stopping the reaction, then cooling the reaction kettle to 40 ℃, carrying out centrifugal separation to obtain filtrate, rectifying the filtrate, wherein the tower bottom temperature is 105 ℃, the tower top temperature is 70 ℃, the tower top pressure is-99.5 KPa, the tower bottom pressure is-98.6 KPa, the theoretical plate number is 30, and the reflux ratio is 1:4. The solvent and the pre-distillation are respectively recovered, when the purity of the fraction reaches 99.95%, the product is received, and 311.63g of 4-trifluoromethyl ethylene carbonate with the purity of 99.95% is obtained, the yield is 90.20%, and the total yield is 50.98%.
Example 3
The preparation method of the 4-trifluoromethyl ethylene carbonate comprises the following steps:
(1) Chlorination reaction: 204g (2 mol) of propylene carbonate is added into a 1L chlorinator, the temperature is raised to 85 ℃, nitrogen is used for half an hour of gas replacement before chlorine is introduced, after the replacement, an ultraviolet lamp is started to light (the ultraviolet lamp penetrates into the liquid level through a jacket), the partial pressure is controlled to be 0.1MPa through a chlorine pressure reducing meter, the introduced quality of the chlorine is represented by the poor quality of a chlorine steel bottle before and after the chlorine is introduced through a chlorine flow meter, the chlorine enters the system through an inward extending introducing pipe, the chlorine flow is controlled to be 224mL/min, and the reaction is started. The progress of the reaction was monitored by gas chromatography, the reaction was carried out for 10 hours, the purity of trichloromethyl ethylene carbonate in the synthetic solution was 70.43%, the impurities in the synthetic solution became more, the introduction of chlorine gas was stopped, and the mass difference of chlorine gas cylinders before and after the introduction of chlorine gas was 425.67g. Introducing nitrogen into the reaction liquid to carry out excessive chlorine and hydrogen chloride gas in the reaction liquid, rectifying and purifying the reaction liquid, wherein the rectifying adopts a laboratory rectifying column, the temperature of the bottom of the column is 110 ℃, the temperature of the top of the column is 75 ℃, the pressure of the top of the column is-99.5 KPa, the pressure of the bottom of the column is-98.6 KPa, the theoretical plate number is 30, and the reflux ratio is 1:4; after rectification 143.27g of trichloromethyl ethylene carbonate with a purity of 90.85% are obtained, with a yield of 31.69%.
(2) Fluorination reaction: firstly, 242g of diethyl carbonate serving as a solvent is added into a fluorination reaction kettle, then stirring is started, 121g of potassium fluoride serving as an alkali metal fluorinating agent is added into the fluorination reaction kettle, the mass of the added diethyl carbonate is 2 times that of the potassium fluoride, then the temperature of a mixed solution of the diethyl carbonate and the potassium fluoride is raised to 85 ℃, the purified trichloromethyl ethylene carbonate is slowly added dropwise into the mixed solution of the diethyl carbonate and the potassium fluoride, the mol ratio of the trichloromethyl ethylene carbonate to the potassium fluoride is 1:3.3, the reaction temperature is controlled to be not more than 115 ℃ (110 ℃ in the embodiment), the reaction is kept for 6 hours, sampling and detection are carried out, the purity of the raw material trichloroethylene carbonate is 0.4%, the reaction is stopped, then the reaction kettle is cooled to 40 ℃, centrifugal separation is carried out, the filtrate is obtained, and then the rectification is carried out by adopting a laboratory rectification column, wherein the bottom temperature is 100 ℃, the top temperature is 70 ℃, the top pressure is-99.5 KPa, the bottom pressure is-98.6 KPa, the theoretical plate number is 30, and the reflux ratio is 1:4. The solvent and the pre-distillation are respectively recovered, when the purity of the fraction reaches 99.95%, the product is received, and 88.82g of 4-trifluoromethyl ethylene carbonate with the purity of 99.95% is obtained, the yield is 89.89%, and the total yield is 28.49%.
Example 4
The preparation method of the 4-trifluoromethyl ethylene carbonate comprises the following steps:
(1) Chlorination reaction: 204g (2 mol) of propylene carbonate is added into a 1L chlorinator, the temperature is raised to 65 ℃, nitrogen is used for half an hour of gas replacement before chlorine is introduced, after the replacement, an ultraviolet lamp is started to light (the ultraviolet lamp penetrates into the liquid level through a jacket), the partial pressure is controlled to be 0.1MPa through a chlorine pressure reducing meter, the introduced quality of the chlorine is represented by the poor quality of a chlorine steel bottle before and after the chlorine is introduced through a chlorine flow meter, the chlorine enters a system through an inward extending introducing pipe, 224mL/min of the chlorine flow meter is controlled, and the reaction is started. Monitoring the reaction progress through gas chromatography, reacting for 10 hours, wherein the purity of trichloromethyl ethylene carbonate in the synthetic liquid is 82.47%, stopping introducing chlorine, wherein the mass difference of a chlorine steel bottle before and after introducing the chlorine is 425.67g, introducing nitrogen into the reaction liquid, taking out excessive chlorine and hydrogen chloride gas in the reaction liquid, and performing fluorination reaction.
(2) Fluorination reaction: adding 436g of diethyl carbonate serving as a solvent into a fluorination reaction kettle, then starting stirring, adding 218g of potassium fluoride serving as an alkali metal fluorinating agent into the fluorination reaction kettle, wherein the mass of the added diethyl carbonate is 2 times that of the potassium fluoride, then heating the mixed solution of the diethyl carbonate and the potassium fluoride to 85 ℃, slowly dropwise adding the purified trichloromethyl ethylene carbonate into the mixed solution of the diethyl carbonate and the potassium fluoride, controlling the reaction temperature to be not more than 115 ℃ (110 ℃ in the embodiment), carrying out heat preservation reaction for 6h, sampling detection, obtaining the raw material trichloroethylene carbonate with the purity of 18.34%, stopping the reaction, then cooling the reaction kettle to 40 ℃, carrying out centrifugal separation to obtain filtrate, rectifying the filtrate, wherein the temperature of the bottom of a laboratory rectifying column is 100 ℃, the temperature of the top of the column is 70 ℃, the pressure of the top of the column is-99.5 KPa, the pressure of the bottom of the column is-98.6 KPa, the theoretical column plate number is 30, and the reflux ratio is 1:4. The solvent and the pre-distillation are respectively recovered, when the purity of the fraction reaches 99.95%, 86.15g of 4-trifluoromethyl ethylene carbonate with the purity of 99.95% is obtained, the yield is 33.5%, and the total yield is 27.61%.
2. Comparative example
Comparative example 1
The preparation method of 4-trifluoromethyl ethylene carbonate of this comparative example is basically the same as that of example 1, except that:
(2) Fluorination reaction: firstly adding 424g of diethyl carbonate serving as a solvent into a fluorination reaction kettle, then starting stirring, adding 424g of potassium fluoride serving as an alkali metal fluorinating agent into the fluorination reaction kettle, wherein the mass of the added diethyl carbonate is 1 time of that of the potassium fluoride, then raising the temperature of a mixed solution of the diethyl carbonate and the potassium fluoride to 85 ℃, slowly dropwise adding the purified trichloromethyl ethylene carbonate into the mixed solution of the diethyl carbonate and the potassium fluoride, controlling the molar ratio of the chloromethylethylene carbonate to the potassium fluoride to be 1:3.3, controlling the reaction temperature to be not more than 115 ℃ (105 ℃ in the embodiment), carrying out heat preservation reaction for 6h, sampling detection, wherein the purity of the 4-trifluoro methyl ethylene carbonate is 34%, the purity of the trichloromethyl ethylene carbonate is 56.4%, continuing the heat preservation reaction for 40h at 105 ℃, sampling detection, wherein the purity of the raw material trichloroethylene carbonate is 0.54%, then cooling the reaction kettle to 40 ℃, carrying out centrifugal separation, and finding that the reaction solution is viscous in the centrifugal separation process, and discharging the reaction solution is difficult.
Claims (9)
1. A method for preparing 4-trifluoro methyl ethylene carbonate, which is characterized by comprising the following steps:
(1) Carrying out chlorination reaction on propylene carbonate and chlorine at the temperature of 60-100 ℃ under ultraviolet light, and obtaining trichloromethyl ethylene carbonate after the reaction;
(2) Carrying out fluorination reaction on trichloromethyl ethylene carbonate and an alkali metal fluorinating agent in a solvent at 80-115 ℃, and separating and purifying to obtain 4-trifluoro methyl ethylene carbonate;
in the step (1), the molar ratio of the propylene carbonate to the chlorine is 1:3-1:4;
in the step (2), the mass of the solvent is 2 to 3 times that of the alkali metal fluorinating agent.
2. The method for producing 4-trifluoromethyl ethylene carbonate according to claim 1, wherein in the step (1), the chlorination reaction temperature is 60 to 80 ℃.
3. The method for producing 4-trifluoromethyl ethylene carbonate according to claim 1 or 2, wherein in the step (1), the chlorination reaction time is 8 to 10 hours.
4. The method for producing 4-trifluoromethylcarbonate according to claim 1, wherein in step (1) and step (2), the method further comprises purifying the trichloromethylcarbonate by distillation, and purging the reaction liquid with nitrogen gas before the distillation to carry out chlorine gas and hydrogen chloride gas in the reaction liquid.
5. The method for producing 4-trifluoromethyl ethylene carbonate according to claim 1, wherein in the step (2), the separation and purification comprises the steps of cooling the system to 40-60 ℃, and then solid-liquid separation and purification; the purification is rectification.
6. The method for producing 4-trifluoromethyl ethylene carbonate according to claim 1, wherein in the step (2), the fluorination reaction is carried out by dropping trichloromethyl ethylene carbonate into a solvent containing an alkali metal fluorinating agent; the fluorination reaction time is 4-6 h.
7. The method for producing 4-trifluoromethyl ethylene carbonate according to claim 1 or 6, wherein the molar ratio of the trichloromethyl ethylene carbonate to the alkali metal fluorinating agent is 1:3 to 5.
8. The method for producing 4-trifluoromethyl ethylene carbonate according to claim 1 or 6, wherein in the step (2), the solvent is any one of diethyl carbonate, dimethyl carbonate and acetonitrile.
9. The method for producing 4-trifluoromethylcarbonate according to claim 1 or 6, wherein in step (2), the alkali metal fluorinating agent is any one of potassium fluoride and sodium fluoride.
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