CN108976126B - Method for preparing methyl ethyl carbonate through ester exchange reaction - Google Patents
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- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
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Abstract
The invention relates to a method for preparing ethyl methyl carbonate by ester exchange reaction, which takes dimethyl carbonate and diethyl carbonate as raw materials, takes one or more of titanium citrate, titanium malate, titanium tartrate, titanium oxalate, titanium malonate, titanium succinate, titanium glutarate and titanium adipate as catalysts, the molar ratio of dimethyl carbonate to diethyl carbonate is 1:1, the dosage of the catalysts is 0.02-0.2 percent of the total mass of the dimethyl carbonate and the diethyl carbonate, the reaction temperature is 80-100 ℃, the reaction time is 2-6 hours, the conversion rate of the dimethyl carbonate is more than 85 percent, and the selectivity of the ethyl methyl carbonate is more than 99 percent. The method has the advantages of low toxicity of raw materials, little pollution, simple process, mild reaction conditions, no corrosion and little consumption of the catalyst, high conversion rate of the raw materials and high selectivity of products, and the like.
Description
Technical Field
The invention belongs to the field of organic chemical industry, and particularly relates to a method for preparing methyl ethyl carbonate through ester exchange reaction.
Background
Ethyl Methyl Carbonate (EMC) is an important asymmetric carbonate and has wide applications in medicine, pesticide and other fields. The EMC molecular structure is asymmetric, so that the EMC molecular structure has remarkable superiority in the aspect of being used as a solvent for paint, cellulose, resin and the like. The lithium ion battery electrolyte has low EMC viscosity, high dielectric constant and good solubility to lithium salt, is used as a non-aqueous solvent of a lithium battery electrolyte, and can improve the safety performance, low-temperature performance, energy density, electric capacity and service life of the battery.
The EMC synthesis method mainly comprises the following steps: (1) a phosgene method; (2) oxidative carbonylation processes; (3) an ester exchange method.
(1) EMC (EMC) preparation by phosgene method: under the condition of catalyst, phosgene reacts with methanol or ethanol to generate methyl chloroformate or ethyl chloroformate, and then the methyl chloroformate or the ethyl chloroformate reacts with ethanol or methanol respectively to generate EMC, the raw material phosgene and an intermediate product are extremely toxic, potential hazards are brought to the health of operators, and equipment is corroded and seriously polluted in the reaction process.
(2) Preparing EMC by an oxidative carbonylation method: under the condition of existence of a catalyst, the EMC is prepared by taking methanol, ethanol, carbon monoxide and oxygen as raw materials, the raw materials are wide in source, but water is generated in the reaction process, the separation and purification difficulty is high, the application of the EMC in non-aqueous lithium ion electrolyte with strict control on water content is limited, and the problems of harsh reaction conditions, low product yield and the like exist.
(3) Preparing EMC by an ester exchange method: under the condition of catalyst, dimethyl carbonate and ethanol or diethyl carbonate are subjected to ester exchange to prepare EMC. The method for preparing EMC by ester exchange has the advantages of low toxicity of raw materials, little pollution, simple process, mild reaction conditions and the like. Especially dimethyl carbonate and diethyl carbonate are subjected to ester exchange to prepare EMC, the product selectivity is high, EMC is not azeotropic with dimethyl carbonate and diethyl carbonate, and the method has the advantages of simple product separation and the like. There are reports in the literature that EMC is prepared by performing an ester exchange reaction between dimethyl carbonate and diethyl carbonate under Catalysis of alkali metal oxide, aluminum phosphate, alkaline ionic liquid, etc., and there are problems of large catalyst usage (about 5% of the total mass of dimethyl carbonate and diethyl carbonate), low conversion rate of dimethyl carbonate (about 50%), and the like (i.e., (guest Zhao, Mingjun Jia, et al, Journal of Molecular Catalysis a: Chemical,2010,327,32 to 37; jishui Shi, Mingjun Jia, et al, Catalysis Communications,2011,12,721 to 725; liu courage, liu tao, etc., Chemical research 2015, 26(1), 19 to 22). ZIF-67 is used as a catalyst, the dosage of the catalyst is about 1 percent of the total mass of dimethyl carbonate and diethyl carbonate, dimethyl carbonate and diethyl carbonate are subjected to ester exchange reaction to prepare EMC, the conversion rate of the dimethyl carbonate can reach more than 80 percent, but the reaction needs 24 hours (Lili Yang, Lin Yu, et al, Catalysis Communications,2014,54, 86-90; Kyoxu, industrial Catalysis, 2016, 24(10), 16-20).
Disclosure of Invention
In order to solve the outstanding problems of large catalyst dosage, low raw material conversion rate, long reaction time and the like in the process of preparing the methyl ethyl carbonate by carrying out ester exchange on dimethyl carbonate and diethyl carbonate at present, the invention aims to: the developed method for preparing the ethyl methyl carbonate by the ester exchange reaction of the dimethyl carbonate and the diethyl carbonate has the advantages of low toxicity of raw materials, little pollution, simple process, mild reaction conditions, small dosage of the catalyst, short reaction time, high raw material conversion rate, high selectivity of the product ethyl methyl carbonate and the like.
In order to achieve the purpose, the invention adopts the technical scheme that: the methyl ethyl carbonate is prepared by performing ester exchange reaction on dimethyl carbonate and diethyl carbonate serving as raw materials in the presence of a catalyst, wherein the reaction formula is as follows:
according to the invention, the catalyst is of great importance. Without catalyst or with low catalyst activity, the conversion of dimethyl carbonate is very low. When the catalyst activity is high, the high conversion rate of dimethyl carbonate and the high selectivity of ethyl methyl carbonate can be obtained. The ester exchange reaction catalyst researched and developed by the invention is one or more than two of titanium citrate, titanium malate, titanium tartrate, titanium oxalate, titanium malonate, titanium succinate, titanium glutarate and titanium adipate.
According to the invention, the molar ratio of dimethyl carbonate to diethyl carbonate is 1: 1; the dosage of the catalyst is 0.02-0.2%, preferably 0.05-0.15% of the total mass of the dimethyl carbonate and the diethyl carbonate; the reaction temperature is 80-100 ℃, and preferably 90-100 ℃; the reaction time is 2 to 6 hours, preferably 3 to 4 hours.
The invention has the beneficial effects that:
(1) the methyl ethyl carbonate is prepared by adopting the ester exchange method of dimethyl carbonate and diethyl carbonate, and has the following advantages: the raw materials have low toxicity, little pollution, simple process and mild reaction conditions; the product methyl ethyl carbonate does not azeotrope with the raw materials dimethyl carbonate and diethyl carbonate, and the product is simple to separate.
(2) The catalyst has no corrosion and less consumption, the conversion rate of the dimethyl carbonate can reach more than 85 percent, and the selectivity of the ethyl methyl carbonate reaches more than 99 percent.
Detailed Description
The following examples are provided to aid in the understanding of the present invention, but the present disclosure is not limited thereto.
Example 1
Adding 9.0 g of dimethyl carbonate (0.1mol), 11.8 g of diethyl carbonate (0.1mol) and 0.03 g of titanium citrate (which is 0.15 percent of the total mass of the dimethyl carbonate and the diethyl carbonate) into a 100ml two-neck round-bottom flask provided with a condenser tube, uniformly stirring, heating to 100 ℃ for reaction for 3 hours, and carrying out qualitative and quantitative analysis on the mixture after the reaction by gas chromatography-mass spectrometry, wherein the conversion rate of the dimethyl carbonate is 85 percent, and the selectivity of the ethyl methyl carbonate is over 99 percent.
Examples 2 to 8
Examples 2-8 were performed similarly to example 1, and the specific reaction conditions and results are shown in Table 1. Titanium malate, titanium tartrate, titanium oxalate, titanium malonate, titanium succinate, titanium glutarate and titanium adipate are used as catalysts, the molar ratio of dimethyl carbonate to diethyl carbonate is 1:1, the reaction temperature is 80-100 ℃, the reaction time is 2-6 hours, the conversion rate of the dimethyl carbonate is over 70 percent, and the selectivity of the ethyl methyl carbonate is over 99 percent.
TABLE 1 transesterification of dimethyl carbonate with diethyl carbonate to produce ethyl methyl carbonate
Comparative examples 9 to 11
To investigate the effect of the catalyst and its composition on the reaction, comparative experiments were performed. Dimethyl carbonate and diethyl carbonate were used as raw materials, and a reaction was carried out under the same conditions as in example 1 without using a catalyst or with titanium phthalate and titanium salicylate as catalysts, and the specific procedure was similar to example 1, and the results are shown in table 2.
TABLE 2 reaction results of comparative examples for the preparation of ethyl methyl carbonate by transesterification
| Comparative examples | Catalyst and process for preparing same | Conversion of dimethyl carbonate,% |
| 9 | - | 5 |
| 10 | Phthalic acid titanium | 6 |
| 11 | Salicylic acid titanium salt | 6 |
Reaction conditions are as follows: the mol ratio of dimethyl carbonate to diethyl carbonate is 1:1, the dosage of the catalyst is 0.15 percent of the total mass of the dimethyl carbonate and the diethyl carbonate, the reaction temperature is 100 ℃, and the reaction time is 3 hours.
In example 1, titanium citrate is used as a catalyst, the conversion rate of dimethyl carbonate is 85%, and the selectivity of ethyl methyl carbonate is more than 99%. However, according to comparative example 9, the conversion of dimethyl carbonate was much lower than that of example 1 under the same reaction conditions without catalyst. According to comparative examples 10-11, it can be seen that in the same reaction conditions, the conversion rate of dimethyl carbonate is much lower than that of example 1 by using titanium phthalate and titanium salicylate as catalysts, which indicates that the catalysts and their compositions have a great influence on the reaction results of the present invention.
In the invention, one or more than two of titanium citrate, titanium malate, titanium tartrate, titanium oxalate, titanium malonate, titanium succinate, titanium glutarate and titanium adipate are used as catalysts, dimethyl carbonate and diethyl carbonate undergo an ester exchange reaction, the conversion rate of the dimethyl carbonate is up to 85%, and the selectivity of ethyl methyl carbonate is up to more than 99%. The method has the advantages of low toxicity of raw materials, little pollution, simple process, mild reaction conditions, no corrosion and little consumption of the catalyst, high conversion rate of the raw materials and high selectivity of products, and the like.
Claims (2)
1. A method for preparing methyl ethyl carbonate by ester exchange reaction is characterized in that: dimethyl carbonate and diethyl carbonate are used as raw materials to prepare methyl ethyl carbonate in the presence of a catalyst, and the reaction formula is as follows:
the catalyst is one or more than two of titanium citrate, titanium malate, titanium tartrate, titanium oxalate, titanium malonate, titanium succinate, titanium glutarate and titanium adipate, and the dosage of the catalyst is 0.02-0.2% of the total mass of the dimethyl carbonate and the diethyl carbonate.
2. The method of claim 1, wherein: the molar ratio of dimethyl carbonate to diethyl carbonate is 1: 1; the dosage of the catalyst is 0.05-0.15% of the total mass of the dimethyl carbonate and the diethyl carbonate; the reaction temperature is 80-100 deg.C oC; the reaction time is 2-6 hours.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102863339A (en) * | 2012-09-18 | 2013-01-09 | 常州大学 | Method for synthesizing methylethyl carbonate by ester exchange of dimethyl carbonate and diethyl carbonate |
| CN103506157A (en) * | 2013-09-26 | 2014-01-15 | 常州大学 | Solid catalyst for synthesizing methyl ethyl carbonate and preparation method thereof |
| CN104540837A (en) * | 2012-06-28 | 2015-04-22 | 沙特基础工业公司 | Novel titanium catalyst end process for the preparation thereof |
| CN105646229A (en) * | 2014-12-04 | 2016-06-08 | 中国科学院大连化学物理研究所 | Method used for preparing higher aliphatic phthalates via ester exchange |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104540837A (en) * | 2012-06-28 | 2015-04-22 | 沙特基础工业公司 | Novel titanium catalyst end process for the preparation thereof |
| CN102863339A (en) * | 2012-09-18 | 2013-01-09 | 常州大学 | Method for synthesizing methylethyl carbonate by ester exchange of dimethyl carbonate and diethyl carbonate |
| CN103506157A (en) * | 2013-09-26 | 2014-01-15 | 常州大学 | Solid catalyst for synthesizing methyl ethyl carbonate and preparation method thereof |
| CN105646229A (en) * | 2014-12-04 | 2016-06-08 | 中国科学院大连化学物理研究所 | Method used for preparing higher aliphatic phthalates via ester exchange |
Non-Patent Citations (1)
| Title |
|---|
| Zeolitic imidazole framework-67 as an efficient heterogeneous catalyst for the synthesis of ethyl methyl carbonate;Lili Yang等;《Catalysis Communications》;20140602(第54期);第86-90页 * |
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