CN101239907A - Method for preparing glycol methyl ether acetate - Google Patents
Method for preparing glycol methyl ether acetate Download PDFInfo
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- CN101239907A CN101239907A CNA2008100338760A CN200810033876A CN101239907A CN 101239907 A CN101239907 A CN 101239907A CN A2008100338760 A CNA2008100338760 A CN A2008100338760A CN 200810033876 A CN200810033876 A CN 200810033876A CN 101239907 A CN101239907 A CN 101239907A
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- ether acetate
- methyl ether
- glycol methyl
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Abstract
The invention discloses a method for preparing glycol monomethyl ether acetate, comprising using ethyl acetate and glycol methyl ether as materials, performing ester changing reaction in the presence of a solid alkali catalyst, distilling by-product ethanol fro a reaction tank through fractionation, filtering and recoverying the catalyst after reaction, fractionating the reaction liquid to obtain glycol monomethyl ether acetate. The invention has the advantages of: (1) high yield of 95.5-99.6%, (2) cheap catalyst and small usage which is 0.1-1.5% of the total weight of reaction materials; (3) gentle reaction condition, reaction under atmosphere pressure; (4) repeatedly-usable catalyst; (5) samll corrosion on the device and no environmental contamination.
Description
Technical field
The present invention relates to the organic chemistry synthesis technical field, specifically a kind of ester-interchange method prepares the method for glycol methyl ether acetate.
Background technology
Existing ehter bond in the glycol ether acetic ester molecule, carbonyl is arranged again, and carbonyl has formed the structure of ester again, thereby it has the not available performance of common organic solvents, both solubilized organic molecules, synthetic or natural macromolecular compound, can dissolve each other with water or water-soluble cpds in various degree again, it is the low toxicity advanced industrial solvent of the good high boiling point bifunctional of a class, its performance is better than glycol ether, at automobile finish, container, mechanical means, art metal furniture, the utensil topcoating, printing ink, water soluble paint, multicolor spray paint, and paint remover, industrial cleaning agent, obtained in the production of products such as woodstain using widely.At present, output in domestic does not satisfy demand far away, most of dependence on import.Therefore, develop this series products and study its performance, have important theory and using value.
The synthetic technology of glycol methyl ether acetate has three kinds of direct esterification method, one-step synthesis and ester-interchange methods.The direct esterification method is to be raw material with acetic acid and ethylene glycol monomethyl ether, with sulfuric acid, phosphoric acid, tosic acid, Zeo-karb, molecular sieve carried TiO
2/ SO
4Rare-earth salts and layer pillared clays etc. are carried out esterification method for catalyzer.Because of generating water in the reaction process, and to neutralize usually during the separating reaction liquid of reaction back, operation such as washing, and reaction raw materials ethylene glycol monomethyl ether and product glycol methyl ether acetate solubleness in water is all very big, and this makes troubles just for Separation and Recovery, wastewater treatment.For this reason, improvement and the product separation that for many years improvement of this method is concentrated on catalyzer reclaims two aspects.One-step synthesis is to be raw material with oxyethane and ritalin, with hydrotalcite calcined material, ZrCl
4-N-Methyl pyrrolidone, Zr (OPr)
4-Et
3N and AlCl
3-Et
3N etc. are catalyzer, and raw materials cost is low, and reactant is formed simple, the product separate easily, and the purity height, but by product is many.Ester-interchange method is to be raw material with vinyl acetic monomer and ethylene glycol monomethyl ether, with aluminum alkoxide, titan-alkoxide, phosphoric acid, tosic acid and organic metal salt etc. is catalyzer, generate alcohol in the product and do not generate water, by product ethanol can be used as the raw material of synthesizing glycol ether, also avoid producing complicated moisture azeotropic system, simplified lock out operation.But, there are shortcomings such as catalyzer costs an arm and a leg, toxicity big, can not recycle at said process.
Summary of the invention
The purpose of this invention is to provide a kind of product yield height, speed of reaction is fast, energy consumption is less, catalyzer is cheap and easy to get and callable ester-interchange method prepares the method for glycol methyl ether acetate.
The object of the present invention is achieved like this:
A kind of method for preparing glycol methyl ether acetate is characterized in that: this method is to be raw material with ethyl acetate and ethylene glycol monomethyl ether, carries out transesterification reaction and prepare glycol methyl ether acetate in the presence of solid base catalyst, specifically may further comprise the steps:
The preparation of the 1st step solid base catalyst
Solid base catalyst is alkaline earth metal oxide or load-type solid;
The preparation of a, alkaline earth metal oxide
Get alkaline earth metal oxide or hydroxide powder, 800～1000 ℃ of following roasting 5～10h in the retort furnace, promptly;
The preparation of b, load type solid body base catalyst
It is 10～50% solution that active ingredient is made into concentration, it in the solid-liquid mass ratio 1: 1～5 ratio, carrier dropped in the aforementioned solution flood, after stirring 1～2h under 50～80 ℃, revolve and steam to doing, solids is put in dry 6～12h in 100 ℃ of baking ovens, 800～1000 ℃ of following roasting 5～10h in the retort furnace, promptly;
The 2nd step transesterification reaction
In the three neck containers that have induction stirring, thermometer, rectifying column, adapting pipe, recovery flask, add ethyl acetate and ethylene glycol monomethyl ether, its mol ratio is 1～6: 1, add the solid base catalyst that accounts for raw material gross weight 0.1～1.5% again, carrying out reflux stirs, heating and temperature control is at 70～120 ℃, the ethanol that reaction is produced steams from still head upper end azeotropic, reacts to still head upper end temperature to be higher than ethyl acetate and ethanol azeotropic temperature (promptly not having ethanol steams) stops;
The separation of the 3rd step catalyzer and the purifying of product
With the material filtering that the last step obtains, leach catalyzer and filtrate, filtrate is collected 140～145 ℃ cut through normal pressure rectifying, obtains water white product and is glycol methyl ether acetate; Catalyzer is reused after drying.
Described alkaline earth metal oxide is calcium oxide or strontium oxide; The carrier of load-type solid is a kind of in aluminum oxide, gac, molecular sieve, the silica gel porous material; Active ingredient is a kind of in alkalimetal oxide, fluorochemical, carbonate, the nitrate.
Compare with background technology, advantage of the present invention is: (1) productive rate height is 95.5～99.6%; (2) catalyzer is cheap, and consumption is little, accounts for 0.1～1.5% of reaction raw materials gross weight; (3) reaction conditions gentleness, normal pressure is reaction down; (4) catalyzer is reusable; (5) equipment corrosion is little, does not have environmental pollution etc.
Embodiment
Below will be further elaborated the present invention by specific embodiment:
Embodiment 1
The preparation of the 1st step solid base catalyst
The preparation of alkaline earth metal oxide
Get the CaO powder, 800 ℃ of following roasting 5h in the retort furnace, promptly;
The 2nd step transesterification reaction
In the 250mL three-necked bottle that has induction stirring, thermometer, rectifying column, adapting pipe, recovery flask, add the 0.6mol ethyl acetate, 0.1mol ethylene glycol monomethyl ether, 0.1g solid base catalyst, carrying out reflux stirs, the ethanol that reaction is produced steams from still head upper end azeotropic, reacts to still head upper end temperature to be higher than ethyl acetate and ethanol azeotropic temperature (promptly not having ethanol steams) stops;
The separation of the 3rd step catalyzer and the purifying of product
With the material filtering that the last step obtains, the catalyzer drying that leaches is directly used in down secondary response, and filtrate is collected 140～145 ℃ cut through normal pressure rectifying, obtains water white product and is glycol methyl ether acetate; Yield is 96%.
Embodiment 2
Except for the following differences, all the other are identical with embodiment 1.
The preparation of load type solid body base catalyst
4 gram KF are dissolved in the 25 gram water, add 10 gram Al
2O
3, 60 ℃ down stir 1h after, revolve and steam to doing, solids is put in dry 12h in 100 ℃ of baking ovens, 800 ℃ of following roasting 5h in the retort furnace, promptly; Yield is 95%.
Embodiment 3-8:
Except for the following differences, all the other are identical with embodiment 2, are active ingredient with KF, adopt different carrier shown in the table 1.
Table 1
| Embodiment | Carrier | Yield/% |
| 3 4 5 6 7 8 | Gac magnesium oxide zirconium white silicon-dioxide beta-molecular sieve pseudo-boehmite | 94 95 93 96 92 94 |
Embodiment 9-14
Except for the following differences, all the other are identical with embodiment 2, are carrier with the aluminum oxide, adopt different active ingredient shown in the table 2.
Table 2
| Embodiment | Active ingredient | Yield/% |
| 9 10 11 12 13 14 | Salt of wormwood saltpetre Potassium ethanoate yellow soda ash sodium oxalate sodium formiate | 94 95 93 96 92 94 |
Embodiment 15-20
Except for the following differences, all the other are identical with embodiment 2, are carried on aluminum oxide with salt of wormwood, and the solid base catalyst recirculation uses the influence to reaction to the results are shown in Table 3.
Table 3
| Embodiment | Catalyzer is reused number of times | Yield/% |
| 9 10 11 12 13 14 | 1 2 3 4 5 6 | 97 97 97 97 96 95 |
Claims (1)
1, a kind of method for preparing glycol methyl ether acetate is characterized in that: this method is to be raw material with ethyl acetate and ethylene glycol monomethyl ether, carries out transesterification reaction and prepare glycol methyl ether acetate in the presence of solid base catalyst, specifically may further comprise the steps:
The preparation of the 1st step solid base catalyst
Solid base catalyst is alkaline earth metal oxide or load-type solid;
The preparation of a, alkaline earth metal oxide
Get alkaline earth metal oxide or hydroxide powder, 800～1000 ℃ of following roasting 5～10h in the retort furnace, promptly; Described alkaline earth metal oxide is calcium oxide or strontium oxide;
The preparation of b, load type solid body base catalyst
It is 10～50% solution that active ingredient is made into concentration, it in the solid-liquid mass ratio 1: 1～5 ratio, carrier dropped in the aforementioned solution flood, after stirring 1～2h under 50～80 ℃, revolve and steam to doing, be put in dry 6～12h in 100 ℃ of baking ovens, 800～1000 ℃ of following roasting 5～10h in the retort furnace, promptly; Described carrier is a kind of in aluminum oxide, gac, molecular sieve, the silica gel porous material; Described active ingredient is a kind of in alkalimetal oxide, fluorochemical, carbonate, the nitrate;
The 2nd step transesterification reaction
In the three neck containers that have induction stirring, thermometer, rectifying column, adapting pipe, recovery flask, add ethyl acetate and ethylene glycol monomethyl ether, its mol ratio is 1～6: 1, add the solid base catalyst that accounts for raw material gross weight 0.1～1.5% again, carrying out reflux stirs, heating and temperature control is at 70～120 ℃, the ethanol that reaction is produced steams from still head upper end azeotropic, reacts to be higher than ethyl acetate and ethanol azeotropic temperature to still head upper end temperature and promptly not have ethanol and steam and stop;
The separation of the 3rd step catalyzer and the purifying of product
With the material filtering that the last step obtains, leach catalyzer and filtrate, filtrate is collected 140～145 ℃ cut through normal pressure rectifying, obtains the water white transparency product and is glycol methyl ether acetate; Catalyzer is reused after drying.
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|---|---|---|---|
| CN2008100338760A CN101239907B (en) | 2008-02-26 | 2008-02-26 | Method for preparing glycol methyl ether acetate |
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| CN2008100338760A CN101239907B (en) | 2008-02-26 | 2008-02-26 | Method for preparing glycol methyl ether acetate |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102992956A (en) * | 2011-09-13 | 2013-03-27 | 湖南长岭石化科技开发有限公司 | Preparation method of 2-butyl alcohol |
| CN102993003A (en) * | 2011-09-13 | 2013-03-27 | 湖南长岭石化科技开发有限公司 | Acetate preparation method |
| CN102993008A (en) * | 2011-09-13 | 2013-03-27 | 湖南长岭石化科技开发有限公司 | Preparation method of polyol alkyl ether acetate |
| CN102993006A (en) * | 2011-09-13 | 2013-03-27 | 湖南长岭石化科技开发有限公司 | Sec-butyl acetate ester exchange method |
| CN103183609A (en) * | 2011-12-31 | 2013-07-03 | 深圳市飞扬骏研技术开发有限公司 | Preparation method of ethylene glycol monoacetate and ethylene glycol diacetate |
| CN103896764A (en) * | 2012-12-27 | 2014-07-02 | 胡先念 | Propylene glycol ether acetate preparation method |
| CN103922931A (en) * | 2014-04-19 | 2014-07-16 | 常州大学 | Method for one-step catalytic synthesis of ethylene glycol ethyl ether acetate |
| CN103920480A (en) * | 2014-04-19 | 2014-07-16 | 江苏怡达化学股份有限公司 | Magnesium-aluminum-zirconium solid catalyst for embedded synthesis of alkoxy alcohol ether ester in one step |
| CN106311207A (en) * | 2016-08-25 | 2017-01-11 | 铜仁学院 | Method for preparing silica-based solid base |
| CN109265314A (en) * | 2018-11-28 | 2019-01-25 | 临沂中天环保科技有限公司 | The preparation method and preparation facilities of propylene glycol methyl ether acetate |
| CN111484432A (en) * | 2020-05-13 | 2020-08-04 | 新乡市瑞丰新材料股份有限公司 | Preparation method of thioether type hindered phenol antioxidant |
| CN113979861A (en) * | 2021-11-29 | 2022-01-28 | 河北工业大学 | Method for preparing propylene glycol monomethyl ether acetate by catalytic distillation |
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| CN1100616C (en) * | 1998-07-29 | 2003-02-05 | 中国科学院大连化学物理研究所 | Catalyst for synthesizing glycol monoether acetate and diethylene glycol monoether acetate |
| CN1079283C (en) * | 1998-11-13 | 2002-02-20 | 北京化工大学 | Load type laminated zirconium sulfate catalyst and its application in preparation of aliphatic alcohol ether acetate |
-
2008
- 2008-02-26 CN CN2008100338760A patent/CN101239907B/en not_active Expired - Fee Related
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| CN102993008B (en) * | 2011-09-13 | 2015-05-06 | 湖南长岭石化科技开发有限公司 | Preparation method of polyol alkyl ether acetate |
| CN102993003A (en) * | 2011-09-13 | 2013-03-27 | 湖南长岭石化科技开发有限公司 | Acetate preparation method |
| CN102993008A (en) * | 2011-09-13 | 2013-03-27 | 湖南长岭石化科技开发有限公司 | Preparation method of polyol alkyl ether acetate |
| CN102993006A (en) * | 2011-09-13 | 2013-03-27 | 湖南长岭石化科技开发有限公司 | Sec-butyl acetate ester exchange method |
| CN102992956A (en) * | 2011-09-13 | 2013-03-27 | 湖南长岭石化科技开发有限公司 | Preparation method of 2-butyl alcohol |
| CN102993003B (en) * | 2011-09-13 | 2016-01-06 | 湖南长岭石化科技开发有限公司 | A kind of preparation method of acetic ester |
| CN102993006B (en) * | 2011-09-13 | 2015-05-06 | 湖南长岭石化科技开发有限公司 | Sec-butyl acetate ester exchange method |
| CN103183609A (en) * | 2011-12-31 | 2013-07-03 | 深圳市飞扬骏研技术开发有限公司 | Preparation method of ethylene glycol monoacetate and ethylene glycol diacetate |
| CN103183609B (en) * | 2011-12-31 | 2015-04-29 | 深圳市飞扬骏研技术开发有限公司 | Preparation method of ethylene glycol monoacetate and ethylene glycol diacetate |
| CN103896764A (en) * | 2012-12-27 | 2014-07-02 | 胡先念 | Propylene glycol ether acetate preparation method |
| CN103920480A (en) * | 2014-04-19 | 2014-07-16 | 江苏怡达化学股份有限公司 | Magnesium-aluminum-zirconium solid catalyst for embedded synthesis of alkoxy alcohol ether ester in one step |
| CN103922931B (en) * | 2014-04-19 | 2015-10-14 | 常州大学 | A kind of method of a step catalytically synthesizing glycol ether acetate |
| CN103920480B (en) * | 2014-04-19 | 2015-12-30 | 江苏怡达化学股份有限公司 | An a kind of step embeds the magnesium-aluminum-zirconium solid catalyst of synthesis alkoxyl alcohol ether-ether |
| CN103922931A (en) * | 2014-04-19 | 2014-07-16 | 常州大学 | Method for one-step catalytic synthesis of ethylene glycol ethyl ether acetate |
| CN106311207A (en) * | 2016-08-25 | 2017-01-11 | 铜仁学院 | Method for preparing silica-based solid base |
| CN109265314A (en) * | 2018-11-28 | 2019-01-25 | 临沂中天环保科技有限公司 | The preparation method and preparation facilities of propylene glycol methyl ether acetate |
| CN111484432A (en) * | 2020-05-13 | 2020-08-04 | 新乡市瑞丰新材料股份有限公司 | Preparation method of thioether type hindered phenol antioxidant |
| CN111484432B (en) * | 2020-05-13 | 2022-03-25 | 新乡市瑞丰新材料股份有限公司 | Preparation method of thioether type hindered phenol antioxidant |
| CN113979861A (en) * | 2021-11-29 | 2022-01-28 | 河北工业大学 | Method for preparing propylene glycol monomethyl ether acetate by catalytic distillation |
| CN113979861B (en) * | 2021-11-29 | 2023-12-22 | 河北工业大学 | Method for preparing propylene glycol methyl ether acetate by catalytic rectification |
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