CN1958554A - Method for preparing monochloro- Ethylene Carbonate - Google Patents
Method for preparing monochloro- Ethylene Carbonate Download PDFInfo
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- CN1958554A CN1958554A CN 200510117334 CN200510117334A CN1958554A CN 1958554 A CN1958554 A CN 1958554A CN 200510117334 CN200510117334 CN 200510117334 CN 200510117334 A CN200510117334 A CN 200510117334A CN 1958554 A CN1958554 A CN 1958554A
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Abstract
This invention discloses a method for preparing ethylene monochlorocarbonate. The method comprises: chlorinating ethylene carbonate in the presence of chlorinating agent in tetrachloroethylene solvent under UV-radiation to obtain ethylene monochlorocarbonate. The yield of ethylene monochlorocarbonate is up to 96%, and the purity is up to 98%. Besides, the toxicity of tetrachloroethylene is much lower than that of CCl4, thus the method is suitable for mass production.
Description
Technical field
The invention relates to a kind of preparation method of monochloro-Ethylene Carbonate, especially about a kind of be the method for feedstock production monochloro-Ethylene Carbonate with the NSC 11801.
Technical background
Lithium-ion secondary cell is the green energy resource that the 1990's new development is got up, with excellent properties such as its high reversible capacity, high-voltage, high cycle performance and high-energy-densities and enjoy common people to favor, be called as the leading power supply in 20th century, its Application Areas constantly enlarges.Cycle performance is an important indicator weighing lithium-ion secondary cell, adds the formation that materials such as a certain amount of monochloro-Ethylene Carbonate, vinylene carbonate can promote the SEI film in electrolytic solution, strengthens the cycle performance of lithium-ion secondary cell.
J.Am.Chem.Soc., 1955,77,3789-3793 discloses a kind of preparation method of monochloro-Ethylene Carbonate, and this method is included in carbon tetrachloride solvent and exists down, under ultraviolet catalytic NSC 11801 is carried out chlorination, prepares monochloro-Ethylene Carbonate.This invention is a raw material with the NSC 11801, is solvent with the tetracol phenixin, synthetic monochloro-Ethylene Carbonate under the ultraviolet catalyzed effect.This method prepares monochloro-Ethylene Carbonate yield height, and purity is good.But well known to a person skilled in the art and be, tetracol phenixin is a kind of strong volatile solvent, boiling point under the normal pressure only is 76.8 ℃, and vapour pressure is 15.26 kPas (25 ℃), and chance is fiery or red-hot thing can be decomposed into the stronger gases of toxicity such as hydrogenchloride, phosgene and chlorine.Prolonged and repeated contact tetracol phenixin can have dizziness, weak, insomnia, hypomnesis, poor appetite, feels sick, symptoms such as diarrhoea, stomachache, dysfunction of liver and pulmonary edema.Severe patient can develop into portal cirrhosis.And ethanol can promote the absorption of tetracol phenixin, increases the weight of toxicity symptom.Show that according to IARC1972 and data in 1979 tetracol phenixin is listed in a class chemical substance of " mankind are had carcinogenic possibility ".And according to Montreal protocol, tetracol phenixin will progressively be eliminated in industry and application experimentally.
Afterwards also relevant for directly under ultraviolet catalytic, the NSC 11801 powder carried out the technical study report that chlorination prepares monochloro-Ethylene Carbonate without solvent, but find under the situation that does not have solvent to exist, because reaction is inhomogeneous, cause the yield of monochloro-Ethylene Carbonate very low, do not have prospects for commercial application.About substituting the research of tetracol phenixin as the chlorination reaction solvent with other solvent such as ether, ethanol equal solvent, also the someone has carried out the research of this respect, but all can not enter industrial production because the yield of monochloro-Ethylene Carbonate product is low.
From above-mentioned analysis as can be known, prepared by NSC 11801 in the reaction of monochloro-Ethylene Carbonate, solvent is the key of decision chlorination reaction yield.Owing to never have suitable solvent, make the production of monochloro-Ethylene Carbonate and application be subjected to very big restriction.
Summary of the invention
The objective of the invention is the too big shortcoming of carbon tetrachloride solvent toxicity, a kind of method for preparing monochloro-Ethylene Carbonate with the less solvent of toxicity is provided in order to adopt among the preparation method who overcomes monochloro-Ethylene Carbonate in the prior art.
The invention provides a kind of preparation method of monochloro-Ethylene Carbonate, this method is included in solvent and exists down, under UV-irradiation, makes NSC 11801 and chlorizating agent generation chlorination reaction make monochloro-Ethylene Carbonate, and wherein, described solvent is a zellon.
The yield for preparing monochloro-Ethylene Carbonate with method provided by the invention up to 96%, the easily separated purification of product, and purity is up to 98%.The toxicity of zellon the most important thing is owing to far below the toxicity of tetracol phenixin, thereby can be used at industrial batch.The monochloro-Ethylene Carbonate that makes with method provided by the invention can be used as the electrolysis additive that improves the lithium ion battery cycle performance, also can be used as the raw material of synthesized vinylene carbonate.
Embodiment
The preparation method of monochloro-Ethylene Carbonate provided by the invention is included in solvent and exists down, under UV-irradiation, makes NSC 11801 and chlorizating agent generation chlorination reaction make monochloro-Ethylene Carbonate, and wherein, described solvent is a zellon.
The present invention is not particularly limited the amount of tetrachloroethylene solvent, and it is the 0.5-10 mol that the add-on of zellon is preferably the volumetric molar concentration that makes the NSC 11801 raw material, and the volumetric molar concentration that more preferably makes the NSC 11801 raw material is the 1-7 mol.
The present invention has no particular limits described tetrachloroethylene solvent, can be the zellon of the commercially available various trades mark that get, and also can obtain according to prepared in various methods.For the ease of purifying, preferably do not contain or contain in the described zellon be lower than 1 weight % can with the material of NSC 11801 reaction.The commercially available various analytically pure zellon that gets of preferred use in the specific embodiment of the invention.
Described NSC 11801 raw material can be the NSC 11801 of the commercially available various trades mark that get, and also can obtain according to prepared in various methods.Separation for the ease of final reacting product is purified, the commercially available various analytically pure NSC 11801 that gets of preferred use in the specific embodiment of the invention.
Described chlorizating agent can be various chlorizating agents, as chlorine, phosphorus trichloride, sulfur oxychloride, phosgene.The preferred chlorine that uses in the specific embodiment of the invention.Described chlorine can be the commercially available chlorine that gets, and also can in all sorts of ways prepares.In order to make chlorination reaction thorough, the add-on of chlorine is generally 1.0-1.5 times of the reinforced molar weight of NSC 11801, and more preferably 1.0-1.2 doubly.In order to reduce the generation of dichloro-product, usually chlorine is slowly fed in the reaction system, the feeding speed of chlorine is different according to the amount of reactant usually.
Described UV-irradiation can be by realizing with ultraviolet lamp.The ultraviolet light intensity is not particularly limited, as long as the carrying out of effectively catalysis (or initiation) chlorination reaction.For example, described ultraviolet light intensity can 5 * 10
17-20 * 10
17The photons/second square centimeter.Usually use ultraviolet lamp to provide UV-light in the experiment as ultraviolet source.Intensity for the employed ultraviolet lamp of reaction of difference amount is also different, for example for 1 molar reactive in 500 ml solns, selects for use 10-50 watt ultraviolet lamp that reaction solution is carried out uv irradiating usually and can reach above-mentioned ultraviolet ray intensity.
The present invention is not particularly limited the time and the temperature of chlorination reaction.For the carrying out of accelerated reaction, preferred reaction is carried out under 60-120 ℃ in the specific embodiment of the invention, more preferably carries out under 80-95 ℃.The time of chlorination reaction is generally 5-15 hour, is preferably 8-12 hour.Reaction times is too short, and reaction conversion ratio is lower; Reaction times is long, and chlorination reaction be there is no obvious benefit.
In order to reduce the generation of side reaction, chlorination reaction is preferably carried out in atmosphere of inert gases such as nitrogen, argon gas, and is therefore preferred with nitrogen and/or argon gas that the replacement of the air in the system is clean before logical chlorine.In addition, in order to make reaction evenly, reaction is under agitation carried out.Described stirring can realize that air-flow stirs by the feeding speed of control rare gas element and chlorine.
After chlorination reaction finishes, can in all sorts of ways reaction product is separated purification, for example distillation, column chromatography, thin-layer chromatography, liquid chromatography, high performance liquid chromatography, gas-chromatography.Preferred use underpressure distillation separates purification to product in the specific embodiment of the invention.Because after reaction finishes, the material that may exist in the reaction system mainly contains unreacted intact material carbon vinyl acetate, solvent zellon, chlorine, by product dichloro NSC 11801 and target product monochloro-Ethylene Carbonate, wherein NSC 11801 is solid under normal pressure, its boiling point is 243-244 ℃ (under 740 mmhg), generally is difficult to distill; The boiling point of zellon is 121.2 ℃ (under 1 normal atmosphere); The boiling point of by product dichloro NSC 11801 is 65 ℃ (under 3 mmhg); The boiling point of monochloro-Ethylene Carbonate is 90 ℃ (under 3 mmhg), and the boiling point between each compound differs bigger, can use distillatory mode separation and Extraction.
The products therefrom monochloro-Ethylene Carbonate detects and characterizes with application of gas chromatorgraphy/mass and WXY (C2WAJ) type Abbe refractometer.Described application of gas chromatorgraphy/mass model is the hp6890-5973 that Hewlett-Packard produces.The test parameter of application of gas chromatorgraphy/mass is as follows:
Capillary column: HP-5MS;
Heating schedule: kept 1.5 minutes for 37 ℃, be warming up to 80 ℃ and kept 2.0 minutes with 5 ℃/minute heat-up rate then, and then be warming up to 280 ℃ and kept 8.0 minutes with 20 ℃/minute heat-up rate;
Sample size: 0.2 microlitre, splitting ratio: 50.0: 1;
Injector temperature: 200 ℃
Electron ionization ion source: 70 electron-volts.
The following examples will the invention will be further described.
Embodiment 1
Present embodiment is used to illustrate the preparation method of monochloro-Ethylene Carbonate provided by the invention.
Be to load onto two on 500 milliliters of glass reactors of 3: 1 to visit end Glass tubing, thermometer and prolongs at aspect ratio, reactor inserted in the constant water bath box that the temperature of regulating constant water bath box is 90 ℃.Then 176 gram NSC 11801 (EC) and 350 milliliters of zellons are joined in the above-mentioned reactor, feed nitrogen with the air in the system of driving away, the ultraviolet lamp that starts 20 watts then (is equivalent to 10.84 * 10
17The photons/second square centimeter), begin logical chlorine reaction, the flow of control chlorine is 0.26 gram/minute, control the flow of nitrogen simultaneously, make the system bubbling and stir, system temperature is controlled at 80 ℃, react and stop logical chlorine after 10 hours, finish reaction, obtain lurid reaction solution.
Above-mentioned reaction solution gone in 500 milliliters of single port flasks carry out underpressure distillation, system pressure is 3 mmhg, collects 88-92 ℃ of colourless cut 240 grams.The colourless cut of gained 240 grams is carried out second distillation, obtain 90-91 ℃ of (3 mmhg) colourless cut monochloro-Ethylene Carbonate of 226.7 grams, yield is 93.68%.20 ℃ of refractive index ns
d=1.4533 (literature values: 1.4531), GC purity is 98.1%, the molecular ion peak that shows 87 highest peaks (destroying the quasi-molecular ions of the fragment behind the chlorine) and 122,125 on the mass spectrum, and the strength ratio of 122 and 125 liang of molecular ion peaks is about 3: 1, and the product that makes of proved response is a monochloro-Ethylene Carbonate thus.
Embodiment 2
Present embodiment is used to illustrate the preparation method of monochloro-Ethylene Carbonate provided by the invention.
Be to load onto two on 5000 milliliters of glass reactors of 3: 1 to visit end Glass tubings and prolong at aspect ratio, reactor inserted in the thermostatical oil bath cabinet that the temperature of regulating the thermostatical oil bath cabinet is 110 ℃.Then 176 gram NSC 11801 (EC) and 2000 milliliters of zellons are joined in the above-mentioned reactor, feed nitrogen with the air in the system of driving away, the ultraviolet lamp that starts 15 watts then (is equivalent to 8.13 * 10
17The photons/second square centimeter), begin logical chlorine reaction, the flow of control chlorine is 0.26 gram/minute, control the flow of nitrogen simultaneously, make the system bubbling and stir, system temperature is controlled at 90 ℃, react and stop logical chlorine after 12 hours, finish reaction, obtain the xanchromatic reaction solution.
Above-mentioned reaction solution gone in 5000 milliliters of single port flasks carry out underpressure distillation, system pressure is 3 mmhg, collects 88-92 ℃ of colourless cut 241 grams.The colourless cut of gained 241 grams is carried out second distillation, obtain 90-90.5 ℃ of (3 mmhg) colourless cut monochloro-Ethylene Carbonate of 227.2 grams, yield is 93.89%.Measure the refractive index n of this colourless liquid
d=1.4533 (20 ℃), GC purity is 98.5%, the molecular ion peak that shows 87 highest peaks (destroying the quasi-molecular ions of the fragment behind the chlorine) and 122,125 on the mass spectrum, and the strength ratio of 122 and 125 liang of molecular ion peaks is about 3: 1, the product that makes of proved response is a monochloro-Ethylene Carbonate thus.
Embodiment 3
Present embodiment is used to illustrate the preparation method of monochloro-Ethylene Carbonate provided by the invention.
Be to load onto two on 1000 milliliters of glass reactors of 3: 1 to visit end Glass tubings and prolong at aspect ratio, reactor inserted in the thermostatical oil bath cabinet that the temperature of regulating the thermostatical oil bath cabinet is 110 ℃.Then 176 gram NSC 11801 (EC) and 500 milliliters of zellons are joined in the above-mentioned reactor, feed nitrogen with the air in the system of driving away, the ultraviolet lamp that opens 15 watts then (is equivalent to 8.13 * 10
17The photons/second square centimeter), begin logical chlorine reaction, the flow of control chlorine is 0.26 gram/minute, control the flow of nitrogen simultaneously, make the system bubbling and stir, system temperature is controlled at 95 ℃, react and stop logical chlorine after 8 hours, finish reaction, obtain the xanchromatic reaction solution.
Above-mentioned reaction solution gone in 1000 milliliters of single port flasks carry out underpressure distillation, system pressure is 3 mmhg, collects 88-92 ℃ of colourless cut 241.5 grams.The colourless cut of gained 241.5 grams is carried out second distillation, obtain 90-91 ℃ of (3 mmhg) colourless cut monochloro-Ethylene Carbonate of 230.5 grams, yield is 95.0%.Measure the refractive index n of this colourless liquid
d=1.4533 (20 ℃), GC purity is 98.9%, the molecular ion peak that shows 87 highest peaks (destroying the quasi-molecular ions of the fragment behind the chlorine) and 122,125 on the mass spectrum, and the strength ratio of 122 and 125 liang of molecular ion peaks is about 3: 1, the product that makes of proved response is a monochloro-Ethylene Carbonate thus.
Claims (10)
1, a kind of preparation method of monochloro-Ethylene Carbonate, this method are included in solvent and exist down, under UV-irradiation, make NSC 11801 and chlorizating agent generation chlorination reaction make monochloro-Ethylene Carbonate, it is characterized in that described solvent is a zellon.
2, method according to claim 1, wherein, it is the 1-7 mol that the add-on of described zellon makes the concentration of NSC 11801 in zellon.
3, method according to claim 1, wherein, the exposure intensity of described UV-light is 5 * 10
17-20 * 10
17The photons/second square centimeter.
4, method according to claim 1, wherein, described chlorizating agent is selected from one or more in chlorine, phosphorus trichloride, sulfur oxychloride, the phosgene.
5, method according to claim 4, wherein, described chlorizating agent is a chlorine, the mol ratio of chlorine and NSC 11801 is 0.8-1.5.
6, method according to claim 5, wherein, the mol ratio of described chlorine and NSC 11801 is 1-1.2.
7, method according to claim 1, wherein, this method comprises that also the monochloro-Ethylene Carbonate that chlorination reaction is made separates purification, and the method that described separation is purified is selected from one or more in distillation, column chromatography, thin-layer chromatography, gas-chromatography separation, the high performance liquid chromatography separation.
8, method according to claim 7, wherein, the method that described separation is purified is distillation, described distillation is underpressure distillation.
9, method according to claim 1, wherein, the temperature of described chlorination reaction is 60-105 ℃, the reaction times is 5-15 hour.
10, method according to claim 9, wherein, the temperature of described chlorination reaction is 80-95 ℃, the reaction times is 8-12 hour.
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| CNB2005101173348A CN100469754C (en) | 2005-11-02 | 2005-11-02 | Method for preparing monochloro- Ethylene Carbonate |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101417993A (en) * | 2007-10-26 | 2009-04-29 | 埃沃尼克德古萨有限责任公司 | Preparation method of vinylene carbonate and method for converting the same to vinylene carbonate |
| CN108586421A (en) * | 2018-01-23 | 2018-09-28 | 长园华盛(泰兴)锂电材料有限公司 | A kind of production method of chlorocarbonic acid vinyl acetate |
| CN109942536A (en) * | 2019-04-16 | 2019-06-28 | 张家港瀚康化工有限公司 | A kind of reactive distillation prepares high-purity chloro for the method for ethylene carbonate |
| CN114192078A (en) * | 2021-11-26 | 2022-03-18 | 江苏理文化工有限公司 | Bubbling reaction device and method for continuously producing chlorinated ethylene carbonate |
| CN116854658A (en) * | 2023-07-11 | 2023-10-10 | 珠海光瑞新材料有限公司 | Method for producing chloroethylene carbonate |
-
2005
- 2005-11-02 CN CNB2005101173348A patent/CN100469754C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101417993A (en) * | 2007-10-26 | 2009-04-29 | 埃沃尼克德古萨有限责任公司 | Preparation method of vinylene carbonate and method for converting the same to vinylene carbonate |
| CN108586421A (en) * | 2018-01-23 | 2018-09-28 | 长园华盛(泰兴)锂电材料有限公司 | A kind of production method of chlorocarbonic acid vinyl acetate |
| CN109942536A (en) * | 2019-04-16 | 2019-06-28 | 张家港瀚康化工有限公司 | A kind of reactive distillation prepares high-purity chloro for the method for ethylene carbonate |
| CN114192078A (en) * | 2021-11-26 | 2022-03-18 | 江苏理文化工有限公司 | Bubbling reaction device and method for continuously producing chlorinated ethylene carbonate |
| CN116854658A (en) * | 2023-07-11 | 2023-10-10 | 珠海光瑞新材料有限公司 | Method for producing chloroethylene carbonate |
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| CN100469754C (en) | 2009-03-18 |
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Granted publication date: 20090318 Termination date: 20191102 |