CN114763322B - Method for preparing diethyl carbonate and methyl ethyl carbonate mixed ester - Google Patents
Method for preparing diethyl carbonate and methyl ethyl carbonate mixed ester Download PDFInfo
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- CN114763322B CN114763322B CN202011637129.5A CN202011637129A CN114763322B CN 114763322 B CN114763322 B CN 114763322B CN 202011637129 A CN202011637129 A CN 202011637129A CN 114763322 B CN114763322 B CN 114763322B
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- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 title claims abstract description 99
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 150000002148 esters Chemical class 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 23
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 78
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000003054 catalyst Substances 0.000 claims abstract description 47
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 39
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 56
- 150000001875 compounds Chemical class 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000002585 base Substances 0.000 description 36
- 239000000203 mixture Substances 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 235000019441 ethanol Nutrition 0.000 description 9
- 239000003513 alkali Substances 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 150000008282 halocarbons Chemical group 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- -1 methylene, ethylene, propylene Chemical group 0.000 description 2
- SUBJHSREKVAVAR-UHFFFAOYSA-N sodium;methanol;methanolate Chemical compound [Na+].OC.[O-]C SUBJHSREKVAVAR-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 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
- 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
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000000694 effects Effects 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
- 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
- 229920001084 poly(chloroprene) Polymers 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
Classifications
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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 Table
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- 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 of low yield of methyl ethyl carbonate in the synthesis of diethyl carbonate and methyl ethyl carbonate mixed ester, and provides a method for preparing diethyl carbonate and methyl ethyl carbonate mixed ester, which takes absolute ethyl alcohol and dimethyl carbonate as raw materials, and carries out transesterification under the action of an organic nonionic phosphine base catalyst to obtain the mixed ester containing diethyl carbonate and methyl ethyl carbonate, wherein the mass ratio of the methyl ethyl carbonate to the diethyl carbonate in the mixed ester is 2:1-15:1. The invention realizes the high-yield generation of the methyl ethyl carbonate by reacting the raw materials such as absolute ethyl alcohol, dimethyl carbonate and the like under the action of the 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 transesterification of dimethyl carbonate and ethanol.
Background
Diethyl carbonate and methyl ethyl carbonate are excellent solvents and important organic synthesis intermediates, and are widely applied to industries such as electrolyte solvents of lithium batteries, synthetic fibers, pharmacy and the like. The current common method for preparing the diethyl carbonate and the methyl ethyl carbonate mixed ester is simpler and safer: dimethyl carbonate and ethanol are used as raw materials, the raw materials are subjected to transesterification, the reaction process is reinforced by reactive distillation, and industrial grade methyl ethyl carbonate is obtained by a light component removal tower. However, the main product of the method is generally diethyl carbonate with a mass ratio of more than 70%, and methyl ethyl carbonate with a mass ratio of less than 30%.
In recent years, along with the fact that the dosage of the methyl ethyl carbonate in the lithium ion battery electrolyte greatly exceeds the dosage of the diethyl carbonate, the mass ratio of the methyl ethyl carbonate to the diethyl carbonate is changed by searching for a high-efficiency catalyst and adjusting the process, so that the market demand is met.
Disclosure of Invention
The invention solves the technical problem that the mass ratio of methyl ethyl carbonate to diethyl carbonate is not high in the synthesis of diethyl carbonate and methyl ethyl carbonate mixed ester in the prior art, thereby providing a method for preparing diethyl carbonate and methyl ethyl carbonate mixed ester by generating methyl ethyl carbonate with high yield.
The invention is realized by the following technical scheme that the method for preparing the diethyl carbonate and methyl ethyl carbonate mixed ester takes absolute ethyl alcohol and dimethyl carbonate as raw materials, and carries out transesterification under the action of an organic nonionic phosphine base catalyst to obtain the diethyl carbonate and methyl ethyl carbonate-containing mixed ester, wherein the mass ratio of the methyl ethyl carbonate to the diethyl carbonate in the mixed ester is 2:1-15:1.
Alternatively, the organic nonionic phosphine base catalyst is a phosphine base compound containing more than two P-N bonds, 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 is 1 、R 2 、R 3 Each independently selected from an alkylene group having 1 to 6 carbon atoms, R 4 、R 5 、R 6 Each independently of the otherSelected from the group consisting of hydrogen, hydrocarbyl, alkoxy, halogenated hydrocarbyl.
Optionally, the organic nonionic phosphine base catalyst has a structural formula 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.
Alternatively, 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, wherein the diethyl carbonate is one or more selected from pure diethyl carbonate, a mixture of diethyl carbonate and methyl ethyl carbonate generated by reaction, and a mixture of diethyl carbonate, methyl ethyl carbonate and methanol generated by reaction.
Optionally, the mass of the diethyl carbonate in the raw materials is 3-15% of the total mass of the anhydrous ethanol and the dimethyl carbonate.
Optionally, the preparation method comprises the following steps: 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 for continuous reaction.
Optionally, when the preparation method is applied to an industrialized device, absolute ethyl alcohol is added at the lower part of a reaction rectifying tower, dimethyl carbonate is added at the middle part, and a mixture of diethyl carbonate and an organic nonionic phosphine base catalyst is added at the upper part; the temperature at the top of the rectifying column is 60-68 ℃, 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 specific conjugated structure, has higher thermal stability and organic super strong base performance, and the mass ratio of the methyl ethyl carbonate to the diethyl carbonate in the product is more than 2:1 through the efficient catalytic activity of the novel organic nonionic phosphine base catalyst, so that the efficient generation of the methyl ethyl carbonate is realized. Meanwhile, the raw materials are easy to obtain, the process is simple, the toxicity of the materials is small, and the method is suitable for industrial production. In addition, the organic nonionic phosphine base catalyst has longer service life, can be recycled, and greatly reduces the production cost.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects solved by the invention more clear, the invention is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
A method for preparing diethyl carbonate and methyl ethyl carbonate mixed ester takes absolute ethyl alcohol and dimethyl carbonate as raw materials, and carries out transesterification under the action of an organic nonionic phosphine base catalyst to obtain the diethyl carbonate and methyl ethyl carbonate-containing mixed ester, wherein the mass ratio of the methyl ethyl carbonate to the diethyl carbonate in the mixed ester is 2:1-15:1.
Preferably, the mass ratio of the methyl ethyl carbonate to the diethyl carbonate in the mixed ester is 5:1-15:1.
The transesterification reaction includes reaction (1) and reaction (2):
in the invention, the organic nonionic phosphine base catalyst has higher thermal stability and organic super strong base performance due to the special conjugated structure, particularly can efficiently catalyze the reaction at the temperature of 75-95 ℃, has good dissolving performance, can be used as a solvent to dissolve reactants, fully plays a catalytic role, has longer service life and can be recycled.
In some embodiments, the organic nonionic phosphine base catalyst is a phosphine base compound comprising more than two P-N bonds, more preferably a phosphine base compound comprising 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 is 1 、R 2 、R 3 Each independently selected from an alkylene group having 1 to 6 carbon atoms, R 4 、R 5 、R 6 Each independently selected from the group consisting of hydrogen, hydrocarbyl, alkoxy, halogenated hydrocarbyl.
Examples of the alkylene group having 1 to 6 carbon atoms include: methylene, ethylene, propylene, isopropylene, butylene, isobutylene, neoprene, t-butylene, and the like.
Preferably, R 4 、R 5 、R 6 Each independently selected from alkyl groups of 1 to 10 carbon atoms, phenyl groups, tolyl groups, alkoxy groups of 1 to 10 carbon atoms, halogenated hydrocarbon groups of 1 to 10 carbon atoms.
Examples of the alkyl group having 1 to 10 carbon atoms include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, neobutyl, t-butyl, and the like.
As the halogenated hydrocarbon group of 1 to 10 carbon atoms, there may be mentioned, in particular, fluoro, chloro, bromo and iodo.
In some embodiments, the organic nonionic phosphine base catalyst is selected from at least one of the following compounds of formulas (1) - (5):
the compounds of the structural formulas (1) - (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 organic nonionic phosphine base catalyst is present in an amount of 0.1% to 5% by mass of the total mass of the feed.
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 methylethyl carbonate produced by the reaction, and a mixture of diethyl carbonate and methylethyl carbonate and methanol produced by the reaction. The diethyl carbonate is added to enable the diethyl carbonate to react with the dimethyl carbonate, so that the dimethyl carbonate is further converted into the 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 industrialized device, absolute ethyl alcohol is added at the lower part of a rectifying tower, dimethyl carbonate is added at the middle part, a mixture of diethyl carbonate and a catalyst is added at the upper part, diethyl carbonate and dimethyl carbonate react at the middle upper part of the rectifying tower (2) first to directly generate methyl ethyl carbonate, and unreacted diethyl carbonate and dimethyl carbonate flow into the lower part of the rectifying tower to react with absolute ethyl alcohol (1), so that methyl ethyl carbonate is further generated, and 100% conversion of ethanol is realized.
In some embodiments, the preparation method comprises the following steps: 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 the reaction, wherein the reaction is actually carried out in multiple steps:
the purpose of the feeding sequence is to enable diethyl carbonate to react with dimethyl carbonate (2) firstly, convert most of the dimethyl carbonate into methyl ethyl carbonate, and finally add ethanol to react (1), wherein diethyl carbonate existing in the reaction system can inhibit the reaction (4) and promote the reaction to proceed to (3), so that the conversion rate of ethanol to methyl ethyl carbonate is increased.
In some embodiments, the mass ratio of absolute ethyl alcohol to dimethyl carbonate is 1:1-1:3, which fully ensures that a sufficient amount of ethyl methyl carbonate can also react with ethanol after the reaction with diethyl carbonate is completed, and the ethanol is completely converted into 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 yields of diethyl carbonate and methylethyl carbonate can be adjusted by varying the amount of diethyl carbonate used.
In some embodiments, the system after the reaction mainly comprises diethyl carbonate, methylethyl carbonate, dimethyl carbonate, methanol and ethanol, the diethyl carbonate and the methylethyl carbonate are purified by rectification, and other components can be returned to the reaction system for cyclic reaction, so that the method is safe and environment-friendly, and the cost is saved.
In some embodiments, the temperature of the tower kettle is controlled between 75 ℃ and 95 ℃, and oil bath heating can be used for avoiding uneven heating in the kettle. Preferably, the temperature of the column top is controlled at 60-68 ℃, preferably 62-64 ℃, so as to enable the column top to distill light component methanol and promote the reversible reaction.
In order to more clearly understand the present invention, specific embodiments are described below.
Example 1:
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 (3) accounting for 0.5 percent of the total feeding mass is weighed and poured into the container, when the system temperature is raised to 85 ℃, the absolute ethyl alcohol is added into the reactor dropwise, and the reaction is carried out for 4 hours under stirring. After the reaction is finished, the composition and the content of the reaction components are monitored, and the mass ratio of the methyl ethyl carbonate to the diethyl carbonate in the obtained mixed ester under the condition is 7.95:1.
Example 2:
200g of absolute ethyl alcohol and 400g of dimethyl carbonate are measured, firstly, the dimethyl carbonate is added into a container, then the phosphorus alkali compound catalyst with the chemical structural formula (1) accounting for 0.5% of the total feeding mass is weighed and poured into the container, when the system temperature is raised to 85 ℃, the absolute ethyl alcohol is added into the reactor in a dropwise manner, and the stirring reaction is continued for 4 hours. After the reaction is finished, the composition and the content of the reaction components are monitored, the added diethyl carbonate is deducted under the condition, and the mass ratio of the methyl ethyl carbonate to the diethyl carbonate generated by the actual reaction is 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% of the total mass of the absolute ethyl alcohol and the dimethyl carbonate is added into the container, then, the phosphorus alkali compound catalyst with the chemical structural formula (3) accounting for 0.5% of the total mass of the materials is weighed and poured into the container, when the system temperature is raised to 85 ℃, the absolute ethyl alcohol is dripped into the reactor, and the stirring reaction is continued for 4 hours. After the reaction is finished, the composition and the content of the reaction components are monitored, the added diethyl carbonate is deducted under the condition, and the mass ratio of the methyl ethyl carbonate to the diethyl carbonate generated by the actual reaction is 8.65:1.
Example 4:
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% of the total mass of the absolute ethyl alcohol and the dimethyl carbonate is added into the container, then, the phosphorus alkali compound catalyst with the chemical structural formula (4) accounting for 0.5% of the total mass of the materials is weighed and poured into the container, when the system temperature is raised to 85 ℃, the absolute ethyl alcohol is dripped into the reactor, and the stirring reaction is continued for 4 hours. After the reaction is finished, the composition and the content of the reaction components are monitored, the added diethyl carbonate is deducted under the condition, and the mass ratio of the methyl ethyl carbonate to the diethyl carbonate generated by the actual reaction is 10.74:1.
Example 5:
on a small rectifying device, as shown in figure 1, absolute ethyl alcohol is added into the lower part of a reaction rectifying tower of 20Kg/h, dimethyl carbonate of 40Kg/h is added into the middle part, diethyl carbonate of 6Kg/h and a phosphorus alkali compound catalyst of a chemical structural formula (3) of 0.33Kg/h are added into the upper part, the feeding speed is guaranteed to be uniformly controlled, the temperature of a tower bottom is heated to 90 ℃, the temperature of the tower top is controlled to 64 ℃, the reflux reaction is carried out for 4 hours, the composition and the content of reaction components are monitored after the reaction is finished, the added diethyl carbonate are deducted under the condition, and the mass ratio of methyl ethyl carbonate and diethyl carbonate which are actually generated by the 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% of the total mass of the absolute ethyl alcohol and the dimethyl carbonate and 1% of the total mass of the phosphorus alkali compound catalyst with the chemical structural formula (3) are weighed, all raw materials are poured into a container together, the system temperature is increased to 90 ℃, and stirring reaction is continued for 4 hours. After the reaction is finished, the composition and the content of the reaction components are monitored, the added diethyl carbonate is deducted under the condition, and the mass ratio of the methyl ethyl carbonate to the diethyl carbonate generated by the actual reaction is 11.47:1.
Comparative example 1:
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% 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% of the total mass of the materials is weighed and poured into the container, when the system temperature is increased to 90 ℃, the absolute ethyl alcohol is dripped into the reactor, and the reaction is continued for 4 hours under stirring. After the reaction is finished, the composition and the content of the reaction components are monitored, the added diethyl carbonate is deducted under the condition, and the mass ratio of the methyl ethyl carbonate to the diethyl carbonate generated by the actual reaction is 1.90:1.
Experimental data for 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, an organic nonionic phosphine base catalyst was used in the preparation of the mixed ester of methyl ethyl carbonate and diethyl carbonate, and the mass ratio of methyl ethyl carbonate to diethyl carbonate in the reaction product reached 7: more than 1; in comparative example 1, sodium methoxide-methanol solution is used as a catalyst, the mass ratio of the prepared methyl ethyl carbonate to diethyl carbonate is only 1.90:1, and the production rate of the methyl ethyl carbonate is far lower than that of the embodiment using an organic nonionic phosphine base catalyst.
In addition, as shown in the data of examples 1-2 and examples 3-4, diethyl carbonate was additionally added to the raw materials in the preparation process of the mixed ester of methylethyl carbonate and diethyl carbonate in examples 3-4, and the mass ratio of methylethyl carbonate to diethyl carbonate was larger than that of examples 1-2 without diethyl carbonate, which indicated that the added diethyl carbonate participated in the reaction, further promoting the improvement of yield of methylethyl carbonate.
In addition, in the embodiment 4, the phosphorus alkali compound of the structural formula (4) is adopted as a catalyst, and the mass ratio of the methyl ethyl carbonate to the diethyl carbonate in the reaction product achieves the excellent effect of 10.74:1, which proves that the organic nonionic phosphine alkali catalyst of the structural formula (4) can obviously improve the yield of the methyl ethyl carbonate.
In addition, in example 5, an industrialized device is adopted, as shown in fig. 1, absolute ethyl alcohol is added at the lower part of a reaction rectifying tower, dimethyl carbonate is added at the middle part, and a mixture of diethyl carbonate and an organic nonionic phosphine base catalyst is added at the upper part; the temperature at the top of the rectifying tower is controlled to be 60-68 ℃, and the mass ratio of the methyl ethyl carbonate to the diethyl carbonate in the reaction product reaches 13.61:1, which indicates that the yield of the methyl ethyl carbonate can be further improved by adopting the process and the condition arrangement in industrial production.
In summary, the novel organic nonionic phosphine base catalyst is adopted in the process of preparing the diethyl carbonate and the methyl ethyl carbonate mixed ester, has a specific conjugated structure, has higher thermal stability and organic super strong base performance, and the mass ratio of the methyl ethyl carbonate to the diethyl carbonate in the product is obviously higher than 2:1 through the efficient catalytic activity of the novel organic nonionic phosphine base catalyst, wherein the compounds of structural formulas (1) - (5) are adopted as the catalyst, and the mass ratio of the methyl ethyl carbonate to the diethyl carbonate is more than 5:1, in the industrial production process, the mass ratio of the methyl ethyl carbonate to the diethyl carbonate reaches 13.61:1 at the highest by adopting the process and condition control, so that the yield of the methyl ethyl carbonate is obviously improved.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (5)
1. A method for preparing diethyl carbonate and methyl ethyl carbonate mixed ester is characterized in that absolute ethyl alcohol and dimethyl carbonate are used as raw materials, transesterification is carried out under the action of an organic nonionic phosphine base catalyst, and mixed ester containing diethyl carbonate and methyl ethyl carbonate is obtained, wherein the mass ratio of the methyl ethyl carbonate to the diethyl carbonate in the mixed ester is 5:1-15:1; the raw materials also contain diethyl carbonate; the organic nonionic phosphine base catalyst is selected from at least one of the following compounds:
the feeding sequence of the method for preparing the diethyl carbonate and methyl ethyl carbonate mixed ester 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 for continuous reaction.
2. The method for preparing diethyl carbonate and methyl ethyl carbonate mixed ester according to claim 1, wherein the mass of the organic nonionic phosphine base catalyst is 0.1% -5% of the total mass of the materials.
3. The method for preparing the diethyl carbonate and methyl ethyl carbonate mixed ester according to claim 1, wherein the mass ratio of the absolute ethyl alcohol to the dimethyl carbonate in the raw materials is 1:1-1:3.
4. The method for preparing the diethyl carbonate and methyl ethyl carbonate mixed ester according to claim 1, wherein the reaction temperature of the transesterification reaction is 75-95 ℃ and the reaction time is 4-6 h.
5. The method for preparing the diethyl carbonate and methyl ethyl carbonate mixed ester according to claim 1, wherein the mass of diethyl carbonate in the raw materials is 3-15% of the total mass of absolute ethyl alcohol and dimethyl carbonate.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (3)
| Title |
|---|
| D. Bradley G. Williams等.Verkade super base-catalyzed transesterification of propylene carbonate with methanol to co-produce dimethyl carbonate and propylene glycol.Journal of Molecular Catalysis A.2009,第304卷147-152. * |
| Palanichamy Ilankumaran and J. G. Verkade.P(RNCH2CH2)3N: Efficient Catalysts for Transesterifications, Acylations, and Deacylations.J. Org. Chem..1999,第64卷3086-3089. * |
| Wang, Zhiguo等.Solvent-free organocatalytic preparation of cyclic organic carbonates under scalable continuous flow conditions.Reaction Chemistry & Engineering.2018,第4卷(第1期),17-26. * |
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