CN102850224B - Method for synthetising methyl ethyl carbonate by exchange of diethyl carbonate and methanol ester - Google Patents
Method for synthetising methyl ethyl carbonate by exchange of diethyl carbonate and methanol ester Download PDFInfo
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- CN102850224B CN102850224B CN201210346612.7A CN201210346612A CN102850224B CN 102850224 B CN102850224 B CN 102850224B CN 201210346612 A CN201210346612 A CN 201210346612A CN 102850224 B CN102850224 B CN 102850224B
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Abstract
The invention relates to a method for synthetising methyl ethyl carbonate by exchange of diethyl carbonate and methanol ester. The method includes that under normal pressure, the diethyl carbonate and methanol are taken as raw materials, imidazolium ionic liquids are taken as catalysts, and synthetic reaction of the methyl ethyl carbonate is performed at a certain reaction temperature and in a certain reaction time. Usage amount of the catalysts only accounts for 1-5% of the mass of the diethyl carbonate, the ionic liquids serving as the catalysts are high in catalytic activity during reaction, the yield of the methyl ethyl carbonate can ultimately reach 68.15%, selectivity can reach 85.39%, the diethyl carbonate can be recovered for continuous cyclic utilization by simple treatment after the reaction, and the methyl ethyl carbonate is long in service life and free of any pollution, so that cost for preparation of the methyl ethyl carbonate is greatly lowered.
Description
Technical field
The present invention relates to a kind of synthetic method of Methyl ethyl carbonate, particularly a kind of ionic liquid that adopts is as the method for catalyzer Catalysts of Preparing Methyl Ethyl Carbonate.
Background technology
Along with the fast development of lithium ion battery, relevant battery security, work-ing life etc. require more and more stricter, have brought challenge to the technical renovation of battery electrolyte.Domestic synthetic electrolyte solvent is not reaching use standard qualitatively at present, so electrolyte solvent generally will be from external import, discovered in recent years Methyl ethyl carbonate can be used as a kind of ionogen of good lithium ion battery, Methyl ethyl carbonate is a kind of broad-spectrum asymmetric carbon ester compound, the main intermediate as solvent and organic synthesis, during as lithium ion battery electrolyte solvent, because its viscosity is little, specific inductivity is large, solvability to lithium salts is strong, can improve well energy density and the charge/discharge capacity of battery, more can improve safety performance and the work-ing life of battery, can alleviate to a certain extent domestic to electrolytical demand.
The synthetic method of Methyl ethyl carbonate mainly contains three kinds at present: phosgenation, oxidation carbonyl process and ester-interchange method.Phosgenation is mainly that because phosgene has severe toxicity, intermediate product has severe corrosive with phosgene and dehydrated alcohol reaction, and byproduct environmental pollution is serious, so the method is eliminated.Oxidation carbonyl process is not perfect, has that selectivity is low, catalyzer is expensive, is difficult to the shortcomings such as operation control.Up to the present Synthesis of Ethyl Methyl Carbonate by Transesterification has had Many researchers to do a lot of research, but mostly work is mainly between methyl-chloroformate and methyl alcohol, between methylcarbonate and methyl alcohol and the transesterification reaction between methylcarbonate and diethyl carbonate, catalyzer for these three kinds of transesterification reactions is main mainly with basic catalyst, also each own relative merits.And about the application report of transesterify Catalysts of Preparing Methyl Ethyl Carbonate between diethyl carbonate and methyl alcohol seldom, so we select the method Catalysts of Preparing Methyl Ethyl Carbonate of this transesterify.
Ionic liquid became the study hotspot in numerous research fields in the last few years, due to it have advantages of unique: (1) steam forces down, non-volatile, nonflammable; (2) wider liquid temperature scope, good electroconductibility and wider potential window; (3) dissolving power is strong; (4) toxicity is low, recoverable; (5) acid-basicity is adjustable etc.Therefore in the fields such as organic synthesis, catalytic applications and organic solvent, obtain studying widely application, still, at present also not by ionic liquid for the synthesis of the relevant report in the reaction of Methyl ethyl carbonate.
Summary of the invention
The technical problem to be solved in the present invention be not high for the products collection efficiency occurring in current Methyl ethyl carbonate synthetic, selectivity is bad, catalyzer is not easy to be recycled, high in cost of production defect, in order to address the above problem, the invention provides that a kind of catalytic activity is high, selectivity is higher, and after reaction, through simple process, just can reclaim continuation recycle, the method for the Catalysts of Preparing Methyl Ethyl Carbonate reducing costs.
The technical solution adopted for the present invention to solve the technical problems is:
Take diethyl carbonate and methyl alcohol as raw material, the two mouthfuls of round-bottomed flasks of take are reactor, under normal pressure, used catalyst be diethyl carbonate quality 1% ~ 5%, temperature of reaction is 80 ~ 120 ℃, and the mol ratio of reaction mass diethyl carbonate and methyl alcohol is 3:1 ~ 1:3, under the condition that the reaction times is 10 ~ 20h, reacts, Methyl ethyl carbonate yield reaches as high as 68.15%, and selectivity can reach 85.39%.
As limitation of the invention, catalyzer of the present invention is ionic liquid 1-R
1-2-R
2-3-R
3imidazole salts, its structural formula is as follows:
X
-=Cl
-，Br
-，OH
-，HCO
3 -，BF
4 -，PF
6 -；
R
1,R
2，R
3=C
nH
2n+1(n=1~4)
The present invention be take ionic liquid as catalyzer is applied in this reaction system, has obtained good effect.At reaction process intermediate ion liquid, not only catalytic activity is high, Methyl ethyl carbonate yield reaches as high as 68.15%, selectivity can reach 85.39% and through simple process, be recyclable continuation recycle after reaction, life-span is long, without any pollution, greatly reduces the cost of preparing Methyl ethyl carbonate.
Embodiment
Embodiment
The present invention will be described further with regard to following examples, but will be appreciated that, these embodiment are the use for illustrating only, and should not be interpreted as restriction of the invention process.
Embodiment 1
In reactor, add reaction mass diethyl carbonate and methyl alcohol, its mol ratio is 1:1,1-Ethyl-2-Methyl-3-ethyl imidazol(e) Bromide is as catalyzer, used catalyst amount is 1% of carbon reactant diethyl phthalate quality, temperature of reaction is 80 ℃, and the reaction times is 10h, under this reaction conditions, reacts, the yield of Methyl ethyl carbonate is 33.54%, and selectivity is 76.71%.
Embodiment 2
In reactor, add reaction mass diethyl carbonate and methyl alcohol, its mol ratio is 3:1,1-methyl-2-butyl-3-Methylimidazole chlorate is as catalyzer, used catalyst amount is 2% of carbon reactant diethyl phthalate quality, temperature of reaction is 120 ℃, and the reaction times is 16h, under this reaction conditions, reacts, the yield of Methyl ethyl carbonate is 51.33%, and selectivity is 72.14%.
Embodiment 3
In reactor, add reaction mass diethyl carbonate and methyl alcohol, its mol ratio is 1:1,1-butyl-2-ethyl-3-butyl imidazole hexafluorophosphate is as catalyzer, used catalyst amount is 4% of carbon reactant diethyl phthalate quality, temperature of reaction is 100 ℃, and the reaction times is 20h, under this reaction conditions, reacts, the yield of Methyl ethyl carbonate is 17.24%, and selectivity is 81.23%.
Embodiment 4
In reactor, add reaction mass diethyl carbonate and methyl alcohol, its mol ratio is 1:3,1-propyl group-2-methyl-3-butyl imidazole hydroxide salt is as catalyzer, used catalyst amount is 5% of carbon reactant diethyl phthalate quality, temperature of reaction is 120 ℃, and the reaction times is 20h, under this reaction conditions, reacts, the yield of Methyl ethyl carbonate is 53.36%, and selectivity is 62.41%.
Embodiment 5
In reactor, add reaction mass diethyl carbonate and methyl alcohol, its mol ratio is 1:1,1-butyl-2-methyl-3-Methylimidazole supercarbonate is as catalyzer, used catalyst amount is 1% of carbon reactant diethyl phthalate quality, temperature of reaction is 100 ℃, and the reaction times is 15h, under this reaction conditions, reacts, the yield of Methyl ethyl carbonate is 51.02%, and selectivity is 74.28%.
Embodiment 6
In reactor, add reaction mass diethyl carbonate and methyl alcohol, its mol ratio is 1:1,1-butyl-2-methyl-3-propyl imidazole a tetrafluoro borate is as catalyzer, used catalyst amount is 5% of carbon reactant diethyl phthalate quality, temperature of reaction is 90 ℃, and the reaction times is 20h, under this reaction conditions, reacts, the yield of Methyl ethyl carbonate is 22.13%, and selectivity is 83.39%.
Embodiment 7
In reactor, add reaction mass diethyl carbonate and methyl alcohol, its mol ratio is 1:1,1-butyl-2-propyl group-3-Methylimidazole Bromide is as catalyzer, used catalyst amount is 2% of carbon reactant diethyl phthalate quality, temperature of reaction is 120 ℃, and the reaction times is 20h, under this reaction conditions, reacts, Methyl ethyl carbonate yield reaches as high as 68.15%, and selectivity can reach 85.39%.
The recycling of embodiment 8 catalyzer:
Reaction product in embodiment 7 and catalyzer are put into Rotary Evaporators and revolve steaming, revolve steaming condition: 60 ℃, 10
-1pa, revolves to steam and finishes to remain a small amount of yellow thick liquid in rear flask and be catalyzer 1-butyl-2-propyl group-3-Methylimidazole Bromide.According to the condition of embodiment 7, again this catalyzer is carried out to 3 evaluation tests continuously, shown in reaction result table 1:
The recycling of table 1 catalyzer
| Cycle index | Methyl ethyl carbonate selectivity (%) | Methyl ethyl carbonate yield (%) |
| 1 | 85.39 | 68.15 |
| 2 | 86.19 | 67.71 |
| 3 | 85.81 | 67.05 |
As can be seen from Table 1, after this catalyzer is recycled through three times, selectivity and the yield of Methyl ethyl carbonate are basicly stable, illustrate that this catalyzer can reuse and not reduce its catalytic activity, has good effect.
The above-mentioned foundation desirable embodiment of the present invention of take is enlightenment, and by above-mentioned description, relevant staff can, within not departing from the scope of this invention technological thought, carry out various change and modification completely.The technical scope of this invention is not limited to the content on specification sheets, must determine its technical scope according to claim scope.
Claims (3)
1. the method for a diethyl carbonate and methyl alcohol transesterify Catalysts of Preparing Methyl Ethyl Carbonate, it is characterized in that the method is under normal pressure, take diethyl carbonate and methyl alcohol as raw material, take ionic liquid as catalyzer, under certain temperature of reaction and reaction times, carry out, it is characterized in that described ionic liquid is 1-R
1-2-R
2-3-R
3imidazole salts, its structural formula is as follows:
X
-＝Cl
-，Br
-，BF
4 -，PF
6 -；
R
1,R
2，R
3＝C
nH
2n+1(n＝1～4)。
2. the method for Catalysts of Preparing Methyl Ethyl Carbonate according to claim 1, is characterized in that the consumption of described catalyst ion liquid is 1%～5% of material carbon diethyl phthalate quality.
3. the method for Catalysts of Preparing Methyl Ethyl Carbonate according to claim 1, is characterized in that described reaction raw materials diethyl carbonate and the mol ratio of methyl alcohol are 3:1～1:3, and temperature of reaction is 80～120 ℃, and the reaction times is 10～20h.
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| CN201210346612.7A CN102850224B (en) | 2012-09-18 | 2012-09-18 | Method for synthetising methyl ethyl carbonate by exchange of diethyl carbonate and methanol ester |
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| CN102850224B true CN102850224B (en) | 2014-10-29 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103506157B (en) * | 2013-09-26 | 2015-08-12 | 常州大学 | A kind of solid catalyst for the synthesis of methyl ethyl carbonate and preparation method thereof |
| CN114634415B (en) * | 2022-04-22 | 2024-03-22 | 天津凯美特化工科技有限公司 | Method for separating azeotrope of dimethyl carbonate and methanol by diethyl carbonate reaction and producing methyl ethyl carbonate |
| CN115784889B (en) * | 2022-11-24 | 2024-02-20 | 南京大学 | Method for preparing methyl ethyl carbonate and diethyl carbonate by taking dimethyl oxalate as raw material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4734518A (en) * | 1987-01-12 | 1988-03-29 | Texaco Inc. | Process for cosynthesis of ethylene glycol and dimethyl carbonate |
| JPH06166660A (en) * | 1992-12-01 | 1994-06-14 | Mitsui Petrochem Ind Ltd | Production of chain carbonic acid ester compound |
-
2012
- 2012-09-18 CN CN201210346612.7A patent/CN102850224B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4734518A (en) * | 1987-01-12 | 1988-03-29 | Texaco Inc. | Process for cosynthesis of ethylene glycol and dimethyl carbonate |
| JPH06166660A (en) * | 1992-12-01 | 1994-06-14 | Mitsui Petrochem Ind Ltd | Production of chain carbonic acid ester compound |
Non-Patent Citations (2)
| Title |
|---|
| 碱性离子液体催化合成碳酸二丙酯;骆铭等;《石油化工》;20111231;第40卷(第12期);1316-1320 * |
| 骆铭等.碱性离子液体催化合成碳酸二丙酯.《石油化工》.2011,第40卷(第12期),1316-1320. |
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