CN116003374B - Method for synthesizing immediately separated vinylene carbonate - Google Patents
Method for synthesizing immediately separated vinylene carbonate Download PDFInfo
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- CN116003374B CN116003374B CN202211623177.8A CN202211623177A CN116003374B CN 116003374 B CN116003374 B CN 116003374B CN 202211623177 A CN202211623177 A CN 202211623177A CN 116003374 B CN116003374 B CN 116003374B
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- 238000000034 method Methods 0.000 title claims abstract description 45
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 80
- OYOKPDLAMOMTEE-UHFFFAOYSA-N 4-chloro-1,3-dioxolan-2-one Chemical compound ClC1COC(=O)O1 OYOKPDLAMOMTEE-UHFFFAOYSA-N 0.000 claims abstract description 57
- 150000001412 amines Chemical class 0.000 claims abstract description 55
- 239000007788 liquid Substances 0.000 claims abstract description 29
- 239000007787 solid Substances 0.000 claims abstract description 22
- 238000000926 separation method Methods 0.000 claims abstract description 21
- 239000000243 solution Substances 0.000 claims abstract description 13
- 239000011550 stock solution Substances 0.000 claims abstract description 5
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 72
- 239000012295 chemical reaction liquid Substances 0.000 claims description 20
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 12
- 239000003112 inhibitor Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims 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 claims description 8
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 8
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 claims description 8
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 6
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 6
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 claims description 3
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims 3
- 238000005292 vacuum distillation Methods 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 17
- 239000002904 solvent Substances 0.000 abstract description 8
- 239000006227 byproduct Substances 0.000 abstract description 5
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- -1 amine hydrochloride Chemical class 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 238000011534 incubation Methods 0.000 description 7
- 230000005484 gravity Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000066 reactive distillation Methods 0.000 description 1
- 238000011410 subtraction method Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
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- 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 provides a method for synthesizing vinylene carbonate by instant separation, which comprises the following steps: and (3) dropwise adding organic amine into the chloroethylene carbonate solution, in the dropwise adding process, carrying out solid-liquid separation immediately after reacting to generate solid, returning the separated liquid to the stock solution, continuously reacting with the dropwise added organic amine, and circularly reciprocating until the chloroethylene carbonate is completely consumed (the content is less than or equal to 0.1%), and finally carrying out reduced pressure rectification on the reaction solution to obtain the pure product of the vinylene carbonate. The method can remove reaction byproducts from the reaction system during the reaction, reduces the dosage of organic amine, does not need solvent participation, has high reaction yield, and is very suitable for large-scale production of vinylene carbonate.
Description
Technical Field
The invention relates to the field of lithium battery additives, in particular to a method for synthesizing vinylene carbonate by instant separation.
Background
The vinylene carbonate (Vinylene Carbonate), called VC for short, can form a stable SEI film on the surface of the electrode, so that the co-intercalation reaction of solvent molecules is effectively inhibited, the charge and discharge performance and the cycle life of the lithium battery can be remarkably improved, and the lithium battery film forming additive is very important. The vinylene carbonate is colorless transparent liquid under the condition of normal temperature in summer, has no special smell, and has the boiling point of 162 ℃ and the melting point of 19-22 ℃ under normal pressure.
At present, the synthesis methods of vinylene carbonate mainly comprise two methods:
the first method is to mix chloroethylene carbonate (CEC) solution with alkali (including organic amine)/acid-binding agent, then to carry out elimination reaction under certain temperature condition and solvent condition to obtain a mixture of vinylene carbonate, byproduct salt and solvent, then to remove byproduct salt by filtration, and finally to obtain pure vinylene carbonate by rectification crystallization. The synthesis principle is shown in figure 1. The method has the defects that a large amount of organic amine and organic amine hydrochloride exist in a reaction system, the organic amine and the organic amine hydrochloride can accelerate the decomposition of vinylene carbonate, the reaction yield is lower and is only 40-50%, and the three wastes are more, so that the method is not beneficial to environmental protection. More importantly, the reaction liquid is a solid-liquid mixture, the solid content is between 35% and 50%, and the pipeline is easy to be blocked in the material transferring process, so that the continuous production is not facilitated. CN 113979988A discloses a method for dropping high boiling point organic amine into a reaction kettle under negative pressure, and extracting vinylene carbonate while reacting, wherein the extracted crude vinylene carbonate has higher purity. However, the method has the problems that the temperature of the reactive distillation system is higher, the VC decomposition rate is accelerated, the reaction yield is not greatly improved, the viscosity of the reaction liquid in the later stage of the reaction is higher, the solid content is more than 60%, the material transfer is difficult, and the industrial production difficulty is higher.
The second method is that chloroethylene carbonate (CEC) is subjected to high-temperature dehydrochlorination under the condition of a catalyst to generate VC, the required temperature is higher than 200 ℃, the VC is easy to decompose and polymerize under the high-temperature condition, the yield is low, and the byproducts are more, so that the method is not suitable for large-scale industrialized production.
In view of the problems and drawbacks of the two methods for synthesizing vinylene carbonate described above, further improvements and developments of the methods for synthesizing vinylene carbonate are needed.
Disclosure of Invention
The invention provides a method for synthesizing vinylene carbonate by immediate separation, which comprises the following specific technical scheme:
a method for synthesizing vinylene carbonate by instant separation, which comprises the following steps:
dropwise adding organic amine into the chloroethylene carbonate solution, in the dropwise adding process, carrying out solid-liquid separation immediately after reacting to generate solid, returning the separated liquid to the stock solution, continuously reacting with the dropwise added organic amine, and circularly reciprocating until the chloroethylene carbonate is completely consumed, and preparing high-purity vinylene carbonate by using the residual reaction solution;
further, adding a polymerization inhibitor into the chloroethylene carbonate before dropwise adding organic amine into the chloroethylene carbonate, wherein the polymerization inhibitor is one or more of 2, 6-di-tert-butyl-p-cresol, hydroquinone, p-benzoquinone, methyl hydroquinone, p-hydroxyanisole and 2, 5-di-tert-butyl hydroquinone;
further, the polymerization inhibitor is added to the chloroethylene carbonate before the organic amine is added dropwise to the chloroethylene carbonate, wherein the amount of the polymerization inhibitor is 0.5-1 per mill of the content of the chloroethylene carbonate.
Further, adding chloroethylene carbonate into a reaction kettle before dripping organic amine into the chloroethylene carbonate, stirring and heating to 20-100 ℃, and preserving heat for 0.5-1h;
further, stirring and heating to 40-80 ℃;
further, the organic amine is one or more of triethylamine, trimethylamine, tri-n-butylamine, aniline, diphenylamine and benzidine;
further, the molar ratio of the organic amine to the total amount of chloroethylene carbonate is 1.03-1.10:1, a step of;
further, the dripping time of the organic amine is 3-5 hours;
further, the solid-liquid separation is realized by a centrifugal machine, a conveying pump is arranged between the centrifugal machine and the reaction kettle, the reaction solution is conveyed from the reaction kettle to the centrifugal machine by the conveying pump for solid-liquid separation, and the separated liquid returns to the reaction kettle to continuously react with the organic amine, and the process is circularly carried out;
further, the centrifuge circulates the reaction solution 60 to 150 times per hour;
further, the centrifugal machine is a centrifugal machine capable of realizing continuous discharging;
further, stopping dripping organic amine when the chloroethylene carbonate content in the reaction liquid is less than or equal to 0.1%, and continuously preserving heat for 2-3 hours after the dripping of the organic amine is finished, and performing vacuum rectification on the reaction liquid.
Further, the rectification vacuum degree of the reaction liquid is controlled to be 5-10mbar.
By adopting the technical scheme, the invention has the beneficial technical effects that:
1. according to the invention, the solid-liquid separation is carried out during the reaction, the organic amine hydrochloride is removed from the reaction system in time, the organic amine consumption is obviously reduced, and meanwhile, the invention does not need solvent participation and solvent recovery procedures, so that continuous production can be realized;
2. the method is simple, the yield of the vinylene carbonate is high, the three wastes are less, and the method is environment-friendly and can be used for producing the vinylene carbonate on a large scale.
Drawings
FIG. 1 is a schematic diagram of vinylene carbonate synthesis;
FIG. 2 is a synthetic process flow diagram of a method for synthesizing immediate separated vinylene carbonate according to the present invention.
In the accompanying drawings: 1. a reaction kettle; 2. and (5) a centrifugal machine.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
A method for synthesizing vinylene carbonate by instant separation, which comprises the following steps:
and (3) dropwise adding organic amine into the chloroethylene carbonate solution, in the dropwise adding process, carrying out solid-liquid separation immediately after the reaction to generate solid, returning the separated liquid to the stock solution, continuously reacting with the dropwise added organic amine, circularly reciprocating until the content of the chloroethylene carbonate is less than or equal to 0.1%, stopping dropwise adding the organic amine, and preserving the heat for a period of time. And (3) carrying out reduced pressure rectification on the residual reaction liquid to obtain a pure product of the vinylene carbonate. The method removes the generated organic amine hydrochloride from the reaction system in the reaction process of the chloroethylene carbonate and the organic amine, the content of the organic amine hydrochloride in the reaction system is less than 1%, the influence of the organic amine hydrochloride on the polymerization of the vinylene carbonate is greatly reduced, the organic amine can fully react with the chloroethylene carbonate, the consumption of the organic amine is reduced by 20% -40% compared with that of the conventional method, the consumption of the organic amine is obviously reduced, and the consumption of the organic amine is obviously reduced because the vinylene carbonate is unstable under alkaline conditions, the polymerization amount of the vinylene carbonate is obviously reduced due to the reduction of the consumption of the organic amine, and the yield of the vinylene carbonate is improved. Moreover, the method does not need solvent to participate in the reaction, reduces the solvent recovery procedure, is simple to operate, has high product yield, and is suitable for large-scale production.
Further, a polymerization inhibitor is added into the chloroethylene carbonate before the dropwise addition of the organic amine into the chloroethylene carbonate, wherein the polymerization inhibitor is one or more of 2, 6-di-tert-butyl-p-cresol, hydroquinone, p-benzoquinone, methyl hydroquinone, p-hydroxyanisole and 2, 5-di-tert-butyl hydroquinone. Adding polymerization inhibitor into chloroethylene carbonate solution in an amount of 0.5-1%
Adding chloroethylene carbonate into the reaction kettle 1 before dripping organic amine into the chloroethylene carbonate, stirring and heating to 20-100 ℃, and preserving heat for 0.5-1h. The reaction temperature is controlled to be 20-100 ℃, under the reaction condition, the organic amine can fully react with the chloroethylene carbonate, and when the temperature is lower than 20 ℃, the lower temperature can inhibit the reaction of the organic amine and the chloroethylene carbonate, and the polymerization rate of the vinylene carbonate is obviously improved due to the overhigh temperature, so that the reaction temperature is reasonably controlled. Specifically, the reaction temperature is 40-80 ℃.
Further, the organic amine is one or more of triethylamine, trimethylamine, tri-n-butylamine, aniline, diphenylamine and benzidine.
Too little organic amine can cause insufficient reaction of chloroethylene carbonate, and lower yield. Excessive use of the organic amine accelerates the decomposition and polymerization of vinylene carbonate, reduces the product yield and increases the production cost, so that the molar ratio of the organic amine to the total use amount of chloroethylene carbonate is controlled to be 1.03-1.10:1.
the dripping time of the organic amine is 3-5h, the organic amine is added at a constant speed in the whole reaction process, the added organic amine and chloroethylene carbonate are ensured to fully react, solid-liquid separation is carried out immediately after the reaction generates solid, and the separated liquid is returned to the stock solution to continuously react with the dripped organic amine, and the cycle is repeated until the solid is not generated any more.
Further, solid-liquid separation is realized by a centrifugal machine 2, a conveying pump is arranged between the centrifugal machine 2 and the reaction kettle 1, reaction liquid is conveyed to the centrifugal machine from the reaction kettle by the conveying pump for solid-liquid separation, the separated liquid returns to the reaction kettle for continuous reaction with organic amine, and the solid enters an organic amine recovery procedure, and the process is circularly carried out. The centrifuge is a centrifuge capable of continuously feeding and continuously discharging, and can be one of a disk centrifuge, a tube centrifuge, a horizontal bipolar pushing centrifuge or a horizontal screw centrifuge.
Specifically, the centrifuge circulates the reaction solution 60 to 150 times per hour. In the whole reaction process, the reaction liquid always circularly flows between the centrifugal machine and the reaction kettle, the centrifugal machine circulates the reaction liquid for 60-150 times per hour, the high-efficiency circulation of the reaction liquid ensures that the solid generated by the reaction can be timely centrifugally separated, and meanwhile, the centrifuged liquid circulates to the reaction kettle to continuously react with the organic amine.
When the content of chloroethylene carbonate in the reaction liquid is less than or equal to 0.1%, finishing the dropwise adding of the organic amine, continuously preserving heat for 2-3 hours after finishing the dropwise adding of the organic amine, and carrying out reduced pressure rectification on the reaction liquid to obtain a pure product of vinylene carbonate.
Example 1
500.00g of chloroethylene carbonate (3.9222 mol) with a content of 96.1001% and 0.5g of 2, 6-di-tert-butyl-p-cresol (BHT) were added to a reaction vessel, and after stirring and dissolution, the temperature was raised to 65℃and kept for 0.5h. After the end of the incubation, triethylamine was added dropwise with the addition time controlled at 5h and the triethylamine mass at 421.82g (99%, 4.1183mol, n (CEC): n (triethylamine) =1:1.05). Simultaneously, the centrifugal machine is started, the material transfer pump is started, the reaction liquid in the reaction kettle is conveyed into the centrifugal machine, the solid salt is discharged from the solid discharge port, clear liquid automatically flows back to the reaction kettle under the action of gravity, and the centrifugal machine circulates 120 times per hour. After the triethylamine is added dropwise and is kept warm for 2 hours, the reaction is finished, vacuum rectification is carried out, and the VC pure product is obtained, wherein the actual yield of the VC is 87.31%.
Example 2
500.00g of chloroethylene carbonate (3.9222 mol) with a content of 96.1001% are added into a reaction kettle, 0.25g of p-hydroxyanisole is added, stirred and dissolved, then the temperature is raised to 40 ℃, and the temperature is kept for 0.5h. After the end of the incubation, triethylamine was added dropwise with the addition time controlled at 4h and the triethylamine mass at 412.93g (99%, 4.0399mol, n (CEC): n (triethylamine) =1:1.03). Simultaneously, the centrifugal machine is started, the material transfer pump is started, the reaction liquid in the reaction kettle is conveyed into the centrifugal machine, the solid salt is discharged from the solid discharge port, clear liquid automatically flows back to the reaction kettle under the action of gravity, and the centrifugal machine circulates 150 times per hour. After the triethylamine is added dropwise and is kept warm for 2 hours, the reaction is finished, and vacuum rectification is carried out to obtain a VC pure product, wherein the VC yield is 85.34%.
Example 3
500.00g of chloroethylene carbonate (3.9222 mol) with a content of 96.1001% are added into a reaction kettle, 0.4g of p-benzoquinone and methyl hydroquinone are added, and after stirring and dissolution, the temperature is raised to 80 ℃ and the temperature is kept for 1h. After the end of the incubation, triethylamine was added dropwise with the addition time controlled at 3h and the triethylamine mass at 470.95g (99%, 4.3144mol, n (CEC): n (triethylamine) =1:1.10). Simultaneously, the centrifugal machine is started, the material transfer pump is started, the reaction liquid in the reaction kettle is conveyed into the centrifugal machine, the solid salt is discharged from the solid discharge port, clear liquid automatically flows back to the reaction kettle under the action of gravity, and the centrifugal machine circulates for 60 times per hour. After the triethylamine is added dropwise and is kept warm for 3 hours, the reaction is finished, and vacuum rectification is carried out to obtain a VC pure product, wherein the VC yield is 82.87%.
Example 4
500.00g of chloroethylene carbonate (3.9222 mol) with a content of 96.1001% and 0.5g of 2, 6-di-tert-butyl-p-cresol (BHT) were added to a reaction vessel, and after stirring and dissolution, the temperature was raised to 65℃and kept for 0.5h. After the end of the incubation, aniline was added dropwise, the time being controlled at 5h, the mass of aniline being 387.40g (99%, 4.1183mol, n (CEC): n (aniline) =1:1.05). Simultaneously, the centrifugal machine is started, the material transfer pump is started, the reaction liquid in the reaction kettle is conveyed into the centrifugal machine, the solid salt is discharged from the solid discharge port, clear liquid automatically flows back to the reaction kettle under the action of gravity, and the centrifugal machine circulates for 60 times per hour. After the aniline is added dropwise and is kept warm for 2 hours, the reaction is finished, and vacuum rectification is carried out to obtain a VC pure product, wherein the actual yield of the VC is 83.16%.
Example 5
500.00g of chloroethylene carbonate (3.9222 mol) with a content of 96.1001% and 0.5g of 2, 6-di-tert-butyl-p-cresol (BHT) were added to a reaction vessel, and after stirring and dissolution, the temperature was raised to 100℃and kept for 0.8h. After the end of the incubation, triethylamine was added dropwise with the addition time controlled at 5h and the triethylamine mass at 420.94g (99%, 4.1183mol, n (CEC): n (triethylamine) =1:1.05). Simultaneously, the centrifugal machine is started, the material transfer pump is started, the reaction liquid in the reaction kettle is conveyed into the centrifugal machine, the solid salt is discharged from the solid discharge port, clear liquid automatically flows back to the reaction kettle under the action of gravity, and the centrifugal machine circulates 150 times per hour. After the triethylamine is added dropwise and is kept warm for 2 hours, the reaction is finished, and vacuum rectification is carried out to obtain a pure VC product, wherein the actual yield of the VC is 81.93%.
Example 6
500.00g of chloroethylene carbonate (3.9222 mol) with a content of 96.1001% and 0.5g of 2, 6-di-tert-butyl-p-cresol (BHT) were added to a reaction vessel, and after stirring and dissolution, the temperature was raised to 20℃and kept for 0.8h. After the end of the incubation, the addition of diphenylamine was started for 5 hours with a mass of 703.95g (99%, 4.1183mol, n (CEC): n (diphenylamine) =1:1.05). Simultaneously, the centrifugal machine is started, the material transfer pump is started, the reaction liquid in the reaction kettle is conveyed into the centrifugal machine, the solid salt is discharged from the solid discharge port, clear liquid automatically flows back to the reaction kettle under the action of gravity, and the centrifugal machine circulates 140 times per hour. After the diphenylamine is added dropwise and the reaction is finished after heat preservation is carried out for 2 hours, rectification and crystallization are carried out, and the actual yield of VC is 80.79%.
Comparative example 1
500.00g of chloroethylene carbonate (3.9222 mol) with a content of 96.1001% and 1000g of dimethyl carbonate with a content of 99.9% are added into a reaction kettle, 0.5g of 2, 6-di-tert-butyl-p-cresol (BHT) is added, stirred and dissolved, then heated to 65 ℃ and the temperature is kept for 0.5h. After the end of the incubation, triethylamine was added dropwise with the addition time controlled at 5h and the triethylamine mass at 420.94g (99%, 4.1183mol, n (CEC): n (triethylamine) =1:1.05). After the triethylamine is added dropwise and the reaction is finished after heat preservation is carried out for 2 hours, rectification and crystallization are carried out, and the actual yield of VC is 59.76%.
Comparative example 2
The reaction temperature was set at 8℃as compared with example 1, and the other conditions were unchanged. At this time, chloroethylene carbonate and triethylamine do not react.
The product yields of examples 1-6 and comparative examples 1-2 were counted to obtain Table 1. Wherein, the content is as follows: the calculation is performed by a subtraction method, i.e. by 100% subtracting the sum of the individual impurity contents in the product. Yield: the theoretical product quality is calculated as the percentage ratio of the actual product quality to the theoretical product quality, with no excess raw materials in the reaction equation.
TABLE 1 yields of products for examples 1-6 and comparative examples 1-2
As can be seen from the above table, compared with the conventional stirring reaction (comparative example 1), the produced organic amine hydrochloride is removed by the centrifuge while chloroethylene carbonate reacts with the organic amine, and the byproduct organic amine hydrochloride can be removed in the reaction stage, so that the product yield is greatly improved, and the method is suitable for mass production.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (9)
1. A method for synthesizing vinylene carbonate by instant separation, which is characterized by comprising the following steps:
dripping organic amine into chloroethylene carbonate, in the dripping process, carrying out solid-liquid separation immediately after reacting to generate solid, returning the separated liquid to the stock solution, continuously reacting with the dripping organic amine, and circularly reciprocating until the chloroethylene carbonate is completely consumed, and preparing vinylene carbonate by using the residual reaction solution;
the molar ratio of the organic amine to the chloroethylene carbonate is 1.03-1.10:1, a step of;
the dripping time of the organic amine is 3-5h;
adding a polymerization inhibitor into chloroethylene carbonate before dropwise adding organic amine into the chloroethylene carbonate, wherein the polymerization inhibitor is one or more of 2, 6-di-tert-butyl-p-cresol, hydroquinone, p-benzoquinone, methyl hydroquinone, p-hydroxyanisole and 2, 5-di-tert-butyl-hydroquinone.
2. The method for synthesizing immediate separation vinylene carbonate according to claim 1, wherein the polymerization inhibitor is added to chloroethylene carbonate in an amount of 0.5-1% by mass of chloroethylene carbonate.
3. The method for synthesizing the immediately separated vinylene carbonate according to claim 1, wherein before the organic amine is added dropwise into the chloroethylene carbonate, the chloroethylene carbonate is added into a reaction kettle, stirred and heated to 20-100 ℃, and then the temperature is kept for 0.5-1h.
4. A process for the synthesis of immediate separation vinylene carbonate according to claim 3, characterized in that the temperature is raised to 40-80 ℃ with stirring.
5. The method for synthesizing ethylene carbonate according to claim 1, wherein the organic amine is one or more of triethylamine, trimethylamine, tri-n-butylamine, aniline, diphenylamine and benzidine.
6. The method for synthesizing the immediately separated vinylene carbonate according to claim 3, wherein the solid-liquid separation is realized by a centrifugal machine, a conveying pump is arranged between the centrifugal machine and the reaction kettle, the reaction liquid is conveyed from the reaction kettle to the centrifugal machine by the conveying pump for solid-liquid separation, and the separated liquid returns to the reaction kettle to continuously react with the organic amine, and the process is circularly carried out.
7. The method for synthesizing ethylene carbonate according to claim 6, wherein the centrifuge circulates the reaction solution 60 to 150 times per hour.
8. The method for synthesizing the immediately separated vinylene carbonate according to claim 1, wherein the temperature is kept for 2-3 hours after the organic amine is added dropwise, and the residual reaction liquid is subjected to vacuum rectification after the temperature is kept.
9. The method for synthesizing ethylene carbonate by immediate separation according to claim 8, wherein the vacuum degree of vacuum distillation is controlled to be 5-10mbar.
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