CN111233641A - Preparation method of diethylene glycol monomethyl ether - Google Patents
Preparation method of diethylene glycol monomethyl ether Download PDFInfo
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- CN111233641A CN111233641A CN201811447867.6A CN201811447867A CN111233641A CN 111233641 A CN111233641 A CN 111233641A CN 201811447867 A CN201811447867 A CN 201811447867A CN 111233641 A CN111233641 A CN 111233641A
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- diethylene glycol
- monomethyl ether
- glycol monomethyl
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
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Abstract
The application discloses a preparation method of diethylene glycol monomethyl ether, which comprises the step of carrying out contact reaction on a raw material containing diethylene glycol and methanol and an acid catalyst under an inactive atmosphere condition to obtain the diethylene glycol monomethyl ether. The method overcomes the defects of an organic synthesis method using alkali and a methylating agent in the prior art, adopts a catalytic synthesis method, and carries out catalytic etherification reaction on diethylene glycol and methanol, thereby providing a green synthesis route for preparing the diethylene glycol monomethyl ether compound, which reduces the environmental pollution, reduces the production cost, does not need the processes of sodium salt generated by post-treatment and the like.
Description
Technical Field
The application relates to a preparation method of diethylene glycol monomethyl ether, belonging to the field of chemical materials.
Background
Diethylene glycol monomethyl ether contains an alcohol ether structure, is an excellent high-boiling point solvent, can dissolve organic molecules, synthetic polymers and natural macromolecules, and has certain water solubility, so that the diethylene glycol monomethyl ether is widely used as a solvent for dyes, synthetic resins, nitrocellulose, cellulose acetate, oils and the like, and is also used as a high-boiling point solvent in printing ink, paint and the like, and is also used as a cleaning agent, a plasticizer, an extracting agent and the like.
At present, the method for synthesizing diethylene glycol monomethyl ether mainly adopts a co-product generated by ethylene oxide and methanol under the catalysis of BF 3-diethyl ether. The process uses ethylene oxide, so that potential safety hazards of easy explosion exist; in addition, the product is abundant and purification is difficult.
Diethylene glycol is an important byproduct in the synthesis of ethylene glycol by the reaction of ethylene oxide and water in petrochemical industry, and has important significance for the utilization of the ethylene glycol. At present, the reports of preparing diglyme by using diglycol as a raw material are less. Diethylene glycol is mainly adopted to react with sodium hydroxide and chloromethane to prepare diethylene glycol mono (di) methyl ether (CN 92108541.9); also, researchers disclosed an improved Williamson synthesis method, which uses diethylene glycol as a raw material and dimethyl sulfate as a methylating agent to prepare diethylene glycol monomethyl ether (CN 91108228.X) under the action of a basic catalyst. The above methods are all organic synthesis methods, using a large amount of methylating agent and a large amount of alkali, and simultaneously generating a large amount of byproducts such as sodium salt and the like. Therefore, the development of a more environment-friendly and green process for synthesizing diethylene glycol monomethyl ether is needed.
Disclosure of Invention
According to one aspect of the application, a method for preparing diethylene glycol monomethyl ether is provided, which overcomes the defects of an organic synthesis method using alkali and a methylating agent in the prior art, adopts a catalytic synthesis method, and carries out catalytic etherification reaction on diethylene glycol and methanol, thereby providing a green synthesis route for preparing diethylene glycol monomethyl ether compounds, which reduces environmental pollution, reduces production cost, does not need processes such as post-treatment of generated sodium salt and the like.
The preparation method of the diethylene glycol monomethyl ether comprises the step of carrying out contact reaction on a raw material containing diethylene glycol and methanol and an acid catalyst under an inactive atmosphere condition to obtain the diethylene glycol monomethyl ether.
The invention provides a synthesis method of diethylene glycol monomethyl ether, which comprises the following reaction equation:
optionally, the acidic catalyst is selected from at least one of a heteropolyacid catalyst, a solid acid catalyst.
The catalyst provided by the application is a high-boiling-point and environment-friendly acid catalyst.
Optionally, the heteropolyacid catalyst is selected from at least one of phosphotungstic acid, phosphomolybdic acid, silicotungstic acid, silicomolybdic acid.
Optionally, the solid acid catalyst is selected from at least one of Amberlyst-15, H-beta, H-ZSM-5.
Optionally, the molar ratio of the diethylene glycol to the methanol is 1: 1-20.
Preferably, the molar ratio of diethylene glycol to methanol is 1: 4.
Optionally, the mass percentage of the acidic catalyst in the raw material is 0.5-20%.
The upper limit of the mass percentage of the acidic catalyst in the raw material is 2%, 2.5%, 5%, 10%, 20%, and the lower limit of the mass percentage of the acidic catalyst in the raw material is 0.5%, 2%, 2.5%, 5%, 10%.
Alternatively, the etherification reaction conditions are: the reaction temperature is 100-250 ℃, and the reaction time is 2-10 h.
The upper limit of the reaction temperature of the etherification reaction is selected from 110 ℃, 150 ℃, 180 ℃, 200 ℃, 220 ℃ and 250 ℃, and the lower limit of the reaction temperature of the etherification reaction is selected from 100 ℃, 110 ℃, 150 ℃, 180 ℃, 200 ℃ and 220 ℃.
The upper limit of the reaction time of the etherification reaction is selected from 4h, 6h, 8h and 10h, and the lower limit of the reaction time of the etherification reaction is selected from 2h, 4h, 6h and 8 h.
Preferably, the etherification reaction conditions are: the reaction temperature is 110-220 ℃, and the reaction time is 2-6 h.
Optionally, the inert atmosphere comprises at least one of nitrogen, helium, argon.
The beneficial effects that this application can produce include:
1) the synthesis method of diethylene glycol monomethyl ether provided by the invention utilizes diethylene glycol as a raw material, which is an important byproduct in ethylene glycol synthesis, so that the preparation of diethylene glycol monomethyl ether by catalytic conversion of diethylene glycol is a high value-added utilization of the synthesized ethylene glycol byproduct.
2) Compared with the prior art, the method for preparing the diethylene glycol monomethyl ether by adopting the catalytic synthesis method can avoid using a large amount of alkali and methylating reagent, reduce the generation of sodium salt, relieve the pressure on the environment, reduce the production cost of enterprises and be a green synthetic route.
3) The invention adopts a high-boiling point and environment-friendly catalyst, and avoids using a large amount of inorganic acid or inorganic base.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the raw materials in the examples of the present application were purchased commercially, and the instruments used were those recommended by the manufacturer.
The molecular sieves used were purchased from south-opening catalyst factories, Amberlyst-15 from south-China synthetic chemical Co., Ltd.
The conversion, selectivity, in the examples of the present application were calculated as follows:
in the examples of the present application, the conversion of diethylene glycol and the selectivity of diethylene glycol monomethyl ether were calculated on a carbon mole basis:
diethylene glycol conversion ═ mole number of diethylene glycol carbon in the feed) - (mole number of diethylene glycol carbon in the product) ]/(mole number of diethylene glycol carbon in the feed) × (100%)
The selectivity for diethylene glycol monomethyl ether is diethylene glycol monomethyl ether in moles of carbon ÷ total of carbon moles of the different organics of the product x 100%.
In the present application, an agilent gas 7890 gas chromatograph is used for gas chromatography for product analysis.
Example 1
This example provides a process for the preparation of diethylene glycol monomethyl ether. Adding 20g of diethylene glycol and methanol in a molar ratio of 1:4 and 1g of phosphotungstic acid catalyst into a 50ml high-pressure reaction kettle, stirring and mixing uniformly at room temperature, sealing the kettle, replacing air with nitrogen for 5 times, heating to 200 ℃, and reacting for 2 hours under the autogenous pressure. The stirring was stopped. The reaction kettle was cooled to room temperature. Taking a proper amount of reaction liquid to neutralize with triethylamine. The neutralized reaction solution was filtered and analyzed by gas chromatography. As a result, the conversion of diethylene glycol was 68.1%, and the selectivity of diethylene glycol monomethyl ether was 60.4%.
Example 2
This example provides a process for the preparation of diethylene glycol monomethyl ether. Adding 20g of diethylene glycol and methanol in a molar ratio of 1:4 and 2g of silicotungstic acid catalyst into a 50ml high-pressure reaction kettle, stirring and mixing uniformly at room temperature, sealing the kettle, replacing air with nitrogen for 3 times, heating to 150 ℃, and reacting for 4 hours under the autogenous pressure. The stirring was stopped. The reaction kettle was cooled to room temperature. Taking a proper amount of reaction liquid to neutralize with triethylamine. The neutralized reaction solution was filtered and analyzed by gas chromatography, and the result was that the conversion of diethylene glycol was 60% and the selectivity of diethylene glycol monomethyl ether was 72%.
Example 3
This example provides a process for the preparation of diethylene glycol monomethyl ether. 20g of diethylene glycol and methanol in a molar ratio of 1:4 and 0.5g of silicomolybdic acid catalyst are added into a 50ml high-pressure reaction kettle, stirred and mixed uniformly at room temperature, the kettle is sealed, air is replaced by nitrogen for 3 times, the temperature is increased to 180 ℃, the reaction pressure is self-pressure, and the reaction lasts for 2 hours. The stirring was stopped. The reaction kettle was cooled to room temperature. Taking a proper amount of reaction liquid to neutralize with triethylamine. The neutralized reaction solution was filtered and analyzed by gas chromatography. As a result, the conversion of diethylene glycol was 68.1%, and the selectivity of diethylene glycol monomethyl ether was 60.4%.
Example 4
This example provides a process for the preparation of diethylene glycol monomethyl ether. 20g of diethylene glycol and methanol with a molar ratio of 1:4 and 0.4g of H-beta (silicon-aluminum ratio of 40) catalyst are added into a 50ml high-pressure reaction kettle, stirred and mixed uniformly at room temperature, the kettle is sealed, air is replaced by nitrogen for 4 times, the temperature is increased to 180 ℃, the reaction pressure is self-pressure, and the reaction is carried out for 8 hours. The stirring was stopped. The reaction kettle was cooled to room temperature. Taking a proper amount of reaction liquid to enter a gas chromatograph for analysis. The result was a conversion of diethylene glycol of 46% and a selectivity of diethylene glycol monomethyl ether of 75%.
Example 5
This example provides a process for the preparation of diethylene glycol monomethyl ether. 20g of diethylene glycol and methanol in a molar ratio of 1:4 and 0.4g of HZSM-5 (silicon to aluminum ratio of 25) catalyst are added into a 50ml high-pressure reaction kettle, stirred and mixed uniformly at room temperature, the kettle is sealed, air is replaced by nitrogen for 5 times, the temperature is raised to 220 ℃, the reaction pressure is self-pressure, and the reaction is carried out for 4 hours. The stirring was stopped. The reaction kettle was cooled to room temperature. Taking a proper amount of reaction liquid to enter a gas chromatograph for analysis. As a result, the conversion of diethylene glycol was 42%, and the selectivity of diethylene glycol monomethyl ether was 77%.
Example 6
This example provides a process for the preparation of diethylene glycol monomethyl ether. 20g of diethylene glycol and methanol in a molar ratio of 1:2 and 1g of Amberlyst-15 catalyst are added into a 50ml high-pressure reaction kettle, the mixture is stirred and mixed evenly at room temperature, the kettle is sealed, air is replaced by nitrogen for 5 times, the temperature is increased to 180 ℃, the reaction pressure is self-pressure, and the reaction lasts for 10 hours. The stirring was stopped. The reaction kettle was cooled to room temperature. Taking a proper amount of reaction liquid to enter a gas chromatograph for analysis. As a result, the conversion of diethylene glycol was 47% and the selectivity of diethylene glycol monomethyl ether was 73%.
The results show that the high-boiling-point environment-friendly catalyst for preparing diethylene glycol monomethyl ether disclosed by the invention can be used for efficiently catalyzing diethylene glycol to convert and prepare diethylene glycol monomethyl ether. The method provides a new green synthesis method of diethylene glycol monomethyl ether with industrial prospect.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. A preparation method of diethylene glycol monomethyl ether is characterized in that a raw material containing diethylene glycol and methanol is in contact reaction with an acid catalyst under the condition of inactive atmosphere to obtain the diethylene glycol monomethyl ether.
2. The production method according to claim 1, wherein the acid catalyst is at least one selected from a heteropoly acid catalyst and a solid acid catalyst.
3. The production method according to claim 2, wherein the heteropolyacid catalyst is at least one member selected from the group consisting of phosphotungstic acid, phosphomolybdic acid, silicotungstic acid and silicomolybdic acid.
4. The method of claim 2, wherein the solid acid catalyst is at least one selected from Amberlyst-15, H-beta, and H-ZSM-5.
5. The method according to claim 1, wherein the molar ratio of diethylene glycol to methanol is 1:1 to 20.
6. The method according to claim 1, wherein the molar ratio of diethylene glycol to methanol is 1: 4.
7. The preparation method according to claim 1, wherein the acid catalyst is present in the raw material in an amount of 0.5 to 20% by mass.
8. The process according to claim 1, wherein the etherification reaction conditions are as follows: the reaction temperature is 100-250 ℃, and the reaction time is 2-10 h.
9. The process according to claim 1, wherein the etherification reaction conditions are as follows: the reaction temperature is 110-220 ℃, and the reaction time is 2-6 h.
10. The method according to claim 1, wherein the inert gas atmosphere is at least one selected from the group consisting of nitrogen, helium, and argon.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114621247A (en) * | 2020-12-11 | 2022-06-14 | 中国科学院大连化学物理研究所 | Method for preparing/synthesizing isosorbide methyl ether |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004020378A2 (en) * | 2002-08-28 | 2004-03-11 | Ferro Corporation | Method of producing glycol ethers |
| CN104250206A (en) * | 2013-06-28 | 2014-12-31 | 中国科学院大连化学物理研究所 | Preparation method of glycol ether |
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- 2018-11-29 CN CN201811447867.6A patent/CN111233641A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004020378A2 (en) * | 2002-08-28 | 2004-03-11 | Ferro Corporation | Method of producing glycol ethers |
| CN104250206A (en) * | 2013-06-28 | 2014-12-31 | 中国科学院大连化学物理研究所 | Preparation method of glycol ether |
Non-Patent Citations (1)
| Title |
|---|
| 戚蕴石等: "杂多酸对于二甘醇和乙醇的醚化反应的催化作用", 《催化学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114621247A (en) * | 2020-12-11 | 2022-06-14 | 中国科学院大连化学物理研究所 | Method for preparing/synthesizing isosorbide methyl ether |
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