CN114763322A - Method for preparing diethyl carbonate and ethyl methyl carbonate mixed ester - Google Patents
Method for preparing diethyl carbonate and ethyl methyl carbonate mixed ester Download PDFInfo
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- CN114763322A CN114763322A CN202011637129.5A CN202011637129A CN114763322A CN 114763322 A CN114763322 A CN 114763322A CN 202011637129 A CN202011637129 A CN 202011637129A CN 114763322 A CN114763322 A CN 114763322A
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- carbonate
- diethyl carbonate
- ethyl methyl
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- mixed ester
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- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 title claims abstract description 104
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 150000002148 esters Chemical class 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 28
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 80
- 238000006243 chemical reaction Methods 0.000 claims abstract description 71
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000003054 catalyst Substances 0.000 claims abstract description 51
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 40
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- ODEXXNNMGSAXBF-UHFFFAOYSA-N diethyl carbonate;ethyl methyl carbonate Chemical compound CCOC(=O)OC.CCOC(=O)OCC ODEXXNNMGSAXBF-UHFFFAOYSA-N 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000002585 base Substances 0.000 description 34
- 235000019441 ethanol Nutrition 0.000 description 11
- 239000003513 alkali Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 238000012544 monitoring process Methods 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- -1 methylene, ethylene, propylene Chemical group 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- SUBJHSREKVAVAR-UHFFFAOYSA-N sodium;methanol;methanolate Chemical compound [Na+].OC.[O-]C SUBJHSREKVAVAR-UHFFFAOYSA-N 0.000 description 2
- 239000004032 superbase Substances 0.000 description 2
- 150000007525 superbases Chemical class 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 150000008282 halocarbons Chemical group 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 125000002346 iodo group Chemical group I* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000000066 reactive distillation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0255—Phosphorus containing compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
- C07F9/659—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms having three phosphorus atoms as ring hetero atoms in the same ring
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- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention aims to solve the problem that the yield of ethyl methyl carbonate is not high in the synthesis of diethyl carbonate and ethyl methyl carbonate, and provides a method for preparing diethyl carbonate and ethyl methyl carbonate, wherein anhydrous ethanol and dimethyl carbonate are used as raw materials, and ester exchange reaction is carried out under the action of an organic nonionic phosphine base catalyst to obtain mixed ester containing diethyl carbonate and ethyl methyl carbonate, wherein the mass ratio of ethyl methyl carbonate to diethyl carbonate in the mixed ester is 2: 1-15: 1. The invention realizes the high yield generation of the methyl ethyl carbonate by the reaction of raw materials such as absolute ethyl alcohol, dimethyl carbonate and the like under the action of a novel catalyst.
Description
Technical Field
The invention relates to a synthetic method of an organic compound, in particular to a method for preparing diethyl carbonate and methyl ethyl carbonate mixed ester by dimethyl carbonate and ethanol through ester exchange reaction.
Background
Diethyl carbonate and methyl ethyl carbonate are excellent solvents and important organic synthesis intermediates, and are widely applied to industries of electrolyte solvents of lithium batteries, synthetic fibers, pharmacy and the like. The common simple and safe method for preparing diethyl carbonate and ethyl methyl carbonate mixed ester at present comprises the following steps: dimethyl carbonate and ethanol are used as raw materials, and the process is characterized in that the reaction process is strengthened by reactive distillation and then the industrial grade methyl ethyl carbonate is obtained by a light component removal tower. However, the main product of the method is that the mass ratio of diethyl carbonate is more than 70 percent, and the mass ratio of ethyl methyl carbonate is less than 30 percent.
In recent years, as the consumption of ethyl methyl carbonate in the lithium ion battery electrolyte greatly exceeds the consumption of diethyl carbonate, the mass ratio of ethyl methyl carbonate to diethyl carbonate needs to be changed by finding a high-efficiency catalyst and adjusting the process, so as to meet the market demand.
Disclosure of Invention
The invention aims at solving the technical problem that the mass ratio of ethyl methyl carbonate to diethyl carbonate is not high in the synthesis of the mixed ester of diethyl carbonate and ethyl methyl carbonate in the prior art, thereby providing a method for preparing the mixed ester of diethyl carbonate and ethyl methyl carbonate by generating ethyl methyl carbonate with high yield.
The method for preparing the mixed ester of diethyl carbonate and ethyl methyl carbonate is realized by the following technical scheme, absolute ethyl alcohol and dimethyl carbonate are used as raw materials, ester exchange reaction is carried out under the action of an organic nonionic phosphine base catalyst, and the mixed ester containing diethyl carbonate and ethyl methyl carbonate is obtained, wherein the mass ratio of ethyl methyl carbonate to diethyl carbonate in the mixed ester is 2: 1-15: 1.
Optionally, the organic nonionic phosphine base catalyst is a phosphine base compound containing more than two P-N bonds, and more preferably a phosphine base compound containing three P-N bonds.
Optionally, the organic nonionic phosphine base catalyst is a heterocyclic phosphine base compound.
Optionally, the organic nonionic phosphine base catalyst comprises the following structural formula:
wherein R is1、R2、R3Each independently selected from alkylene groups having 1 to 6 carbon atoms, R4、R5、R6Each independently selected from hydrogen, hydrocarbyl, alkoxy, halogenated hydrocarbyl.
Optionally, the structural formula of the organic nonionic phosphine base catalyst is selected from at least one of the following compounds of structural formulas (1) to (5):
optionally, the mass of the organic nonionic phosphine base catalyst is 0.1-5% of the total mass of the materials.
Optionally, the mass ratio of the absolute ethyl alcohol to the dimethyl carbonate in the raw materials is 1: 1-1: 3.
Optionally, the reaction temperature of the transesterification reaction is 75-95 ℃, the reaction time is 4-6 h, and the preferable reaction temperature is 80-90 ℃.
Optionally, the raw material further contains diethyl carbonate, and the diethyl carbonate is selected from one or more of pure diethyl carbonate, a mixture of diethyl carbonate and ethyl methyl carbonate generated by the reaction, and a mixture of diethyl carbonate and ethyl methyl carbonate generated by the reaction and methanol.
Optionally, the mass of diethyl carbonate in the raw material is 3% -15% of the total mass of the anhydrous ethanol and the dimethyl carbonate.
Optionally, the feeding sequence of the preparation method is as follows: firstly, adding dimethyl carbonate and an organic non-ionic phosphine base catalyst into a container, then adding diethyl carbonate, heating to 75-95 ℃, and finally adding absolute ethyl alcohol to continue reaction.
Optionally, when the preparation method is applied to an industrial device, anhydrous ethanol is added to the lower part of the reaction rectifying tower, dimethyl carbonate is added to the middle part of the reaction rectifying tower, and a mixture of diethyl carbonate and an organic nonionic phosphine base catalyst is added to the upper part of the reaction rectifying tower; the temperature at the top of the rectifying tower is 60-68 ℃, and preferably 62-64 ℃.
The invention has the beneficial effects that: compared with the prior art, the novel organic nonionic phosphine base catalyst is adopted in the process of preparing the diethyl carbonate and methyl ethyl carbonate mixed ester, has a special conjugated structure, has higher thermal stability and organic super-strong base performance, and realizes the efficient generation of the methyl ethyl carbonate by the efficient catalytic activity of the novel organic nonionic phosphine base catalyst, wherein the mass ratio of the methyl ethyl carbonate to the diethyl carbonate in the product is more than 2: 1. Meanwhile, the raw materials are easy to obtain, the process is simple, the material toxicity is low, and the method is suitable for industrial production. In addition, the organic nonionic phosphine base catalyst has long service life and can be recycled, so that the production cost is greatly reduced.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more clear, the present invention is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
The method for preparing diethyl carbonate and ethyl methyl carbonate mixed ester comprises the steps of taking absolute ethyl alcohol and dimethyl carbonate as raw materials, and carrying out ester exchange reaction under the action of an organic nonionic phosphine base catalyst to obtain mixed ester containing diethyl carbonate and ethyl methyl carbonate, wherein the mass ratio of ethyl methyl carbonate to diethyl carbonate in the mixed ester is 2: 1-15: 1.
Preferably, the mass ratio of the ethyl methyl carbonate to the diethyl carbonate in the mixed ester is 5: 1-15: 1.
The above transesterification reaction includes reaction (1) and reaction (2):
in the invention, the organic nonionic phosphine base catalyst has higher thermal stability and organic superbase performance due to the specific conjugated structure, can efficiently catalyze the reaction at the temperature of 75-95 ℃, has good solubility, can be used as a solvent to dissolve reactants, fully plays a role in catalysis, has longer service life and can be recycled.
In some embodiments, the organic nonionic phosphine base catalyst is a phosphine base compound containing more than two P-N bonds, more preferably three P-N bonds. In some embodiments, the organic nonionic phosphine base catalyst is a heterocyclic phosphine base compound. By adopting the catalyst in the embodiment, the mass ratio of the methyl ethyl carbonate to the diethyl carbonate in the product can be further improved in the preparation process of the mixed ester of the methyl ethyl carbonate and the diethyl carbonate.
In some embodiments, the organic nonionic phosphine base catalyst comprises the following structural formula:
wherein R is1、R2、R3Each independently selected from alkylene groups having 1 to 6 carbon atoms, R4、R5、R6Each independently selected from hydrogen, hydrocarbyl, alkoxy, halogenated hydrocarbyl.
Examples of the alkylene group having 1 to 6 carbon atoms include: methylene, ethylene, propylene, isopropylene, butylene, isobutylene, neopentylene, tertiarybutylene, and the like.
Preferably, R4、R5、R6Each independently selected from the group consisting of alkyl of 1 to 10 carbon atoms, phenyl, tolyl, alkoxy of 1 to 10 carbon atoms, and halogenated hydrocarbyl of 1 to 10 carbon atoms.
Examples of the alkyl group having 1 to 10 carbon atoms include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, neo-butyl, tert-butyl and the like.
The halogenated hydrocarbon group having 1 to 10 carbon atoms may specifically be fluoro, chloro, bromo or iodo.
In some embodiments, the organic nonionic phosphine base catalyst structural formula is selected from at least one of the following compounds of structural formulae (1) - (5):
the compounds in the structural formulas (1) to (5) are used as catalysts, and the mass ratio of the methyl ethyl carbonate to the diethyl carbonate in the product can be further improved in the preparation process of the mixed ester of the methyl ethyl carbonate and the diethyl carbonate.
In some embodiments, the mass of the organic nonionic phosphine base catalyst is 0.1% to 5% of the total feed mass.
Preferably, the mass of the organic nonionic phosphine base catalyst is 0.1-3% of the total mass of the materials.
Further, the mass of the organic nonionic phosphine base catalyst is 0.1-2% of the total mass of the materials.
Optionally, the mass of the organic nonionic phosphine base catalyst is 0.1-0.8% of the total mass of the materials.
In some embodiments, the feedstock further comprises diethyl carbonate selected from one or more of pure diethyl carbonate, a mixture of diethyl carbonate and ethyl methyl carbonate formed by the reaction, and a mixture of diethyl carbonate and ethyl methyl carbonate formed by the reaction and methanol. The diethyl carbonate is added to react with dimethyl carbonate, so that the dimethyl carbonate is further converted into ethyl methyl carbonate, and the yield of the ethyl methyl carbonate is improved.
In some embodiments, as shown in fig. 1, when the preparation method is applied to an industrial device, anhydrous ethanol is added to the lower part of a rectifying tower, dimethyl carbonate is added to the middle part of the rectifying tower, a mixture of diethyl carbonate and a catalyst is added to the upper part of the rectifying tower, diethyl carbonate and dimethyl carbonate firstly react on the middle upper part of the rectifying tower (2) to directly generate ethyl methyl carbonate, and then unreacted diethyl carbonate and dimethyl carbonate flow into the lower part of the rectifying tower and then react with anhydrous ethanol (1) to further generate ethyl methyl carbonate, so that 100% conversion of ethanol is realized.
In some embodiments, the feed sequence of the preparation method is: firstly, adding dimethyl carbonate and an organic nonionic phosphine base catalyst into a container, then adding diethyl carbonate or a mixture containing diethyl carbonate, heating to 75-95 ℃, and finally adding absolute ethyl alcohol to continue reaction, wherein actually, the reaction is carried out in multiple steps:
the feeding sequence aims to enable diethyl carbonate to react with dimethyl carbonate firstly (2), convert most of dimethyl carbonate into ethyl methyl carbonate, and finally add ethanol to react (1), wherein the diethyl carbonate existing in a reaction system can inhibit the reaction (4), promote the reaction to proceed to (3), and increase the conversion rate of ethyl methyl carbonate by ethanol.
In some embodiments, the mass ratio of the absolute ethyl alcohol to the dimethyl carbonate is 1: 1-1: 3, which sufficiently ensures that the ethyl methyl carbonate can react with the ethyl alcohol after reacting with the diethyl carbonate, and the ethyl alcohol is completely converted into the ethyl methyl carbonate.
In some embodiments, the mass of diethyl carbonate in the feed solution is 3% to 15% of the total mass of ethanol and dimethyl carbonate. The yield of diethyl carbonate and ethyl methyl carbonate can be adjusted by changing the amount of diethyl carbonate used.
In some embodiments, the system after the reaction mainly comprises diethyl carbonate, ethyl methyl carbonate, dimethyl carbonate, methanol and ethanol, the diethyl carbonate and the ethyl methyl carbonate are purified by rectification, and other components can return to the reaction system for circular reaction, so that the method is safe, environment-friendly and cost-saving.
In some embodiments, the temperature of the tower kettle is controlled at 75-95 ℃, and in order to avoid uneven heating in the kettle, oil bath heating can be used. Preferably, the temperature at the top of the tower is controlled to be 60-68 ℃, preferably 62-64 ℃ in order to promote the reversible reaction by distilling light methanol at the top of the tower.
In order that the present invention may be more clearly understood, the following detailed description will be given by way of example.
Example 1:
200g of absolute ethyl alcohol and 400g of dimethyl carbonate are measured, the dimethyl carbonate is firstly added into a container, then a phosphorus alkali compound catalyst with a chemical structural formula (3) accounting for 0.5 percent of the total mass of the materials is weighed and poured into the container, when the temperature of the system is raised to 85 ℃, the absolute ethyl alcohol is dripped into the reactor, and the stirring reaction is carried out for 4 hours. After the reaction is finished, the composition and the content of reaction components are monitored, and the mass ratio of the ethyl methyl carbonate to the diethyl carbonate in the mixed ester obtained under the condition is 7.95: 1.
Example 2:
200g of absolute ethyl alcohol and 400g of dimethyl carbonate are measured, the dimethyl carbonate is firstly added into a container, then the phosphorus alkali compound catalyst with the chemical structural formula (1) accounting for 0.5 percent of the total mass of the materials is weighed and poured into the container, when the temperature of the system is raised to 85 ℃, the absolute ethyl alcohol is dripped into the reactor, and the stirring reaction is continued for 4 hours. And after the reaction is finished, monitoring the composition and the content of reaction components, deducting the added diethyl carbonate under the condition, and controlling the mass ratio of the ethyl methyl carbonate to the diethyl carbonate generated in the actual reaction to be 7.47: 1.
Example 3:
200g of absolute ethyl alcohol and 400g of dimethyl carbonate are measured, firstly, the dimethyl carbonate is added into a container, 60g of diethyl carbonate accounting for 10 percent of the total mass of the absolute ethyl alcohol and the dimethyl carbonate is weighed and added into the container, then, a phosphorus alkali compound catalyst of a chemical structural formula (3) accounting for 0.5 percent of the total mass of the absolute ethyl alcohol and the dimethyl carbonate is weighed and poured into the container, when the temperature of a system is raised to 85 ℃, the absolute ethyl alcohol is dripped into a reactor, and the stirring reaction is continued for 4 hours. And after the reaction is finished, monitoring the composition and the content of reaction components, and deducting the added diethyl carbonate under the condition, wherein the mass ratio of the ethyl methyl carbonate to the diethyl carbonate generated in the actual reaction is 8.65: 1.
Example 4:
200g of absolute ethyl alcohol and 400g of dimethyl carbonate are measured, the dimethyl carbonate is firstly added into a container, 60g of diethyl carbonate accounting for 10 percent of the total mass of the absolute ethyl alcohol and the dimethyl carbonate is weighed and added into the container, then a phosphorus alkali compound catalyst of a chemical structural formula (4) accounting for 0.5 percent of the total mass of the anhydrous ethyl alcohol and the dimethyl carbonate is weighed and poured into the container, when the temperature of a system is raised to 85 ℃, the absolute ethyl alcohol is dripped into a reactor, and the stirring reaction is continuously carried out for 4 hours. And after the reaction is finished, monitoring the composition and the content of reaction components, deducting the added diethyl carbonate under the condition, and controlling the mass ratio of the ethyl methyl carbonate to the diethyl carbonate generated in the actual reaction to be 10.74: 1.
Example 5:
on a small-sized rectifying device, as shown in figure 1, 20Kg/h of anhydrous ethanol is added at the lower part of a reaction rectifying tower, 40Kg/h of dimethyl carbonate is added at the middle part, 6Kg/h of diethyl carbonate and 0.33Kg/h of a phosphorus-alkali compound catalyst with a chemical structural formula (3) are added at the upper part, the feeding speed is ensured to be uniformly controlled, the temperature of a tower kettle is heated to 90 ℃, the temperature of the tower top is controlled to 64 ℃, the reflux reaction is carried out for 4h, the reaction component composition and the content thereof are monitored after the reaction is finished, the added diethyl carbonate is deducted under the condition, and the mass ratio of the ethyl methyl carbonate and the diethyl carbonate generated in the actual reaction is 13.61: 1.
Example 6:
200g of absolute ethyl alcohol and 400g of dimethyl carbonate are weighed, 60g of diethyl carbonate accounting for 10 percent of the total mass of the absolute ethyl alcohol and the dimethyl carbonate and a phosphorus-base compound catalyst of a chemical structural formula (3) accounting for 1 percent of the total mass of the anhydrous ethyl alcohol and the dimethyl carbonate are weighed, all raw materials are poured into a container together, the temperature of the system is raised to 90 ℃, and the stirring reaction is continued for 4 hours. And after the reaction is finished, monitoring the composition and the content of reaction components, deducting the added diethyl carbonate under the condition, and controlling the mass ratio of the ethyl methyl carbonate to the diethyl carbonate generated in the actual reaction to be 11.47: 1.
Comparative example 1:
200g of absolute ethyl alcohol and 400g of dimethyl carbonate are weighed, firstly, the dimethyl carbonate is added into a container, 60g of diethyl carbonate accounting for 10 percent of the total mass of the absolute ethyl alcohol and the dimethyl carbonate is weighed and added into the container, then, sodium methoxide-methanol solution accounting for 0.5 percent of the total mass of the dimethyl carbonate is weighed and poured into the container, when the temperature of a system is raised to 90 ℃, the absolute ethyl alcohol is dripped into a reactor, and the stirring reaction is continuously carried out for 4 hours. And after the reaction is finished, monitoring the composition and the content of reaction components, deducting the added diethyl carbonate under the condition, and controlling the mass ratio of the ethyl methyl carbonate to the diethyl carbonate generated in the actual reaction to be 1.90: 1.
The experimental data of the above examples and comparative examples are shown in the following table:
as can be seen from the comparison of the data of comparative example 1 and examples 1-6, in examples 1-6, when the organic nonionic phosphine base catalyst is used in the preparation of the mixed ester of ethyl methyl carbonate and diethyl carbonate, the mass ratio of ethyl methyl carbonate to diethyl carbonate in the reaction product reaches 7:1 or more; in contrast, in comparative example 1, a sodium methoxide-methanol solution was used as a catalyst, the mass ratio of the prepared ethyl methyl carbonate to the prepared diethyl carbonate was only 1.90:1, and the yield of the ethyl methyl carbonate was much lower than that of the example using the organic nonionic phosphine base catalyst.
In addition, as shown in the data of examples 1-2 and 3-4, diethyl carbonate was additionally added to the raw materials in the production of the ethyl methyl carbonate and diethyl carbonate mixed ester of examples 3-4, and the mass ratio of ethyl methyl carbonate to diethyl carbonate was larger than that of example 1-2 in which diethyl carbonate was not added, indicating that the added diethyl carbonate participated in the reaction, further promoting the improvement of the yield of ethyl methyl carbonate.
In addition, in example 4, the phosphorus alkali compound of structural formula (4) is used as a catalyst, and the excellent effect of 10.74:1 of the mass ratio of ethyl methyl carbonate to diethyl carbonate in the reaction product is achieved, which indicates that the organic nonionic phosphine alkali catalyst of structural formula (4) can obviously improve the yield of ethyl methyl carbonate.
In addition, an industrial device is adopted in example 5, as shown in figure 1, anhydrous ethanol is added into the lower part of a reaction rectifying tower, dimethyl carbonate is added into the middle part of the reaction rectifying tower, and a mixture of diethyl carbonate and an organic nonionic phosphine base catalyst is added into the upper part of the reaction rectifying tower; the temperature at the top of the rectifying tower is controlled to be 60-68 ℃, the mass ratio of the methyl ethyl carbonate to the diethyl carbonate in the reaction product reaches an excellent yield of 13.61:1, and the process and the condition setting are adopted in industrial production, so that the yield of the methyl ethyl carbonate can be further improved.
In conclusion, the novel organic nonionic phosphine base catalyst is adopted in the process of preparing the diethyl carbonate and ethyl methyl carbonate mixed ester, the catalyst has a special conjugated structure, so that the catalyst has higher thermal stability and organic superbase performance, the mass ratio of ethyl methyl carbonate to diethyl carbonate in a product is obviously higher than 2:1 through the high-efficiency catalytic activity of the novel organic nonionic phosphine base catalyst, wherein compounds of structural formulas (1) to (5) are adopted as the catalyst, and the mass ratio of ethyl methyl carbonate to diethyl carbonate is higher than 5:1, in the industrial production process, the process and condition control of the invention are adopted, the mass ratio of the methyl ethyl carbonate to the diethyl carbonate is up to 13.61:1, and the yield of the methyl ethyl carbonate is obviously improved.
The above description is intended to be illustrative of the preferred embodiment of the present invention and should not be taken as limiting the invention, but rather, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (10)
1. The method for preparing the diethyl carbonate and ethyl methyl carbonate mixed ester is characterized in that absolute ethyl alcohol and dimethyl carbonate are used as raw materials, ester exchange reaction is carried out under the action of an organic non-ionic phosphine base catalyst, and the mixed ester containing diethyl carbonate and ethyl methyl carbonate is obtained, wherein the mass ratio of ethyl methyl carbonate to diethyl carbonate in the mixed ester is 2: 1-15: 1.
2. The process of claim 1, wherein the organic nonionic phosphine base catalyst comprises the formula:
wherein R is1、R2、R3Each independently selected from alkylene groups having 1 to 6 carbon atoms, R4、R5、R6Each independently selected from hydrogen, hydrocarbyl, alkoxy, halogenated hydrocarbyl.
3. The method for preparing diethyl carbonate and ethyl methyl carbonate mixed ester according to claim 2, wherein the organic nonionic phosphine base catalyst is at least one compound selected from the following structural formulas (1) to (5):
4. the method for preparing the diethyl carbonate and ethyl methyl carbonate mixed ester according to claim 1, wherein the mass of the organic nonionic phosphine base catalyst is 0.1-5% of the mass of the total material.
5. The method for preparing the mixed ester of diethyl carbonate and ethyl methyl carbonate according to claim 1, wherein the mass ratio of the anhydrous ethanol to the dimethyl carbonate in the raw materials is 1: 1-1: 3.
6. The method for preparing the mixed ester of diethyl carbonate and ethyl methyl carbonate according to claim 1, wherein the reaction temperature of the ester exchange reaction is 75-95 ℃ and the reaction time is 4-6 h.
7. The method of claim 1, wherein the raw material further comprises diethyl carbonate, and the diethyl carbonate is selected from one or more of pure diethyl carbonate, a mixture of diethyl carbonate and ethyl methyl carbonate generated by the reaction, and a mixture of diethyl carbonate and ethyl methyl carbonate and methanol generated by the reaction.
8. The method for preparing the mixed ester of diethyl carbonate and ethyl methyl carbonate according to claim 7, wherein the mass of diethyl carbonate in the raw material is 3-15% of the total mass of absolute ethyl alcohol and dimethyl carbonate.
9. The method for preparing diethyl carbonate and ethyl methyl carbonate mixed ester according to claim 7, wherein the feeding sequence of the preparation method is as follows: firstly, adding dimethyl carbonate and an organic nonionic phosphine base catalyst into a container, then adding diethyl carbonate, heating to 75-95 ℃, and finally adding absolute ethyl alcohol to continue reaction.
10. The method for preparing the diethyl carbonate-ethyl methyl carbonate mixed ester according to claim 7, wherein when the preparation method is applied to an industrial device, the anhydrous ethanol is added into the lower part of a reaction rectifying tower, the dimethyl carbonate is added into the middle part of the reaction rectifying tower, and the mixture of the diethyl carbonate and the organic nonionic phosphine base catalyst is added into the upper part of the reaction rectifying tower; the temperature at the top of the rectifying tower is 60-68 ℃.
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| US20050176978A1 (en) * | 2003-12-15 | 2005-08-11 | Verkade John G. | Immobilized iminophosphatranes useful for transesterification |
| CN101381308A (en) * | 2008-10-22 | 2009-03-11 | 天津大学 | Preparation method of diethyl carbonate and methyl ethyl carbonate mixed ester |
| CN111072480A (en) * | 2019-11-27 | 2020-04-28 | 屈强好 | Method for producing methyl ethyl carbonate by using ionic liquid catalysis ester exchange method |
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| US20050176978A1 (en) * | 2003-12-15 | 2005-08-11 | Verkade John G. | Immobilized iminophosphatranes useful for transesterification |
| CN101381308A (en) * | 2008-10-22 | 2009-03-11 | 天津大学 | Preparation method of diethyl carbonate and methyl ethyl carbonate mixed ester |
| CN111072480A (en) * | 2019-11-27 | 2020-04-28 | 屈强好 | Method for producing methyl ethyl carbonate by using ionic liquid catalysis ester exchange method |
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