CN115894429A - Method for preparing vinylene carbonate - Google Patents
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- CN115894429A CN115894429A CN202211616918.XA CN202211616918A CN115894429A CN 115894429 A CN115894429 A CN 115894429A CN 202211616918 A CN202211616918 A CN 202211616918A CN 115894429 A CN115894429 A CN 115894429A
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- vinylene carbonate
- chlorine
- blue light
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- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 25
- 239000003112 inhibitor Substances 0.000 claims abstract description 21
- OYOKPDLAMOMTEE-UHFFFAOYSA-N 4-chloro-1,3-dioxolan-2-one Chemical compound ClC1COC(=O)O1 OYOKPDLAMOMTEE-UHFFFAOYSA-N 0.000 claims abstract description 17
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 16
- 239000000460 chlorine Substances 0.000 claims abstract description 16
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims abstract description 13
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 7
- 238000004321 preservation Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- ZBEBOOQVKXZARN-UHFFFAOYSA-N carbonochloridic acid;ethene Chemical compound C=C.OC(Cl)=O ZBEBOOQVKXZARN-UHFFFAOYSA-N 0.000 claims description 10
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 8
- UBUCNCOMADRQHX-UHFFFAOYSA-N N-Nitrosodiphenylamine Chemical compound C=1C=CC=CC=1N(N=O)C1=CC=CC=C1 UBUCNCOMADRQHX-UHFFFAOYSA-N 0.000 claims description 8
- 229950000688 phenothiazine Drugs 0.000 claims description 8
- -1 N, N-di-tert-butyl nitroxide free radical Chemical class 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
- HIGQQEOWQNDHJD-UHFFFAOYSA-N 4,4-dichloro-1,3-dioxolan-2-one Chemical compound ClC1(Cl)COC(=O)O1 HIGQQEOWQNDHJD-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 abstract description 12
- 238000004821 distillation Methods 0.000 abstract description 9
- 239000012046 mixed solvent Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 231100000086 high toxicity Toxicity 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 238000007086 side reaction Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 16
- 239000000706 filtrate Substances 0.000 description 11
- 239000012043 crude product Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 4
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000006298 dechlorination reaction Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- XJHDWSFEGCYSFP-UHFFFAOYSA-N C=C.ClC(Cl)=O Chemical compound C=C.ClC(Cl)=O XJHDWSFEGCYSFP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002000 Electrolyte additive Substances 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
Classifications
-
- 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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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing vinylene carbonate, which comprises the following steps: taking ethylene carbonate as a raw material, and carrying out chlorination reaction with chlorine under blue light irradiation to obtain chlorinated ethylene carbonate; carrying out reduced pressure distillation on the chlorination product to obtain high-purity monochloroethylene carbonate; mixing monochloroethylene carbonate with an organic solvent, adding a polymerization inhibitor, heating to a reaction temperature under stirring, then dropwise adding triethylamine, and continuing a heat preservation reaction after the dropwise adding is finished; after the reaction, the reaction solution is subjected to post-treatment to obtain vinylene carbonate. The invention uses high-purity chloroethylene carbonate and the mixed polymerization inhibitor, reduces the using amount of high-toxicity substances, prevents polymerization side reaction to a great extent, and improves the product yield and purity; the mixed solvent of diethyl carbonate and trimethyl phosphate is adopted, so that the solvent reduction is avoided, the product yield is improved, the use amount of the solvent in the production process is reduced, and the cost is saved.
Description
Technical Field
The invention relates to a method for preparing vinylene carbonate, belonging to the technical field of lithium battery electrolyte additives.
Background
Vinylene Carbonate (VC for short) has a chemical formula of C 3 H 2 O 3 1,3-dioxol-2-one, is the most ideal additive for battery electrolyte. Aurbach studyIt was found that vinylene carbonate can cause a polymerization reaction on the surface of the battery negative electrode, thereby producing a polyalkyl lithium carbonate compound. The formation of the substance not only can not damage the battery anode, but also can well prevent the co-intercalation reaction between solvent molecules in the electrolyte. Because vinylene carbonate can generate polymerization reaction, a layer of SEI (solid electrolyte interface) film can be formed on the negative electrode of the battery (graphite), and the film can reduce the decomposition degree of the electrolyte of the graphite battery to the minimum, thereby effectively prolonging the cycle service life of the lithium battery.
Vinylene carbonate is used as a new film forming additive in lithium ion battery electrolyte, has an overcharge protection function, and can be used for medical organic polymer materials and modified intermediates for enzyme immobilization and organic synthesis. The vinylene carbonate has great application potential, can play obvious action effect in many aspects of different fields, and is a product with high economic value.
At present, the reaction principle involved in the synthesis process of vinylene carbonate at home and abroad is generally consistent, namely, firstly, vinyl carbonate is taken as a reaction raw material to carry out chlorination reaction to obtain chloroethylene carbonate, then the generated chloroethylene carbonate is subjected to dechlorination reaction to obtain a Vinylene Carbonate (VC) crude product, and finally, a battery-grade VC finished product meeting the production requirement is obtained through crystallization and purification. However, there are many problems in the existing product synthesis process, such as: the purity of the chloroethylene carbonate is low, so that the yield of the synthesized vinylene carbonate is reduced; the usage amount of the solvent is large, and the production cost is high; the dechlorination reaction has low conversion rate and the obtained product has low yield. Therefore, it is necessary to find a more suitable preparation process.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the method for preparing the vinylene carbonate, which improves the process steps, optimizes the reaction conditions of the dechlorination reaction, improves the yield and the purity of the product, reduces the dosage of the organic solvent of the dechlorination reaction, reduces the cost and is more suitable for industrial application.
The specific technical scheme of the invention is as follows:
a method for preparing vinylene carbonate, comprising:
(1) Performing chlorination reaction on vinyl carbonate serving as a raw material and chlorine under blue light irradiation to obtain chloroethylene carbonate;
(2) Carrying out reduced pressure distillation on the product obtained in the step (1) to remove dichloroethylene carbonate and obtain high-purity monochlorethylene carbonate;
(3) Mixing the monochloroethylene carbonate obtained in the step (2) with an organic solvent, adding a polymerization inhibitor, heating to the reaction temperature under stirring, then dropwise adding triethylamine, and continuing the heat preservation reaction after the dropwise adding is finished;
(4) After the reaction, the reaction solution is subjected to post-treatment to obtain vinylene carbonate.
Further, in the step (1), ethylene carbonate is heated to be melted and then reacts with chlorine, and the heating temperature can be 35-40 ℃.
Further, in the step (1), the blue light is provided by a blue light lamp, and the power of the blue light lamp is 300w to 2000w, for example, 300w, 500w, 800w, 1000w, 1200w, 1400w, 1600w, 1800w, 2000w, preferably 300w to 800w.
Further, in the step (1), chlorine is introduced for reaction at 60-70 ℃ under the irradiation of blue light, and the reaction time is generally 5-6h. In order to bring the chlorine gas into contact with the ethylene carbonate more sufficiently, it is preferable that the chlorine gas is introduced from below the liquid level of the ethylene carbonate.
Further, in the step (1), chlorine gas is continuously introduced until the reaction is complete, and the container is in a sealed state in order to prevent the chlorine gas from overflowing during the chlorination reaction.
Further, in the step (1), the introduction speed of the chlorine is 100 to 120mL/min.
Further, in the step (2), the purpose of reduced pressure distillation is to remove byproducts of chlorination reaction and improve the purity of the product, the vacuum degree of the reduced pressure distillation is generally 0.099MPa to 0.1MPa, and the temperature of the reduced pressure distillation is controlled to be 110 ℃ to 130 ℃.
Further, in the step (3), the organic solvent is a mixture of diethyl carbonate and trimethylphosphate, and preferably, the mass ratio of diethyl carbonate to trimethylphosphate is 2 to 5. The mass ratio of the monochloroethylene carbonate to the organic solvent is 1.
Further, in the step (3), the stirring can be realized by a common stirring device, and the stirring speed is generally 150-300rpm.
Further, in the step (3), the polymerization inhibitor is a mixture of N, N-di-tert-butyl nitroxide free radical, phenothiazine and N-nitrosodiphenylamine, and the mass ratio of the N, N-di-tert-butyl nitroxide free radical, phenothiazine and N-nitrosodiphenylamine is preferably 3. The mass of the polymerization inhibitor is 0.3-0.6% of that of the monochloroethylene carbonate.
In the step (3), the molar ratio of the ethylene monochlorocarbonate to the triethylamine is 1.2 to 1.25.
And (3) further, heating to 62-65 ℃, starting to dropwise add triethylamine for 1-1.25h, and after dropwise adding, keeping the temperature and reacting for 4.5-5 h.
Further, in the step (4), after the reaction is finished, the reaction solution is filtered, and the solvent is removed from the obtained filtrate to obtain a vinylene carbonate crude product. And rectifying and crystallizing the vinylene carbonate crude product to obtain a vinylene carbonate finished product. The operation mode of crystallization is as follows: crystallizing the liquid obtained by rectification at 12-15 ℃ by using vinylene carbonate, and performing suction filtration to obtain a product after no crystal is precipitated, wherein the purity of the obtained product is high and can meet the requirement of electronic-grade products.
Compared with the prior art, the invention has the following advantages:
1. the invention utilizes the high-power blue light lamp to directly react without using a solvent, thereby being green, environment-friendly and low in pollution.
2. In the vinylene carbonate synthesis reaction, the chlorinated product is distilled and purified, and monochloroethylene carbonate with high purity and a mixed polymerization inhibitor are used, so that the use amount of high-toxicity substances is reduced, the polymerization side reaction is prevented to a great extent, and the product yield and purity are improved.
3. In the vinylene carbonate synthesis reaction, diethyl carbonate and trimethyl phosphate are used as solvents, so that the solvent reduction is avoided, the reaction yield is improved, the use amount of the solvents in the production process is reduced, and the cost is saved.
Detailed Description
In order to explain the technical content of the technical solution, the achieved objects and the achieved effects in detail, the following is further described with reference to the specific embodiments.
Example 1
1. Heating and melting ethylene carbonate at 35-40 ℃, adding the ethylene carbonate into a three-neck flask, putting the three-neck flask into a water bath kettle, immersing a blue light lamp tube (465 nm-470 nm, 300w) into the water bath kettle, turning on light when the water bath temperature is raised to 60-70 ℃, continuously introducing chlorine into the sealed three-neck flask by using an introduction tube extending below the liquid level until the reaction is finished, wherein the introduction speed of the chlorine is 120mL/min, and carrying out heat preservation at the temperature to synthesize ethylene chlorocarbonate; after the reaction is completed for 5 to 6 hours, ethylene dichlorocarbonate is removed by reduced pressure distillation (the temperature is 110 to 130 ℃, and the vacuum degree is 0.099MPa to 0.1MPa), and 168.4g of ethylene monochlorocarbonate with the purity of 98.2 percent is obtained.
2. 110g of monochloroethylene carbonate with the purity of 98.2 percent and 275.3g of mixed solvent (the mass ratio of diethyl carbonate to trimethyl phosphate is 5:1) are added into a flask, 0.43g of mixed polymerization inhibitor (0.19gN, N-ditert-butyl nitroxide radical, 0.12g of phenothiazine and 0.12g of N-nitrosodiphenylamine) is added into the flask, the flask is stirred and heated at the rotation speed of 200rpm, triethylamine (109.8 g) is dropwise added when the temperature is 62-65 ℃, the dropwise addition time is 1.2 hours, and the reaction is continued at 65 ℃ for 5 hours after the dropwise addition.
3. After the reaction is finished, carrying out suction filtration on the reaction liquid, washing a filter cake with 50g of diethyl carbonate, merging the filtrates, adding 0.2g of polymerization inhibitor 2,6-di-tert-butyl-p-cresol into the filtrate to prevent vinylene carbonate from polymerizing due to overhigh temperature in the distillation process, adding the polymerization inhibitor into the filtrate, distilling the filtrate to remove the solvent to obtain a vinylene carbonate crude product, rectifying the vinylene carbonate crude product, slowly crystallizing the liquid obtained by rectification with vinylene carbonate at the temperature of 12-15 ℃, and carrying out suction filtration after no crystal is separated out to obtain 54.3g of colorless and transparent vinylene carbonate, wherein the product purity is 99.9%, and the yield is 75.6% calculated by the vinylene carbonate.
Example 2
1. Heating and melting ethylene carbonate at 35-40 ℃, adding the ethylene carbonate into a three-neck flask, putting the three-neck flask into a water bath kettle, immersing a blue light lamp tube (465 nm-470 nm, 600w) into the water bath kettle, turning on lamplight when the water bath temperature is raised to 60-70 ℃, continuously introducing chlorine into the sealed three-neck flask by using an introduction tube extending below the liquid level until the reaction is finished, wherein the introduction speed of the chlorine is 120mL/min, and carrying out heat preservation at the temperature to synthesize ethylene chlorocarbonate; after the reaction is completed for 5 to 6 hours, removing the dichloroethylene carbonate by reduced pressure distillation (the temperature is 110 to 130 ℃, and the vacuum degree is 0.099MPa to 0.1MPa) to obtain 159.3g of monochlorocarbonic ethylene carbonate with the purity of 98.5 percent.
2. 100g of ethylene monochlorocarbonate with the purity of 98.5 percent and 254.6g of mixed solvent (the mass ratio of diethyl carbonate to trimethyl phosphate is 2:1) are added into a flask, 0.59g of mixed polymerization inhibitor (0.25gN, N-di-tert-butyl nitroxide radical, 0.17g of phenothiazine and 0.17g of N-nitrosodiphenylamine) is added, stirring and heating are carried out at the rotating speed of 200rpm, triethylamine (100.08 g) is added dropwise when the temperature is 62-65 ℃, the dropwise adding time is 1h, and the reaction is continued at 65 ℃ for 5h after the dropwise adding is finished.
3. After the reaction is finished, suction-filtering the reaction liquid, washing a filter cake by 50g of diethyl carbonate, merging the filtrates, adding a polymerization inhibitor 2,6-di-tert-butyl-p-cresol 0.26g into the filtrate, distilling the filtrate to remove the solvent to obtain a vinylene carbonate crude product, rectifying the vinylene carbonate crude product, slowly crystallizing the liquid obtained by rectification by using vinylene carbonate at the temperature of 12-15 ℃, after no crystal is separated out, suction-filtering to obtain 51.0g of colorless and transparent vinylene carbonate, wherein the purity of the product is 99.9%, and the yield is 78.7% calculated by the vinylene carbonate.
Example 3
1. Heating and melting ethylene carbonate at 35-40 ℃, adding the ethylene carbonate into a three-neck flask, putting the three-neck flask into a water bath kettle, immersing a blue light lamp tube (465 nm-470 nm, 800w) into the water bath kettle, turning on lamplight when the water bath temperature is raised to 60-70 ℃, continuously introducing chlorine into the sealed three-neck flask by using an introduction tube extending below the liquid level until the reaction is finished, wherein the introduction speed of the chlorine is 120mL/min, and carrying out heat preservation at the temperature to synthesize ethylene chlorocarbonate; after the reaction is completed for 5 to 6 hours, ethylene dichlorocarbonate is removed by reduced pressure distillation (the temperature is 110 to 130 ℃, and the vacuum degree is 0.099MPa to 0.1MPa), and 176.8g of ethylene monochlorocarbonate with the purity of 98.7 percent is obtained.
2. 104g of ethylene monochlorocarbonate with the purity of 98.7 percent and 262.4g of a mixed solvent (the mass ratio of diethyl carbonate to trimethyl phosphate is 3:1) are added into a flask, 0.63g of a mixed polymerization inhibitor (0.27gN, N-di-tert-butyl nitroxide radical, 0.18g of phenothiazine and 0.18g of N-nitrosodiphenylamine) is added into the flask, the flask is stirred and heated at the rotating speed of 200rpm, triethylamine (105.8 g) is added dropwise when the temperature is 62-65 ℃, the dropwise adding time is 1 hour, and the reaction is continued at 65 ℃ for 5 hours after the dropwise adding is finished.
3. After the reaction is finished, suction-filtering the reaction liquid, washing a filter cake with 50g of diethyl carbonate, merging the filtrates, adding 0.25g of polymerization inhibitor 2,6-di-tert-butyl-p-cresol into the filtrate, distilling the filtrate to remove the solvent to obtain a vinylene carbonate crude product, rectifying the vinylene carbonate crude product, slowly crystallizing the liquid obtained by rectification at the temperature of 12 to 15 ℃ with vinylene carbonate, after no crystal is separated out, suction-filtering to obtain 54.2g of colorless and transparent vinylene carbonate, wherein the purity of the product is 99.9%, and the yield is 81.3% of the vinylene carbonate.
Comparative example 1
Vinylene carbonate was prepared according to the procedure of example 3, except that: in step 2, 262.4g of the mixed solvent was replaced with 262.4g of diethyl carbonate. The final vinylene carbonate had a purity of 99.6% and a yield of 70.2% based on the vinylene carbonate.
Comparative example 2
Vinylene carbonate was prepared according to the procedure of example 3, except that: in step 2, 262.4g of the mixed solvent was replaced with 262.4g of dimethyl carbonate. The finally obtained vinylene carbonate had a purity of 99.2% and a yield of 68.4% based on the vinylene carbonate.
Comparative example 3
Vinylene carbonate was prepared according to the procedure of example 3, except that: in step 2, 262.4g of the mixed solvent was replaced with 262.4g of trimethylphosphate. The purity of the finally obtained vinylene carbonate was 98.7%, and the yield was 59.1% based on the vinylene carbonate.
Comparative example 4
Vinylene carbonate was prepared according to the procedure of example 3, except that: in step 2, 0.63g of the mixed polymerization inhibitor was replaced with 0.63g of N, N-di-t-butylnitroxide radical. The purity of the finally obtained vinylene carbonate was 97.4%, and the yield was 65.8% based on the vinylene carbonate.
Comparative example 5
Vinylene carbonate was prepared according to the procedure of example 3, except that: in step 2, 0.63g of the mixed polymerization inhibitor was replaced with 0.63g of phenothiazine. The purity of the finally obtained vinylene carbonate was 98.2%, and the yield was 63.7% based on the vinylene carbonate.
Comparative example 6
Vinylene carbonate was prepared according to the procedure of example 3, except that: in step 2, 0.63g of the mixed polymerization inhibitor was replaced with 0.63g of N-nitrosodiphenylamine. The final vinylene carbonate had a purity of 96.5% and a yield of 56.9% based on the vinylene carbonate.
Comparative example 7
Vinylene carbonate was prepared according to the procedure of example 3, except that: in step 2, 0.63g of the mixed polymerization inhibitor was replaced with 0.63g of 2,6-di-tert-butyl-p-cresol. The finally obtained vinylene carbonate had a purity of 98.4% and a yield of 65.2% based on the vinylene carbonate.
Comparative example 8
Vinylene carbonate was prepared according to the procedure of example 3, except that: in step 2, 0.63g of the mixed polymerization inhibitor was replaced with 0.63g of 2,6-di-t-butyl-p-cresol and p-benzoquinone. The final vinylene carbonate had a purity of 98.6% and a yield of 67.8% based on the vinylene carbonate.
The above-mentioned embodiments are merely illustrative of the technical idea and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the present invention, and not to limit the protection scope of the present invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered in the protection scope of the present invention.
Claims (9)
1. A method for preparing vinylene carbonate is characterized by comprising the following steps:
(1) Performing chlorination reaction on vinyl carbonate serving as a raw material and chlorine under blue light irradiation to obtain chloroethylene carbonate;
(2) Distilling the product obtained in the step (1) under reduced pressure to remove dichloroethylene carbonate and obtain monochloroethylene carbonate with high purity;
(3) Mixing the monochloroethylene carbonate obtained in the step (2) with an organic solvent, adding a polymerization inhibitor, heating to the reaction temperature under stirring, then dropwise adding triethylamine, and continuing the heat preservation reaction after the dropwise adding is finished;
(4) After the reaction, the reaction solution is subjected to post-treatment to obtain vinylene carbonate.
2. The method of claim 1, wherein: in the step (1), the blue light is provided by a blue light lamp, and the power of the blue light lamp is 300w to 2000w, preferably 300w to 800w.
3. A method according to claim 1 or 2, characterized by: in the step (1), introducing chlorine for reaction at the temperature of 60-70 ℃ under the irradiation of blue light; preferably, chlorine is introduced below the level of ethylene carbonate.
4. A method according to claim 1 or 2, characterized by: in the step (1), chlorine is continuously introduced until the reaction is finished, and the introduction speed of the chlorine is 100 to 120mL/min.
5. The method of claim 1, further comprising: in the step (3), the organic solvent is a mixture of diethyl carbonate and trimethyl phosphate, and the polymerization inhibitor is a mixture of N, N-di-tert-butyl nitroxide free radical, phenothiazine and N-nitrosodiphenylamine.
6. The method of claim 5, wherein: in the step (3), the mass ratio of diethyl carbonate to trimethyl phosphate is 2-5, and the mass ratio of the N, N-di-tert-butyl nitroxide radical to the phenothiazine to the N-nitrosodiphenylamine is 3:1-2:1-2.
7. The method of claim 1, 5 or 6, wherein: in the step (3), the mass ratio of the ethylene monochlorocarbonate to the organic solvent is 1 to 2 to 3, and the molar ratio of the ethylene monochlorocarbonate to the triethylamine is 1.2 to 1.25.
8. The method of claim 1, 5 or 6, wherein: in the step (3), the mass of the polymerization inhibitor is 0.3-0.6% of that of the monochloroethylene carbonate.
9. The method of claim 1, further comprising: and (3) heating to 62 to 65 ℃, dropwise adding triethylamine for 1 to 1.25h, and after dropwise adding, continuously carrying out a heat preservation reaction for 4.5to 5h.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304935A (en) * | 1999-11-19 | 2001-07-25 | 默克专利股份有限公司 | Preparation method of vinylene carbonate and its application |
| CN110483471A (en) * | 2019-09-08 | 2019-11-22 | 淮安瀚康新材料有限公司 | A kind of synthetic method of vinylene carbonate |
| CN114957194A (en) * | 2022-06-14 | 2022-08-30 | 华东理工大学 | Method for improving yield of vinylene carbonate |
| CN115286612A (en) * | 2022-07-27 | 2022-11-04 | 珠海正杏新材料科技有限公司 | Production method of chloroethylene carbonate |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304935A (en) * | 1999-11-19 | 2001-07-25 | 默克专利股份有限公司 | Preparation method of vinylene carbonate and its application |
| CN110483471A (en) * | 2019-09-08 | 2019-11-22 | 淮安瀚康新材料有限公司 | A kind of synthetic method of vinylene carbonate |
| CN114957194A (en) * | 2022-06-14 | 2022-08-30 | 华东理工大学 | Method for improving yield of vinylene carbonate |
| CN115286612A (en) * | 2022-07-27 | 2022-11-04 | 珠海正杏新材料科技有限公司 | Production method of chloroethylene carbonate |
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