CN1609085A - Prepn process of diethylene glycol methyl ethyl ether - Google Patents
Prepn process of diethylene glycol methyl ethyl ether Download PDFInfo
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- CN1609085A CN1609085A CN 200410069589 CN200410069589A CN1609085A CN 1609085 A CN1609085 A CN 1609085A CN 200410069589 CN200410069589 CN 200410069589 CN 200410069589 A CN200410069589 A CN 200410069589A CN 1609085 A CN1609085 A CN 1609085A
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- diethylene glycol
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Abstract
Diethylene glycol methyl ethyl ether is one kind of polyhydric alcohol ether as high boiling point organic solvent in fine organic chemical industry. It is prepared with diethylene glycol ethyl ether and alkali mixture of NaOH, KOH, Na2CO3 and K2CO3 as material through reaction of 1-7 hr while introducing N2 and at 30-120 deg.c to produce sodium alcoholate and/or potassium alcoholate; Williamson reaction between sodium alcoholate and/or potassium alcoholate and halogenomethane at 30-110 deg.c for 0.5-6.0 hr and ageing for 0.5-5 hr; separating reacted material to obtain diethylene glycol methyl ethyl ether mother liquid and filter residue containing diethylene glycol methyl ethyl ether; soaking the filter residue in methanol, washing and separation to obtain methanol solution of diethylene glycol methyl ethyl ether; and rectifying the mother liquid and the methanol solution to obtain diethylene glycol methyl ethyl ether product while recovering methanol.
Description
Technical field
The synthetic method of diethylene glycol methyl ethyl ether involved in the present invention belongs to preparation method's technical field of polyvalent alcohol ethers high boiling point polar organic solvent in the Fine Organic Chemical product.
Background technology
Diethylene glycol methyl ethyl ether is called diethylene glycol ethylmethyl ether again, is one of important derivatives of ethylene glycol and Diethylene Glycol.Existing typical ehter bond has the alkyl of low-carbon (LC)---methyl and ethyl again in the molecular structure of diethylene glycol ethylmethyl ether; There is not strong polar oh group in the glycol molecule structure again in the basic structure that had both had ethylene glycol.These constructional features make diethylene glycol ethylmethyl ether not only to some small molecules organic compound (as alcohol, ether, aldehyde, ketone, aromatic hydrocarbons, halohydrocarbon, alkane etc.) extraordinary dissolving power be arranged, and to the relatively large organic compound of some carbon numbers even macromolecular organic compound reasonable dissolving dispersive ability is also arranged; Simultaneously diethylene glycol ethylmethyl ether also has good dissolving ability to some micromolecular mineral compound (as the oxide compound of alkali-metal oxyhydroxide, tin etc.).The solvent that all these characteristics make diethylene glycol ethylmethyl ether not only can be used as excellent property is used for the production of multiple Chemicals, and has a wide range of applications in the production of the recycling of the production of products such as speciality coating such as high-performance clean-out system, radiosensitive extraordinary resin, electrically conducting coating and waste polymer and photosensitivity printing drawing board, the field of surface treatment printed with production, mechanical means and the printed circuit board (PCB) of extraordinary ink.Report according to document, at present the basic production method of diethylene glycol ethylmethyl ether mainly comprises following several: (1) is raw material with TC (being also referred to as diethylene glycol monoethyl ether) and methyl alcohol, in the presence of the catalyzer (as the vitriol oil, heteropolyacid, macropore cation resin etc.) by TC and methanol molecules between dehydration method prepare; (2) be raw material with diethylene glycol monomethyl ether and ethanol, in the presence of the catalyzer (as the vitriol oil, heteropolyacid, macropore cation resin etc.) by diethylene glycol monomethyl ether and ethanol molecule between dehydration method preparation; (3) be raw material with TC and methyl-sulfate, in the presence of alkali, prepare by the method for methyl-sulfate to the methylation of TC; (4) be raw material with TC and methylcarbonate, in the presence of alkali, prepare by the method for methylcarbonate to the methylation of TC; (5) with the TC be basic raw material, earlier itself and active basic metal (as sodium, potassium etc.) reaction are generated sodium alkoxide or potassium alcoholate, carry out Williamson ether condensation reaction (Williamson's reaction) with the sodium alkoxide that generates or potassium alcoholate and halomethane (as methyl chloride, monobromethane, methyl iodide etc.) again and prepare; (6) with the diethylene glycol monomethyl ether be basic raw material, earlier itself and active basic metal (as sodium, potassium etc.) reaction are generated sodium alkoxide or potassium alcoholate, carry out Williamson ether condensation reaction (Williamson's reaction) preparation with sodium alkoxide that generates and halogen ethane (as monochloroethane, monobromethane etc.) again; (7) be basic raw material with diethylene glycol monoethyl ether and alkali metal hydroxide, at first refluxing under the certain reaction temperature in the presence of band such as benzene, toluene aqua and fractionation generates sodium alkoxide or potassium alcoholate, is that the Williamson ether condensation reaction (Williamson's reaction) that raw material passes through to take place between it and halomethane prepares with the sodium alkoxide that generates or potassium alcoholate again; (8) be basic raw material with diethylene glycol monomethyl ether and alkali metal hydroxide, at first refluxing under the certain reaction temperature in the presence of band such as benzene, toluene aqua and fractionation generates sodium alkoxide or potassium alcoholate, is that the Williamson ether condensation reaction (Williamson's reaction) that raw material passes through to take place between it and halogen ethane prepares with the sodium alkoxide that generates or potassium alcoholate again.
(1) and (2) in these production methods are owing to be similar to and prepare mixed ether by the intermolecular dehydration method of alcohol with different alcohol in the presence of catalyzer and prepare diethylene glycol ethylmethyl ether, thereby not only the yield of product is lower, and the selectivity of product is also poor; In the method (3) since the basic raw material methyl-sulfate that uses the brush poison is arranged and in the presence of water, also can partial hydrolysis generate sulfuric acid, thereby to the requirement of production unit than higher, and in process of production also relatively seriously to the corrosion of equipment; Higher and reaction needs to carry out under a higher relatively temperature because of employed basic raw material methylcarbonate price in the method (4), thereby not only production cost of products is higher but also selectivity product is low; Make the Diethylene Glycol production cost of products also than higher because of the active alkali-metal price height of basic raw material that uses in method (5) and (6); Need in method (7) and (8) under refluxad to take the water that generates out of reaction system by the band aqua when the first step is reacted, this not only makes the energy consumption of reaction higher, and has the recycling problem of band aqua.
Combine in the present invention existing about diethylene glycol ethylmethyl ether production and when preparation the whole bag of tricks characteristics, and utilize the condensation reaction of Williamson ether to have the characteristics of highly selective when the synthetic mixed ether by technological improvement to existing preparation method, be that basic raw material has prepared and has CH with diethylene glycol monoethyl ether, alkali metal hydroxide, alkaline carbonate, halomethane
3OCH
2CH
2OCH
2CH
2OCH
2CH
3The diethylene glycol ethylmethyl ether product that structural formula is represented.
In the building-up process of diethylene glycol ethylmethyl ether, contacted the preparation of a lot of relevant ethers, the technical information of character and application facet, wherein the present invention there be mainly comprising of certain reference value: " phase-transfer catalysis is synthesized dibutyl ethylene glycol ether " (Hebei chemical industry, 1990, No4), " the polyoxyethylene glycol phase-transfer catalysis is synthesized monocycle oxygen propyl ether " (chemical reagent, 1990, Vol 12, No3), " glycol ether and ethanol is synthetic diethylene glycol ethyl ether in the presence of heteropolyacid salt catalyst " (East China University of Science's journal, 1995, Vol 21, No5), " Study of Synthetic Diethylene Glycol Dimethyl Ether " (Yunnan University's journal.Natural science edition, 1997, Vol 19, No4), " the synthetic and application of glycol ether diglycidylether " (Hubei chemical industry 1994, Vol 11, No1), " preparation of diethylene glycol monobutyl ether " (Jiangsu chemical industry, 1998, Vol 26, No2), " Decarboxylation of alkyl carbonate to alkyl ether " (BE92-930,1992-1028), " Preparation of (poly) ethylene glycol diether from the correspondingmonoethers and carbonate esters " (JP 09227435A2,1997-09-02), " Preparation of photosensitivelithographic plates using dithylene diethylene glycol dimethyl ether-based coating solvent " (JP03141355A2,1991-06-17), " Detergent compositions for screen printing plates " (JP1007426A2,1998-03-24), " Agents for dissolving and removing tin oxides from apparatus forplating or peeling of tin and tin alloys " (JP 1995-149765,1995-05-25), " PVC dissolving agents andtreatment of PVC therewith " (JP 1999-103629,1999-04-12), " Radiation-sensitive resin compositionfor the partition formation of color filter " (JP 11281815A2,1999-10-15), " Ink compositionscontaining pyrrolidinedione or piperidinedione for ink-jet printing " (JP2003003096A2,2003-07-08), " synthetic method of dialkyl capped polyether " (CN 1276391A, 2000-12-13), " synthetic method of methyl or ethyl capping polether " (CN 1311265A, 2001-09-05), " production of triethylene glycol methyl ether and environmental issue " (Speciality Petrochemicals, 1998, No6), " progress of glycol ether production technology " (petrochemical complex, 1999, Vol 28, No3), " Fine Organic Chemical product technical manual " (Chemical Industry Press, 1991).
Summary of the invention
The preparation method's of related diethylene glycol ethylmethyl ether purpose mainly is for by being basic raw material with diethylene glycol monoethyl ether, sodium hydroxide and/or potassium hydroxide and/or yellow soda ash and/or salt of wormwood and halomethane among the present invention, and can generate diethylene glycol monoethyl ether sodium and/or diethylene glycol monoethyl ether potassium and sodium alkoxide and/or potassium alcoholate with sodium hydroxide and/or potassium hydroxide and/or yellow soda ash and/or salt of wormwood reaction under certain condition by means of diethylene glycol monoethyl ether can carry out the condensation reaction of Williamson ether to generate diethylene glycol ethylmethyl ether with halomethane.When preparing diethylene glycol monoethyl ether sodium and/or diethylene glycol monoethyl ether potassium by diethylene glycol monoethyl ether, by in reaction mass, feeding N
2Realize protection on the one hand, on the other hand the N by going into again to reaction
2Take the water that generates in the reaction out of to promote the generation of diethylene glycol monoethyl ether sodium and/or diethylene glycol monoethyl ether potassium.When carrying out the condensation reaction of Williamson ether, pass through the feeding speed or the adding speed of control halomethane and stirring and feeding N
2Reach the abundant contact of realization response material under the bubbling condition; By being handled with methyl alcohol, the filter residue that obtains in the reaction reclaimed the diethylene glycol ethylmethyl ether product that is present in wherein.Application through above a series of control methods and treatment process, the manufacturing cost of diethylene glycol ethylmethyl ether is reduced, reduced in general synthetic diethylene glycol ethylmethyl ether method because of using strong acid as catalyzer and in reaction process, can produce the corrosion that the raw material of acidic substance brings production unit, the potential hazard that when having reduced in the general production method of diethylene glycol ethylmethyl ether because of the methyl-sulfate that uses severe toxicity to raw material simultaneously the production operation personnel has been brought and to the high request of production unit has improved utilization ratio and the selectivity of reaction and the yield of diethylene glycol ethylmethyl ether of basic raw material diethylene glycol monoethyl ether in the diethylene glycol ethylmethyl ether production process.
Concrete implementation method
The preparation process of diethylene glycol ethylmethyl ether mainly comprises following components: (1) diethylene glycol monoethyl ether with by sodium hydroxide and/or potassium hydroxide and/or yellow soda ash and/or salt of wormwood by certain mass than the solid caustic soda component that is made at logical N
2Condition under carry out sodium alkoxide and/or potassium alcoholate reaction and generate diethylene glycol monoethyl ether sodium and/or diethylene glycol monoethyl ether potassium; (2) sodium and/or potassium alcoholate reaction generation diethylene glycol monoethyl ether sodium and/or diethylene glycol monoethyl ether potassium and halomethane carry out the mixture that Williamson ether condensation reaction generation includes diethylene glycol ethylmethyl ether; (3) filter residue that the mixture that contains diethylene glycol ethylmethyl ether that obtains after the etherificate obtains including the mother liquor of diethylene glycol ethylmethyl ether and is inclusive with a small amount of diethylene glycol ethylmethyl ether by centrifugal or filtering method; (4) filter residue that is inclusive with a small amount of diethylene glycol ethylmethyl ether with methyl alcohol soak, centrifugal again or filter methanol solution and sodium-chlor and/or the Repone K filter residue that obtains containing diethylene glycol ethylmethyl ether after the washing; (5) carrying out rectifying again after diethylene glycol ethylmethyl ether mother liquor and the methanol solution that contains diethylene glycol ethylmethyl ether are merged obtains the diethylene glycol ethylmethyl ether product and reclaims methyl alcohol.The preparation technology of diethylene glycol ethylmethyl ether and related process parameter are that the diethylene glycol monoethyl ether of 80-100% is that the raw material typical case is exemplified below with the 100kg mass content: (1) 100kg mass content is that the diethylene glycol monoethyl ether product of 80-100% joins in the reactor of strap clamp cover and/or coil pipe heating unit and whipping appts, under agitation adds 50-200kg by mass ratio m (NaOH): m (KOH): m (Na in batches
2CO
3): m (K
2CO
3The composite solid caustic soda component that forms of)=0.5-1.0: 0-0.5: 0-0.7: 0-0.4, heating makes the temperature of reaction mass rise to 30-120 ℃ under the condition that feeds N2, and reacts 1.0-7.0h down to finish sodium alkoxide and/or potassium alcoholate reaction at 30-120 ℃; (2) continuing to feed N
2Condition under adjust reaction mass temperature be feeding methyl chloride and/or dripping bromine methane and/or methyl iodide in 30-110 ℃ and the material that obtains after sodium alkoxide and/or the potassium alcoholate reaction, the feeding speed of control methyl chloride and/or the rate of addition of monobromethane and/or methyl iodide, methyl chloride and/or monobromethane and/or methyl iodide are added in 0.5-6.0h, the add-on of methyl chloride and/or monobromethane and/or methyl iodide is pressed m (halomethane): m (diethylene glycol monoethyl ether)=0.3-1.5: 1 adds, and the formation of halomethane is pressed m (methyl chloride): m (monobromethane): m (methyl iodide)=0-1: 0-1: 0-1; (3) reaction mass that adds be over methyl chloride and/or monobromethane and/or methyl iodide is proceeded aging reaction 0.5-5.0h under 30-110 ℃; (4) reaction mass after aging separates the filter residue that obtains including the mother liquor of diethylene glycol ethylmethyl ether and be inclusive with a small amount of diethylene glycol ethylmethyl ether by centrifugal or filtering method; (5) filter residue that will be inclusive with a small amount of diethylene glycol ethylmethyl ether with methyl alcohol soak, centrifugal again or filter after the washing to obtain containing methanol solution and the sodium-chlor and/or the potassium oxide filter residue of diethylene glycol ethylmethyl ether, the consumption of methyl alcohol is undertaken by m (methyl alcohol): m (filter residue)=2.0-10.0: 0.5-5.0; (6) carry out rectifying again after diethylene glycol ethylmethyl ether mother liquor and the methanol solution that contains diethylene glycol ethylmethyl ether are merged, collect corresponding fraction to reclaim methyl alcohol, collect corresponding fraction to obtain the diethylene glycol ethylmethyl ether product at 166-180 ℃ at 50-70 ℃; The mass content of diethylene glycol ethylmethyl ether is greater than 95-99.5% (mass ratio) in the diethylene glycol ethylmethyl ether product that obtains, and water content is less than 0.1-0.5% (mass ratio).
Claims (7)
1, obtained structural formula CH by the method for utilizing the condensation reaction of Williamson ether
3OCH
2CH
2OCH
2CH
2OCH
2CH
3The diethylene glycol ethylmethyl ether product of expression.
2, the preparation of diethylene glycol ethylmethyl ether product according to claim 1, it is characterized in that: the diethylene glycol monoethyl ether that with the mass content is 80-100% is a raw material, and press m (solid caustic soda component): m (diethylene glycol monoethyl ether)=0.5-2.0: 1.0 proportioning is at logical N
2Reach in diethylene glycol monoethyl ether, to add under the stirring condition and press mass ratio m (NaOH): m (KOH): m (Na
2CO
3): m (K
2CO
3)=0.5-1.0: 0-0.5: 0-0.7: 0-0.4 is by sodium hydroxide and/or potassium hydroxide and/or yellow soda ash and/or the composite solid caustic soda component that forms of salt of wormwood.
3, the preparation of diethylene glycol ethylmethyl ether product according to claim 1, it is characterized in that: the temperature of reaction of correspondence is 30-120 ℃ when preparing diethylene glycol monoethyl ether sodium and/or diethylene glycol monoethyl ether potassium by diethylene glycol monoethyl ether, and the reaction times is 1.0-7.0h; In reaction, realize the protection and the part of reaction are taken out of the water that generates in pure sodium and/or the potassium alcoholate reaction process simultaneously, promoted the generation of diethylene glycol monoethyl ether sodium and/or diethylene glycol monoethyl ether potassium with the N2 that feeds.
4, the preparation of diethylene glycol ethylmethyl ether product according to claim 1, it is characterized in that: under 30-110 ℃ temperature of reaction, by in pure sodium and/or the reacted material of potassium alcoholateization, feeding methyl chloride and/or dripping bromine methane and/or methyl iodide to finish the condensation reaction of Williamson ether.The add-on of methyl chloride and/or monobromethane and/or methyl iodide is pressed m (halomethane): m (diethylene glycol monoethyl ether)=0.3-1.5: 1 adds, and the formation of halomethane is pressed m (methyl chloride): m (monobromethane): m (methyl iodide)=0-1: 0-1: 0-1 and constituted.
5, the preparation of diethylene glycol ethylmethyl ether product according to claim 1, it is characterized in that: when carrying out the condensation reaction of Williamson ether, methyl chloride and/or monobromethane and/or methyl iodide are added in 0.5-6.0h by the feeding speed of control methyl chloride and/or the rate of addition of monobromethane and/or methyl iodide; The reaction mass that adds methyl chloride and/or monobromethane and/or methyl iodide is proceeded aging reaction under 30-110 ℃, the reaction times is 0.5-5.0h.
6, the preparation of diethylene glycol ethylmethyl ether product according to claim 1, it is characterized in that: the reaction mass that obtains after the condensation reaction of Williamson ether separates by centrifugal or filtering method, the filter residue that has obtained including the mother liquor of diethylene glycol ethylmethyl ether and be inclusive with a small amount of diethylene glycol ethylmethyl ether; Centrifugal again or filter the methanol solution that has obtained containing diethylene glycol ethylmethyl ether after the filter residue that is inclusive with a small amount of diethylene glycol ethylmethyl ether soaks, washs with methyl alcohol, carry out that methyl alcohol soaks, the consumption of methyl alcohol is undertaken by m (methyl alcohol): m (filter residue)=2.0-10.0: 0.5-5.0 during carrying out washing treatment.
7, the preparation of diethylene glycol ethylmethyl ether product according to claim 1, it is characterized in that: distill again after diethylene glycol ethylmethyl ether mother liquor and the methanol solution that contains diethylene glycol ethylmethyl ether are merged, collect corresponding fraction to reclaim methyl alcohol at 50-70 ℃, collect corresponding fraction to obtain the diethylene glycol ethylmethyl ether product at 166-180 ℃: the amount of the holding content of diethylene glycol ethylmethyl ether is greater than 95-99.5% (mass ratio) in the diethylene glycol ethylmethyl ether product that obtains, and water content is less than 0.1-0.5% (mass ratio).
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| CN 200410069589 CN1609085A (en) | 2004-07-22 | 2004-07-22 | Prepn process of diethylene glycol methyl ethyl ether |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106631711A (en) * | 2016-11-17 | 2017-05-10 | 黄山学院 | Method for synthesizing diethylene glycol methyl hexyl ether |
| WO2017163981A1 (en) * | 2016-03-23 | 2017-09-28 | 日本ゼオン株式会社 | Resin composition, resin film, and electronic component |
-
2004
- 2004-07-22 CN CN 200410069589 patent/CN1609085A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017163981A1 (en) * | 2016-03-23 | 2017-09-28 | 日本ゼオン株式会社 | Resin composition, resin film, and electronic component |
| CN106631711A (en) * | 2016-11-17 | 2017-05-10 | 黄山学院 | Method for synthesizing diethylene glycol methyl hexyl ether |
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