CN102850223A - Method for synthesizing methylethyl carbonate - Google Patents
Method for synthesizing methylethyl carbonate Download PDFInfo
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- CN102850223A CN102850223A CN2012103465923A CN201210346592A CN102850223A CN 102850223 A CN102850223 A CN 102850223A CN 2012103465923 A CN2012103465923 A CN 2012103465923A CN 201210346592 A CN201210346592 A CN 201210346592A CN 102850223 A CN102850223 A CN 102850223A
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- methyl ethyl
- ethyl carbonate
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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
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- Y02P20/584—Recycling of catalysts
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Abstract
The invention relates to a method for synthesizing methylethyl carbonate. According to the method, under ordinary pressure, dimethyl carbonate and ethanol which are used as raw materials are subjected to synthetic reaction of methylethyl carbonate at certain reaction temperature for some time by using an imidazole ionic liquid as a catalyst. The invention has the following advantages: the catalyst consumption is only 0.5-5 wt% of the dimethyl carbonate; the ionic liquid catalyst has high catalytic activity in the reaction process, the maximum yield of methylethyl carbonate is up to 71.22%, and the selectivity is up to 88.52%; and the catalyst can be recycled for cyclic utilization after being subjected to simple treatment after reaction, has the advantages of long service life and no pollution, and greatly lowers the preparation cost of methylethyl carbonate.
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 for the technical renovation of battery electrolyte.Domestic synthetic electrolyte solvent is not reaching Application standard qualitatively at present, so electrolyte solvent generally will be from external import, the 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, main intermediate as solvent and organic synthesis, during as the 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 mainly is that because phosgene has severe toxicity, intermediate product has severe corrosive with phosgene and dehydrated alcohol reaction, and the byproduct environmental pollution is serious, so the method is eliminated.The oxidation carbonyl process is not perfect, has that selectivity is low, catalyzer is expensive, is difficult to the shortcoming such as operation control.Therefore by contrast, methylcarbonate and ethanol carry out the method for transesterify Catalysts of Preparing Methyl Ethyl Carbonate, and having advantages of nontoxic raw materials, production process and product all is the advantages such as green non-pollution.Therefore we select the method Catalysts of Preparing Methyl Ethyl Carbonate of this transesterify.
A lot of scholars are studied the catalyzer of methylcarbonate and ethanol transesterification reaction system, and for example JP6166660 adopts alkaline carbonate such as K
2CO
3Make catalyzer, methylcarbonate is excessive, at 100 ℃ of reaction 7h, the yield 42% of Methyl ethyl carbonate.But this catalyzer easily runs off in reaction, and affects the purity of reaction product.
US4691041 adopts quaternary amine type strong alkali resin, sulfonic acid type weak acid resin, carboxylic acid type weak acid resin, has flooded the SiO of basic metal or alkaline earth metal silicate
2Deng some heterogeneous catalyst, reached certain effect, but the activity of these catalyzer is not high yet, the yield of Methyl ethyl carbonate is very low.
It is catalyzer that CN1320594 and CN1314338 adopt the complex compound of salt of wormwood and polyoxyethylene glycol, although the solubleness of this catalyzer in this reaction system is high, catalytic activity is fine, easily runs off, and affects follow-up recycling.
US4734518 is with organophosphorus such as PBu
3, PPh
3, P (OBu)
3, AsPh
3, SPh
2, P (NMe
2)
3Deng being catalyzer, these catalyzer are not only active low, and Costco Wholesale other are higher relatively.
Yao Jie etc. (gas chemical industry, 2004(1): 57 ~ 59) NaOH, KOH, the NaOCH of report
3, KOCH
3Deng the alkali metal derivant catalyzer, the catalytic activity of these catalyzer is higher, but they have very large shortcoming be exactly in reaction system solubleness bad, easily precipitation, fouling.
Ionic liquid became the study hotspot in numerous research fields in the last few years, because that it has advantages of is 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, studied widely application, still, at present also not with 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 that occurs in present Methyl ethyl carbonate synthetic, selectivity is bad, catalyzer is not easy to be recycled, the high in cost of production defective, in order to address the above problem, the invention provides that a kind of catalytic activity is high, selectivity is higher, and after reaction, just can reclaim the continuation recycle through simple process, reduce the method for the Catalysts of Preparing Methyl Ethyl Carbonate of cost.
The technical solution adopted for the present invention to solve the technical problems is:
Take methylcarbonate and ethanol as raw material, take two mouthfuls of round-bottomed flasks as reactor, under normal pressure, catalyst system therefor be methylcarbonate quality 0.5% ~ 5%, temperature of reaction is 50 ~ 150 ℃, and the mol ratio of reaction mass methylcarbonate and ethanol is 3:1 ~ 1:3, and the reaction times is to react under the condition of 6 ~ 24h, the Methyl ethyl carbonate yield reaches as high as 71.22%, and selectivity can reach 88.52%.
As limitation of the invention, catalyzer of the present invention is ionic liquid 1-R
1-3-R
2Imidazole salts, its structural formula is as follows:
X-=Cl
-，Br
-，OH
-，HCO
3 -，BF
4 -，PF
6 -
R
1，R
2=C
nH
2n+1（n=1~4）
The present invention is applied in this reaction system take ionic liquid as catalyzer, has obtained good effect.Not only catalytic activity is high, the Methyl ethyl carbonate yield reaches as high as 71.22% at reaction process intermediate ion liquid, selectivity can reach 88.52% and be recyclable continuation recycle through simple process after reaction, life-span is long, without any pollution, greatly reduces the cost of preparation 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 usefulness for illustrating only, and should not be interpreted as restriction of the invention process.
Embodiment 1
In reactor, add reaction mass methylcarbonate and ethanol, its mol ratio is 1:1,1-ethyl-3-ethyl imidazol(e) Bromide is as catalyzer, the catalyst system therefor amount is 1% of carbon reactant dimethyl phthalate quality, temperature of reaction is 50 ℃, and the reaction times is 10h, reacts under this reaction conditions, the yield of Methyl ethyl carbonate is 32.41%, and selectivity is 74.98%.
Embodiment 2
In reactor, add reaction mass methylcarbonate and ethanol, its mol ratio is 3:1,1-methyl-3-Methylimidazole chlorate is as catalyzer, the catalyst system therefor amount is 0.5% of carbon reactant dimethyl phthalate quality, temperature of reaction is 150 ℃, and the reaction times is 6h, reacts under this reaction conditions, the yield of Methyl ethyl carbonate is 41.27%, and selectivity is 82.19%.
Embodiment 3
In reactor, add reaction mass methylcarbonate and ethanol, its mol ratio is 1:1,1-butyl-3-butyl imidazole hexafluorophosphate is as catalyzer, the catalyst system therefor amount is 1% of carbon reactant dimethyl phthalate quality, temperature of reaction is 80 ℃, and the reaction times is 10h, reacts under this reaction conditions, the yield of Methyl ethyl carbonate is 12.24%, and selectivity is 80.35%.
Embodiment 4
In reactor, add reaction mass methylcarbonate and ethanol, its mol ratio is 1:3,1-propyl group-3-butyl hydroxide salt is as catalyzer, the catalyst system therefor amount is 5% of carbon reactant dimethyl phthalate quality, temperature of reaction is 130 ℃, and the reaction times is 18h, reacts under this reaction conditions, the yield of Methyl ethyl carbonate is 53.36%, and selectivity is 69.41%.
Embodiment 5
In reactor, add reaction mass methylcarbonate and ethanol, its mol ratio is 1:1,1-butyl-3-Methylimidazole supercarbonate is as catalyzer, the catalyst system therefor amount is 1% of carbon reactant dimethyl phthalate quality, temperature of reaction is 100 ℃, and the reaction times is 10h, reacts under this reaction conditions, the yield of Methyl ethyl carbonate is 50.64%, and selectivity is 71.69%.
Embodiment 6
In reactor, add reaction mass methylcarbonate and ethanol, its mol ratio is 1:1,1-butyl-3-propyl imidazole a tetrafluoro borate is as catalyzer, the catalyst system therefor amount is 5% of carbon reactant dimethyl phthalate quality, temperature of reaction is 90 ℃, and the reaction times is 24h, reacts under this reaction conditions, the yield of Methyl ethyl carbonate is 25.33%, and selectivity is 81.29%.
Embodiment 7
In reactor, add reaction mass methylcarbonate and ethanol, its mol ratio is 1:1,1-butyl-3-Methylimidazole Bromide is as catalyzer, the catalyst system therefor amount is 2% of carbon reactant dimethyl phthalate quality, temperature of reaction is 140 ℃, and the reaction times is 20h, reacts under this reaction conditions, the Methyl ethyl carbonate yield reaches as high as 71.22%, and selectivity can reach 88.52%.
Embodiment 8
The recovery method of catalyzer: the reaction product among the embodiment 7 and catalyzer are put into Rotary Evaporators revolve steaming, revolve the steaming condition: 60 ℃, 10-1Pa, revolve steam to finish after in the flask a small amount of yellow thick liquid of residue be catalyzer 1-butyl-3-Methylimidazole Bromide.Condition according to embodiment 7 is carried out 3 evaluation tests continuously to this catalyzer again, shown in the reaction result table 1:
The recycling of table 1 catalyzer
| Cycle index | Methyl ethyl carbonate selectivity (%) | Methyl ethyl carbonate yield (%) |
| 1 | 88.52 | 71.22 |
| 2 | 88.61 | 70.47 |
| 3 | 87.85 | 71.59 |
As can be seen from Table 1, after this catalyzer was recycled through three times, selectivity and the yield of Methyl ethyl carbonate were basicly stable, illustrated that this catalyzer can reuse and do not reduce its catalytic activity, has good effect.
Take above-mentioned foundation desirable embodiment of the present invention as enlightenment, by above-mentioned description, the relevant staff can in the scope that does not depart from this invention technological thought, carry out various change and modification fully.The technical scope of this invention is not limited to the content on the specification sheets, must determine its technical scope according to the claim scope.
Claims (6)
1. the method for a Catalysts of Preparing Methyl Ethyl Carbonate is characterized in that the method is under normal pressure, take methylcarbonate and ethanol as raw material, take ionic liquid as catalyzer, carries out the building-up reactions of Methyl ethyl carbonate under certain temperature of reaction and reaction times.
2. the method for Catalysts of Preparing Methyl Ethyl Carbonate according to claim 1 is characterized in that described ionic liquid is 1-R
1-3-R
2Imidazole salts, its structural formula is as follows:
X-=Cl
-，Br
-，OH
-，HCO
3 -，BF
4 -，PF
6 -；
R
1，R
2=C
nH
2n+1(n=1~4)。
3. the method for Catalysts of Preparing Methyl Ethyl Carbonate according to claim 1, the consumption that it is characterized in that described catalyst ion liquid is 0.5% ~ 5% of material carbon dimethyl phthalate quality.
4. the method for Catalysts of Preparing Methyl Ethyl Carbonate according to claim 1 is characterized in that the mol ratio of described reaction raw materials methylcarbonate and ethanol is 3:1 ~ 1:3.
5. the method for Catalysts of Preparing Methyl Ethyl Carbonate according to claim 1 is characterized in that described temperature of reaction is 50 ~ 150 ℃.
6. the method for Catalysts of Preparing Methyl Ethyl Carbonate according to claim 1 is characterized in that the described reaction times is 6 ~ 24h.
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|---|---|---|---|
| CN201210346592.3A CN102850223B (en) | 2012-09-18 | 2012-09-18 | Method for synthesizing methylethyl carbonate |
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|---|---|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103537318A (en) * | 2013-09-24 | 2014-01-29 | 常州大学 | Solid catalyst for process of preparing ethylene glycol by hydrolyzing ethylene carbonate and preparation method thereof |
| CN103537319A (en) * | 2013-09-26 | 2014-01-29 | 常州大学 | Solid catalyst for ester exchange reactions and preparation method thereof |
| 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 |
| CN113248379A (en) * | 2021-06-04 | 2021-08-13 | 重庆微而易科技有限公司 | Method for preparing methyl ethyl carbonate by adopting pipeline continuous reactor |
| CN114210365A (en) * | 2021-12-23 | 2022-03-22 | 抚顺东科精细化工有限公司 | Catalyst for synthesizing methyl ethyl carbonate and diethyl carbonate and method thereof |
Citations (3)
| 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 |
| CN1314338A (en) * | 2001-04-05 | 2001-09-26 | 华东理工大学 | Process for preparing diethyl carbonate |
-
2012
- 2012-09-18 CN CN201210346592.3A patent/CN102850223B/en active Active
Patent Citations (3)
| 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 |
| CN1314338A (en) * | 2001-04-05 | 2001-09-26 | 华东理工大学 | Process for preparing diethyl carbonate |
Non-Patent Citations (1)
| Title |
|---|
| 骆铭等: "碱性离子液体催化合成碳酸二丙酯", 《石油化工》, vol. 40, no. 12, 31 December 2011 (2011-12-31), pages 1316 - 1320 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103537318A (en) * | 2013-09-24 | 2014-01-29 | 常州大学 | Solid catalyst for process of preparing ethylene glycol by hydrolyzing ethylene carbonate and preparation method thereof |
| CN103537318B (en) * | 2013-09-24 | 2015-07-01 | 常州大学 | Solid catalyst for process of preparing ethylene glycol by hydrolyzing ethylene carbonate and preparation method thereof |
| CN103537319A (en) * | 2013-09-26 | 2014-01-29 | 常州大学 | Solid catalyst for ester exchange reactions and preparation method thereof |
| CN103537319B (en) * | 2013-09-26 | 2015-07-01 | 常州大学 | Solid catalyst for ester exchange reactions and preparation method thereof |
| 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 |
| CN113248379A (en) * | 2021-06-04 | 2021-08-13 | 重庆微而易科技有限公司 | Method for preparing methyl ethyl carbonate by adopting pipeline continuous reactor |
| CN114210365A (en) * | 2021-12-23 | 2022-03-22 | 抚顺东科精细化工有限公司 | Catalyst for synthesizing methyl ethyl carbonate and diethyl carbonate and method thereof |
| CN114210365B (en) * | 2021-12-23 | 2022-11-29 | 抚顺东科精细化工有限公司 | Catalyst for synthesizing methyl ethyl carbonate and diethyl carbonate and method thereof |
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|---|---|
| CN102850223B (en) | 2014-10-29 |
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Effective date of registration: 20180518 Address after: 111300 economic and Technological Development Zone of Lighthouse City, Liaoning Patentee after: Liaoyang Dongchang chemical industry Limited by Share Ltd Address before: No. 1, Wujin District, Wujin District, Changzhou, Jiangsu Patentee before: Changzhou University |