CN103012183A - Preparation method of N,-N-diethyl-formamide - Google Patents
Preparation method of N,-N-diethyl-formamide Download PDFInfo
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- CN103012183A CN103012183A CN2012105506398A CN201210550639A CN103012183A CN 103012183 A CN103012183 A CN 103012183A CN 2012105506398 A CN2012105506398 A CN 2012105506398A CN 201210550639 A CN201210550639 A CN 201210550639A CN 103012183 A CN103012183 A CN 103012183A
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- diethylamine
- methyl
- diethylformamide
- formiate
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 title abstract description 17
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 44
- 238000003756 stirring Methods 0.000 claims description 30
- 239000000047 product Substances 0.000 claims description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 14
- 230000035484 reaction time Effects 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 239000006227 byproduct Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000003039 volatile agent Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 230000009466 transformation Effects 0.000 claims description 6
- 238000010907 mechanical stirring Methods 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000004458 analytical method Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 11
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 abstract 6
- 230000006181 N-acylation Effects 0.000 abstract 1
- 238000004817 gas chromatography Methods 0.000 description 16
- 238000000605 extraction Methods 0.000 description 10
- 238000009835 boiling Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000012267 brine Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 238000013019 agitation Methods 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 241000282326 Felis catus Species 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- -1 amido pyrazine compounds Chemical class 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000004434 industrial solvent Substances 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- ORMHZBNNECIKOH-UHFFFAOYSA-N 4-(4-hydroxy-4-methylpentyl)cyclohex-3-ene-1-carbaldehyde Chemical compound CC(C)(O)CCCC1=CCC(C=O)CC1 ORMHZBNNECIKOH-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229920001986 Vinylidene chloride-vinyl chloride copolymer Polymers 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L Zinc chloride Inorganic materials [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of N,-N-diethyl-formamide. In the preparation method, diethylamine and methyl formate are used as raw materials; and the molar ratio (mol) of the diethylamine to the methyl formate is 1: (1 to 1.3). According to the invention, the methyl formate which is cheap, is easy to obtain and has high N-acylation activity is used as an acylating agent to be synthesized with diethylamine under normal pressure in a high conversation rate to form the N,-N-diethyl-formamide; the high-quality N,-N-diethyl-formamide can be simply, conveniently, rapidly and industrially synthesized by adopting a universal normal pressure reactor, a distilling apparatus and a rectifying apparatus which are well known by technicists in the field; and the preparation method has the advantages of simple synthetic process, good safety and low cost.
Description
Technical field
The present invention relates to a kind of N, the preparation method of N-diethylformamide, particularly a kind of take diethylamine and methyl-formiate as raw material prepares highly purified N, the preparation method of N-diethylformamide.
Background technology
At present, N, the N-diethylformamide is widely used industrial solvent, CAS: 617-84-5; English N by name, N-Diethylformamide is abbreviated as DEF; Molecular formula is C5H11NO; Molecular weight is 101.15; Density 0.9049,177～178 ℃ of boiling points are water white low density high boiling point polar organic solvent, with water and alcohol, ether, ketone, benzene etc. are miscible, have very strong solvability, can dissolve many organic polymers, such as polyacrylonitrile, urethane prepolymer, PVC, vinylidene chloride-vinyl chloride copolymer, polyvinyl formal, the high molecular polymers such as polyimide.At the industrial solvent that is commonly used for, extraction agent is the fine solvent of composite crystals, the metal-organic framework materials synthetic, and as the solvent of novel absorption refrigeration working medium to (R22-DEF), efficient lithium ion battery solvent etc.; And organic synthesis intermediate, make radical protection reagent etc. such as the synthetic drugs fumaric acid for sulphur good fortune Wei ester.
CN1194007 discloses a kind of method of separating polyhydroxy-alkanoates from biomass, wherein uses DEF and composition as extraction agent; CN1280711 discloses the electrolyte solvent that is used for the room temperature lithium-sulfur cell, wherein uses DEF and composition to make solvent; CN101179139 discloses a kind of preparation method of novel polymer lithium ion battery, wherein uses DEF to make solvent; CN101475586 discloses a kind of synthetic method of chlorinated phosphonate compounds, wherein uses DEF as reaction solvent; CN101503405 discloses a kind of preparation method of LYRAL VC acetal, wherein uses DEF as strong polar reaction solvent; CN102260218A discloses a kind of method that is prepared spices amido pyrazine compounds by halo pyrazine and the reaction of organic amine zinc chloride complex compound, wherein uses DEF to make reaction solvent; CN102293207A discloses a kind of compound medicine, wherein uses DEF as the formula of medicine composition; CN102558215A discloses a kind of technique of high boiling organosilicon cracking, wherein uses DEF as catalysts.
This material is of many uses in industry, yet about N, the synthetic method of N-diethylformamide is reported but seldom, be there is no industrial production device in China.[applied chemistry] magazine, the 5th phase of the 13rd volume, published the Liu Xing of Chengdu Organic Chemistry Inst., Chinese Academy of Sciences spring in October, 1996, [Synthesis of Diethyl Formamide by Catalytic Carbonylation of Diethylamine in Liquid Phase] literary composition that deliver on the Wu Yu pool etc., its method is: under high pressure, take sodium methylate as Primary Catalysts, propylene oxide is promotor, in autoclave, add diethylamine and pass into catalyzing carbon monoxide and synthesized N, the N-diethylformamide.The weak point of this method is under high pressure to react, and needs catalyzer, has used the very strong carbon monoxide of toxicity; Facility investment is high, and technology controlling and process is complicated, and product separation is difficult, and safety requirements is high, is difficult for industrialization.
Summary of the invention
In order to overcome existing N, the deficiency of the synthetic method of N-diethylformamide the invention provides a kind of N, the preparation method of N-diethylformamide.
The technical solution adopted for the present invention to solve the technical problems is:
N, the preparation method of N-diethylformamide, adopting diethylamine and methyl-formiate is raw material, and the mol ratio of diethylamine and methyl-formiate (mol) is 1: 1～1.3, and reaction equation is:
HCO-OCH
3 +?HN（CH
2CH
3）
2＝HCO-N(CH
2CH
3)
2? +?CH
3OH
Its preparation process is as follows:
A). in normal pressure downhill reaction still, add methyl-formiate;
B). under mechanical stirring, diethylamine is added dropwise in the reactor that adds methyl-formiate, carries out synthesis under normal pressure, time for adding is controlled at 3～9 hours; Simultaneously, by passing into cold water or icy salt solution cools in reacting kettle jacketing or interior spiral coil cooling tube, the control drip reacting temperature is 5 ℃～40 ℃;
C). after diethylamine was added dropwise to complete, the cold water or the icy salt solution that pass in off-response still chuck or the interior spiral coil cooling tube continued to keep stirring; The control temperature of reaction is 5 ℃～40 ℃ and carries out stirring reaction; The stirring reaction time is controlled to be 1～15 hour;
D). it is 4～24 hours that the control dropwise reaction time adds the total time of stirring reaction time; Reaction end is for adopting the gas chromatograph analysis to measure diethylamine residual quantity in the synthetic liquid, when the diethylamine transformation efficiency reaches 95% or be reaction end when above.
Step D) after reaction finishes, control first 95 ℃～100 ℃ of temperature and distill out front-end volatiles under normal pressure, the front composition that heats up in a steamer obtains N for the methyl alcohol of reaction by-product and excessive methyl-formiate and micro-diethylamine in the still kettle, the thick product of N-diethylformamide, purity are 95%～97%.By-product carbinol and lower boiling raw material excessive and that unreacted is complete that the reaction generation is removed in air distillation are that front-end volatiles reclaim as byproduct, and are conducive to N, the follow-up rectifying purifying of N-diethylformamide product.
After normal pressure steamed front-end volatiles, the thick product that obtains was again by rectification under vacuum, and the control condition of rectification under vacuum is: vacuum tightness is-0.08～-0.09mMPa, return and heat up in a steamer than being 1: 1 to 2: 1; Recovered temperature is 95 ℃～100 ℃, obtains N after the rectification under vacuum, and N-diethylformamide essence product purity is 99.5%～99.97%.Adopt rectification under vacuum can reduce the boiling point of product, prevent the disadvantageous effect that Yin Gaowen and oxidation bring.
The invention has the beneficial effects as follows, selected methyl-formiate with height N-acidylate activity cheap and easy to get be acylating agent and diethylamine under normal pressure high conversion synthesized N, N-diethylformamide; Employing is at the known general normal pressure reactor of those skilled in the art, water distilling apparatus, and rectifier unit just can easy rapidly industrialization synthesize high-quality N, the N-diethylformamide, it becomes very much, and technique is simple, security good, cost is low.
Embodiment
Below in conjunction with embodiment invention is described further.
Embodiment 1
At the stainless steel of 1000L with the 316L material of stirring, thermometer, reflux exchanger, dropping header tank
BandIn the reactor of chuck, add first methyl-formiate (industrial goods, content 99.2%, moisture 780ppm) 303 kilograms (5.0kmol).
In reactor, slowly be added dropwise to diethylamine (industrial goods, content 99.5%, moisture 750ppm) 368 kilograms (5.0kmol) from dripping header tank; Proportioning raw materials is for being methyl-formiate: diethylamine=1: 1mol; Begin to drip simultaneously, under agitation with the logical chilled brine mode of chuck fluid temperature in the reactor is down to 5 ℃; Keep good continuously stirring in the dropwise reaction process, control reactor internal reaction liquid temp is 5 ℃～10 ℃; Share 9 hours and drip diethylamine.
Dropwise, close the chuck chilled brine, continue to stir, the control temperature of reaction is 5 ℃～40 ℃ and carries out stirring reaction; Gave free rein to stirring reaction 15 hours.
Sampling detects residual diethylamine content through gas-chromatography (GC) and shows, the transformation efficiency of diethylamine reaches 95.4%, reaches reaction end; The reaction solution terminal temperature is 24 ℃, and total reaction time is 24 hours.
Embodiment 2
Stir at the 1000L band, thermometer, reflux exchanger adds first methyl-formiate (industrial goods, content 99.2%, moisture 780ppm) 363 kilograms (6.0kmol) in the enamel reaction still of dropping header tank.
Under the mechanical stirring, in reactor, slowly be added dropwise to diethylamine (industrial goods, content 99.5%, moisture 750ppm) 368 kilograms (5.0kmol) from dripping header tank; Proportioning raw materials is methyl-formiate: diethylamine=1.2: 1.0(mol).Begin to drip simultaneously, under agitation with the logical chilled brine mode of chuck fluid temperature in the reactor is down to 20 ℃; Keep good continuously stirring in the dropping process, control reactor internal reaction liquid temp is 20 ℃～30 ℃; Share 5 hours and drip diethylamine.
Dropwise, close the chuck chilled brine, continue to stir, the control temperature of reaction is 5 ℃～40 ℃ and carries out stirring reaction; Gave free rein to stirring reaction 10 hours.
Sampling detects residual diethylamine content through gas-chromatography (GC) and shows, the transformation efficiency of diethylamine reaches 97.3%, to reaction end.The reaction solution terminal temperature is 25 ℃.Total reaction time is 15 hours.
Embodiment 3
First add methyl-formiate (industrial goods, content 99.2%, moisture 780ppm) 393 kilogram (6.5kmol) in the stainless steel cauldron of spiral coil cooling tube at 1000L in the band of the 316L material of stirring, thermometer, reflux exchanger, dropping header tank,
Under the mechanical stirring, in reactor, slowly be added dropwise to diethylamine (industrial goods, content 99.5%, moisture 750ppm) 368 kilograms (5.0kmol) from dripping header tank; Proportioning raw materials is: methyl-formiate: diethylamine=1.3: 1.0(mol).Begin to drip simultaneously, under agitation with the mode of the logical cooling of interior spiral coil cooling tube tap water fluid temperature in the reactor is down to 25 ℃; Keep good continuously stirring in the dropping process, control reactor internal reaction liquid temp is 25 ℃～40 ℃; Share 3 hours and drip diethylamine.
Dropwise, close the cooling tap water of interior spiral coil cooling tube, continue to stir, the control temperature of reaction is 5 ℃～40 ℃ and carries out stirring reaction; Nature stirring reaction 1 hour.
Sampling detects residual diethylamine content through gas-chromatography (GC) and shows, the transformation efficiency of diethylamine reaches 96.5%, to reaction end.The reaction solution terminal temperature is 35 ℃.Total reaction time is 4 hours.
Embodiment 4
In the stainless steel jacket reactor of 1000L with the 316L material of stirring, thermometer, reflux exchanger, dropping header tank, add first methyl-formiate (industrial goods, content 99.2%, moisture 780ppm) 378 kilograms (6.5mol);
Under mechanical stirring, in reactor, slowly be added dropwise to diethylamine (industrial goods, content 99.5%, moisture 750ppm) 368 kilograms (5.0kmol) from dripping header tank; Proportioning raw materials is: methyl-formiate: diethylamine=1.25: 1.0(mol).Begin to drip simultaneously, under agitation with the logical chilled brine mode of chuck fluid temperature in the reactor is down to 15 ℃; Keep good continuously stirring in the dropping process, control reactor internal reaction liquid temp is 15 ℃～30 ℃; Share 7 hours and drip diethylamine.
Dropwise, close the chuck chilled brine, continue to stir, the control temperature of reaction is 5 ℃～40 ℃ and carries out stirring reaction; Stirring reaction 5 hours.
Sampling detects residual diethylamine content through gas-chromatography (GC) and shows, the transformation efficiency of diethylamine reaches 98.1%, to reaction end.The reaction solution terminal temperature is 32 ℃, and total reaction time is 12 hours.
Embodiment 5
The synthetic liquid that embodiment 3 is made changes in the lass lining still kettle of 1000L, under stirring, slowly is warming up to 95 ℃ with the logical vapor heated mode of chuck, steams thing and is collected in after condenser condenses in the byproduct tank.After temperature of charge in the still reaches 95 ℃, keep temperature-resistant, when almost not having overhead product, distilled out the methyl alcohol of reaction generation, excessive methyl-formiate and complete these lower boiling front-end volatiles by products of diethylamine of traces of unreacted.Get material detection in the still kettle, be light yellow transparent liquid, adopt gas-chromatography (GC) to analyze N, N-diethylformamide content is 98.2%.Get thick product.
Embodiment 6
The synthetic liquid that embodiment 4 is made changes in the lass lining still kettle of 1000L, under stirring, slowly is warming up to 100 ℃ with the logical vapor heated mode of chuck, steams thing and is collected in after condenser condenses in the byproduct tank.After temperature of charge in the still reaches 100 ℃, keep temperature-resistant, and when almost not having overhead product, distilled out the methyl alcohol that reaction generates, excessive methyl-formiate and complete these lower boiling front-end volatiles by products of diethylamine of traces of unreacted.Get material detection in the still kettle, be light yellow transparent liquid, gas-chromatography (GC) is analyzed N, and N-diethylformamide content is 98.9%.Get thick product.
Embodiment 7
The thick product that embodiment 5 is made changes in the lass lining rectifying still of 1000L, connects rectifying tower (diameter 400mm, height 8m) on the rectifying still, and solidifying condenser returns and heats up in a steamer pump, under meter, extraction tank, the devices such as vacuum entirely.Carry out product rectifying with slow intensification of the logical vapor heated mode of chuck, steam thing after the condensation of cat head total condenser, control condition is: reflux ratio is 1: 1, and vacuum tightness is-0.08MPa 100 ℃ of recovered temperatures; Evenly the extraction tower top temperature is that 100 ℃ cut is in smart product extraction tank.The smart product of getting the extraction tank detects, and is colourless transparent liquid, and gas-chromatography (GC) is analyzed N, and N-diethylformamide content is 99.5%.Get smart product.Take diethylamine elaboration yield as: 97.15%.
Embodiment 8
To change in the lass lining rectifying still of 1000L by the thick product that real embodiment 6 makes, and connect rectifying tower (diameter 400mm, height 8m) on the rectifying still, solidifying condenser returns and heats up in a steamer pump, under meter, extraction tank, the devices such as vacuum entirely.Carry out product rectifying with slow intensification of the logical vapor heated mode of chuck, steam thing after the condensation of cat head total condenser, control condition is: reflux ratio is 2: 1, and vacuum tightness is-0.09MPa that recovered temperature is 95 ℃; Evenly the extraction tower top temperature is that 95 ℃ cut is in smart product extraction tank.The smart product of getting the extraction tank detects, and is colourless transparent liquid, and gas-chromatography (GC) is analyzed N, and N-diethylformamide content is 99.97%.Get smart product.Take diethylamine elaboration yield as: 96.85%.
Above-mentioned discussion and case study on implementation only for the explanation specific embodiments of the present invention, limit absolutely not its actual range.Protection scope of the present invention is as the criterion with the claim protection domain.
Claims (3)
1. N, the preparation method of N-diethylformamide is characterized in that, and adopting diethylamine and methyl-formiate is raw material, and the mol ratio of described diethylamine and methyl-formiate (mol) is 1: 1～1.3, reaction equation:
HCO-OCH
3?+?HN（CH
2CH
3）
2＝HCO-N(CH
2CH
3)
2?+?CH
3OH
Its preparation process is as follows:
A). in normal pressure downhill reaction still, add methyl-formiate;
B). under mechanical stirring, diethylamine is added dropwise in the reactor that adds methyl-formiate, carries out synthesis under normal pressure, time for adding is controlled at 3～9 hours; Simultaneously, by passing into cold water or icy salt solution cools in reacting kettle jacketing or interior spiral coil cooling tube, the temperature of control dropwise reaction is 5 ℃～40 ℃;
C). after diethylamine was added dropwise to complete, the cold water or the icy salt solution that pass in off-response still chuck or the interior spiral coil cooling tube continued to keep stirring; The control temperature of reaction is 5 ℃～40 ℃ and carries out stirring reaction; The stirring reaction time is controlled to be 1～15 hour;
D). the total time of control dropwise reaction time and stirring reaction time is 4～24 hours; Reaction end is for adopting the gas chromatograph analysis to measure diethylamine residual quantity in the synthetic liquid, when the diethylamine transformation efficiency reaches 95% or be reaction end when above.
2. N according to claim 1, the preparation method of N-diethylformamide, it is characterized in that, described step D) after reaction finishes, control first 95 ℃～100 ℃ of temperature and distill out front-end volatiles under normal pressure, the front composition that heats up in a steamer obtains N for the methyl alcohol of reaction by-product and excessive methyl-formiate and micro-diethylamine in the still kettle, the thick product of N-diethylformamide, purity are 95%～97%.
3. N according to claim 2, the preparation method of N-diethylformamide is characterized in that, after described normal pressure steams front-end volatiles, the thick product that obtains is again by rectification under vacuum, and the vacuum degree control of rectification under vacuum is-0.08～-0.09MPa, return and heat up in a steamer than being controlled to be 1: 1 to 2: 1; Recovered temperature is 95 ℃～100 ℃, obtains N after the rectification under vacuum, and N-diethylformamide essence product purity is 99.5%～99.97%.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103435508A (en) * | 2013-08-16 | 2013-12-11 | 山东华鲁恒升化工股份有限公司 | Preparation process and device for N,N-diethylformamide |
| CN104262189A (en) * | 2014-10-11 | 2015-01-07 | 昊华(成都)科技有限公司 | Method for liquid-phase preparation of high-purity N, N-diethylformamide |
| CN105330559A (en) * | 2015-10-14 | 2016-02-17 | 宿迁新亚科技有限公司 | Electronic-grade formamide compound preparation method |
| CN103922957B (en) * | 2014-03-21 | 2016-05-18 | 迈奇化学股份有限公司 | A kind of preparation method of continuous production DEF |
| CN107286041A (en) * | 2016-04-01 | 2017-10-24 | 成都川科化工有限公司 | A kind of preparation method of N, N- diethylformamide |
| CN108997156A (en) * | 2018-08-06 | 2018-12-14 | 浙江新化化工股份有限公司 | A kind of method of one-step method continuous production N, N- diethylformamide |
| CN111253274A (en) * | 2020-02-13 | 2020-06-09 | 南京工业大学 | Preparation method of dialkyl formamide |
| CN115385813A (en) * | 2022-08-25 | 2022-11-25 | 宿迁新亚科技有限公司 | Production process for preparing dibutyl formamide |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103435508A (en) * | 2013-08-16 | 2013-12-11 | 山东华鲁恒升化工股份有限公司 | Preparation process and device for N,N-diethylformamide |
| CN103435508B (en) * | 2013-08-16 | 2015-09-23 | 山东华鲁恒升化工股份有限公司 | The preparation technology of N, N-diethylformamide and device thereof |
| CN103922957B (en) * | 2014-03-21 | 2016-05-18 | 迈奇化学股份有限公司 | A kind of preparation method of continuous production DEF |
| CN104262189A (en) * | 2014-10-11 | 2015-01-07 | 昊华(成都)科技有限公司 | Method for liquid-phase preparation of high-purity N, N-diethylformamide |
| CN105330559A (en) * | 2015-10-14 | 2016-02-17 | 宿迁新亚科技有限公司 | Electronic-grade formamide compound preparation method |
| CN107286041A (en) * | 2016-04-01 | 2017-10-24 | 成都川科化工有限公司 | A kind of preparation method of N, N- diethylformamide |
| CN108997156A (en) * | 2018-08-06 | 2018-12-14 | 浙江新化化工股份有限公司 | A kind of method of one-step method continuous production N, N- diethylformamide |
| CN108997156B (en) * | 2018-08-06 | 2021-01-05 | 浙江新化化工股份有限公司 | Method for continuously producing N, N-diethylformamide by one-step method |
| CN111253274A (en) * | 2020-02-13 | 2020-06-09 | 南京工业大学 | Preparation method of dialkyl formamide |
| CN115385813A (en) * | 2022-08-25 | 2022-11-25 | 宿迁新亚科技有限公司 | Production process for preparing dibutyl formamide |
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