CN101891761B - Method for catalytically synthesizing triethyl phosphate by phase transfer - Google Patents
Method for catalytically synthesizing triethyl phosphate by phase transfer Download PDFInfo
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- CN101891761B CN101891761B CN2010102296238A CN201010229623A CN101891761B CN 101891761 B CN101891761 B CN 101891761B CN 2010102296238 A CN2010102296238 A CN 2010102296238A CN 201010229623 A CN201010229623 A CN 201010229623A CN 101891761 B CN101891761 B CN 101891761B
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- triethyl phosphate
- sodium salt
- organic solvent
- acid ester
- phase transfer
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Abstract
The invention relates to a method for catalytically synthesizing triethyl phosphate by phase transfer. Diethyl phosphate sodium salt is used as a raw material, phase transfer catalyst is added into the material, and ethylation reagent is added in an organic solvent and water system to generate triethyl phosphate; and the triethyl phosphate is separated and purified to obtain a finished product. Compared with the prior art, the catalyst has lower cost, the organic solvent and water are adopted as mixed solvent, the organic solvent can be recycled, so the method is friendly to environment, reduces the synthesizing cost, not only recycles the diethyl phosphate sodium salt, changes waste into valuable organic phosphor resources, reduces environmental pollution, but also provides a novel way for industrial production of the triethyl phosphate. The method not only has the advantages of few reacting steps, convenient operation, high yield, high product purity and easy industrial production, but also reduces environmental pollution of side product phosphoric acid, diethyl ester and sodium salt in a fluorescent whitening agent production process.
Description
Technical field
The present invention relates to a kind of method of organic synthesis, especially the synthetic method for preparing triethyl phosphate of phase-transfer catalysis.
Background technology
The triethyl phosphate molecular formula is (CH
3CH
2O)
3PO, English name Triethyl Phosphate is called for short TEP.Molecular weight 182.16 is a kind of colourless transparent liquids, fusing point-56.5 ℃, 215～216 ℃ of boiling points, specific density 1.064 (20/4 ℃), water-soluble entirely, be soluble in organic solvents such as ethanol, ether, benzene, but along with temperature rises can hydrolysis gradually in water.As a kind of high boiling solvent, the purposes of triethyl phosphate very extensively.In rubber and plastics, can be used as softening agent, catalyzer, solvent, stablizer, solidifying agent and tenderizer etc.; It is one of main raw material of preparation agricultural chemicals; Also can be used for plant-growth regulator, skimmer, the dyeing auxiliary of acetate fiber, the production of luminescent lamp glass paint etc.The synthetic two lines that mainly contain of the preparation triethyl phosphate of reporting both at home and abroad at present.Article one, being the U.S.6673955 report, is phosphorus esterification reagent with the POCl3, obtains compound with ethanol synthesis again, and this compound method causes product to decompose yield and purity drop in reaction process owing to generate hydrogen chloride by-product.U.S.2636048 discharges the hydrogenchloride that generates through feeding nitrogen, causes a large amount of ethanol losses, and productive rate is decreased.Produce at present problems such as the technology ubiquity yield (50%～60%) of triethyl phosphate is lower (as: " Hubei University Of Technology's journal " the 22nd the 5th phase of volume 63～65 pages " research of triethyl phosphate new synthetic process ").Another route, the U.S.3136805 report is a starting raw material with the triethyl-phosphite, under alkaline condition, obtains triethyl phosphate with hydrogen peroxide oxidation.The deficiency of this compound method is: triethyl-phosphite is understood hydrolysis and then is caused the yield of triethyl phosphate to reduce.Therefore must strictly control the generation that the pH value reduces side reaction.All there is contaminate environment in various degree in by product diethyl phosphoric acid sodium in the existing white dyes production process, is difficult to problems such as processing.
Summary of the invention
The object of the invention just is the deficiency to above-mentioned prior art, and a kind of method of catalytically synthesizing triethyl phosphate by phase transfer is provided.
The objective of the invention is to realize through following technical scheme:
The preparation method of catalytically synthesizing triethyl phosphate by phase transfer comprises following order and step: each raw material add-on is in mol
A, with the by product p diethylaminobenzoic acid ester sodium salt in the white dyes production process and phase-transfer catalyst by 1: 0.01～0.15mol, put in the reactor drum that reflux exchanger, feed hopper, whipping appts and TM are housed; Add organic solvent 400ml～800ml, water 0～200ml by every mole of phosphoric acid diethyl ester sodium salt again;
B, heated and stirred make p diethylaminobenzoic acid ester sodium salt and catalyst dissolution, are warming up to backflow;
C, adding ethyl sulfate, the molar ratio of p diethylaminobenzoic acid ester sodium salt and ethyl sulfate is 1: 0.5～3mol;
70～100 ℃ of d, maintenance back flow reaction temperature, reaction times 4～10h, cooling, suction filtration gets yellow solution;
E, be washed till neutrality, wash once with saturated sodium-chloride with twice back of washing again, use anhydrous magnesium sulfate drying at last with saturated sodium bicarbonate;
F, revolve and steam solvent and obtain triethyl phosphate bullion, yellow transparent liquid;
G, get pure triethyl phosphate, colourless transparent liquid through underpressure distillation again.
The objective of the invention is to realize through following technical scheme:
Organic solvent comprises toluene, YLENE, chlorobenzene, acetonitrile or MIBK.Phase-transfer catalyst is benzyltriethylammoinium chloride, cetyl trimethylammonium bromide or Tetrabutyl amonium bromide.
Beneficial effect: the present invention compared with prior art, used catalyzer cost is lower, adopts organic solvent and water as mixed solvent; Organic solvent can recycle, and is environmentally friendly, reduced synthetic cost; Not only the p diethylaminobenzoic acid ester sodium salt has been carried out utilizing again; Waste is converted into the organophosphorus resource with practical value, has reduced environmental pollution, and new approach is provided for the industrial production of triethyl phosphate.It is few that this method not only has reactions step, easy and simple to handle, and yield is high, and product purity is high, is easy to suitability for industrialized production, and has reduced the environmental pollution of the by product p diethylaminobenzoic acid ester sodium salt in the white dyes production process.
Embodiment
Do further detailed description below in conjunction with embodiment:
The method of catalytically synthesizing triethyl phosphate by phase transfer of the present invention is a raw material with the p diethylaminobenzoic acid ester sodium salt; Add phase-transfer catalyst; In organic solvent and aqueous systems, add ethylization reagent (is example with the ethyl sulfate), the triethyl phosphate of generation gets finished product through separating purification.This esterification process is a nucleophilic substitution; Organic phase is an ethyl sulfate; Solid phase is the p diethylaminobenzoic acid ester sodium salt; The p diethylaminobenzoic acid ester sodium salt is generating the diethyl phosphoric acid negative ion in mutually accordingly, and it is as a nucleophilic reagent then, is carried to get in the organic phase by phase-transfer catalyst and carries out nucleophilic substitution reaction with ethyl sulfate.
Reaction formula is following:
Phase-transfer catalyst is a quaternary ammonium salt, has following structure:
R in the formula
1, R
2, R
3, R
4Be respectively C
nH
2n+1The aliphatic alkyl or the aryl of (n=1～16).Wherein alkyl can be identical also can be different.The concrete quaternary ammonium salt of using is like benzyltriethylammoinium chloride, cetyl trimethylammonium bromide, Tetrabutyl amonium bromide etc.; The concrete organic solvent of using comprises toluene, YLENE, chlorobenzene, acetonitrile, MIBK etc.Wherein best phase-transfer catalyst is a Tetrabutyl amonium bromide, and best solvent is a toluene, and the reactive behavior of Tetrabutyl amonium bromide in toluene is the highest.
The present invention mixes p diethylaminobenzoic acid ester sodium salt, phase-transfer catalyst and toluene and water, slowly is warming up to reflux temperature, adds ethyl sulfate, isothermal reaction 6h.After reaction finishes, cooling, suction filtration is washed till neutrality with saturated sodium bicarbonate solution, washing, saturated sodium-chloride is washed, and tells organic layer, uses anhydrous magnesium sulfate drying, revolves the steaming solvent and promptly gets the triethyl phosphate bullion.
The ethyl sulfate water of the p diethylaminobenzoic acid ester sodium salt of said every 1mol (closing 176.0g) and 1mol (closing 154.18g) is: water is 0～200ml, and organic solvent is 400～800ml.Described phase-transfer catalyst is a quaternary ammonium salt, and the raw material p diethylaminobenzoic acid ester sodium salt of adding and the mol ratio of phase-transfer catalyst are 1: 0.01～0.15.
Embodiment 1:
Get p diethylaminobenzoic acid ester sodium salt 176.0g, Tetrabutyl amonium bromide 12.89g, mixed solvent toluene 400ml and water 30ml and join in the reactor drum that reflux exchanger, feed hopper, whipping appts and TM are housed, heated and stirred makes p diethylaminobenzoic acid ester sodium salt and Tetrabutyl amonium bromide dissolving, is warming up to backflow; Add ethyl sulfate 154.18g, keep back flow reaction 6h, cooling; Suction filtration gets yellow solution, is washed till neutrality with saturated sodium bicarbonate then; Wash once with saturated sodium-chloride with twice back of washing, anhydrous magnesium sulfate drying revolves the steaming solvent at last and obtains the triethyl phosphate bullion again; Yellow transparent liquid, yield 63.61%～91.30%, content 95%.Underpressure distillation can get pure triethyl phosphate, colourless transparent liquid, refractive index n=1.4055, content 99%.
Embodiment 2:
Get p diethylaminobenzoic acid ester sodium salt 176.0g, cetyl trimethylammonium bromide 14.58g, mixed solvent YLENE 500ml and water 80ml join in the reactor drum that reflux exchanger, feed hopper, whipping appts and TM are housed, and heated and stirred makes p diethylaminobenzoic acid ester sodium salt and catalyst dissolution; Be warming up to backflow, add ethyl sulfate 154.18g, keep back flow reaction 4h, cooling; Suction filtration gets yellow solution, is washed till neutrality with saturated sodium bicarbonate then; Wash once with saturated sodium-chloride with twice back of washing, anhydrous magnesium sulfate drying revolves the steaming solvent at last and obtains the triethyl phosphate bullion again; Yellow transparent liquid, yield be from 62.70%～91.65%, content 95%.Underpressure distillation can get pure triethyl phosphate, colourless transparent liquid, refractive index n=1.4055, content 99%.
Embodiment 3:
Get p diethylaminobenzoic acid ester sodium salt 176.0g, benzyltriethylammoinium chloride 9.09g, mixed solvent chlorobenzene 600ml and water 100ml join in the reactor drum that reflux exchanger, feed hopper, whipping appts and TM are housed, and heated and stirred makes p diethylaminobenzoic acid ester sodium salt and catalyst dissolution; Be warming up to backflow, add ethyl sulfate 77.09g, keep back flow reaction 7h, cooling; Suction filtration gets yellow solution, is washed till neutrality with saturated sodium bicarbonate then; Wash once with saturated sodium-chloride with twice back of washing, anhydrous magnesium sulfate drying revolves the steaming solvent at last and obtains the triethyl phosphate bullion again; Yellow transparent liquid, yield be from 53.69%～91.30%, content 95%.Underpressure distillation can get pure triethyl phosphate, colourless transparent liquid, refractive index n=1.4055, content 99%.
Embodiment 4:
Get p diethylaminobenzoic acid ester sodium salt 176.0g, Tetrabutyl amonium bromide 12.89g, mixed solvent MIBK 800ml and water 120ml join in the reactor drum that reflux exchanger, feed hopper, whipping appts and TM are housed, and heated and stirred makes p diethylaminobenzoic acid ester sodium salt and catalyst dissolution; Be warming up to backflow, add ethyl sulfate 154.18g, keep back flow reaction 5h, cooling; Suction filtration gets yellow solution, is washed till neutrality with saturated sodium bicarbonate then; Wash once with saturated sodium-chloride with twice back of washing, anhydrous magnesium sulfate drying revolves the steaming solvent at last and obtains the triethyl phosphate bullion again; Yellow transparent liquid, yield reaches as high as 95.98%, content 95%.Underpressure distillation can get pure triethyl phosphate, colourless transparent liquid, refractive index n=1.4055, content 99%.
Claims (2)
1. the method for a catalytically synthesizing triethyl phosphate by phase transfer is characterized in that, comprises following order and step: each raw material add-on is in mol
A, put into the by product p diethylaminobenzoic acid ester sodium salt in the white dyes production process and benzyltriethylammoinium chloride, cetyl trimethylammonium bromide or Tetrabutyl amonium bromide phase-transfer catalyst in the reactor drum that reflux exchanger, feed hopper, whipping appts and TM are housed by 1mol: 0.01～0.15mol; Add organic solvent 400ml～800ml, water 0～200ml by every mole of phosphoric acid diethyl ester sodium salt again;
B, heated and stirred make p diethylaminobenzoic acid ester sodium salt and catalyst dissolution, are warming up to backflow;
C, adding ethyl sulfate, the molar ratio of p diethylaminobenzoic acid ester sodium salt and ethyl sulfate is 1: 0.5～3;
70～100 ℃ of d, maintenance back flow reaction temperature, reaction times 4～10h, cooling, suction filtration gets yellow solution;
E, be washed till neutrality, wash once with saturated sodium-chloride with twice back of washing again, use anhydrous magnesium sulfate drying at last with saturated sodium bicarbonate;
F, revolve and steam solvent and obtain triethyl phosphate bullion, yellow transparent liquid;
G, get pure triethyl phosphate, colourless transparent liquid through underpressure distillation again.
2. according to the method for the said catalytically synthesizing triethyl phosphate by phase transfer of claim 1, it is characterized in that described organic solvent is selected from toluene, YLENE, chlorobenzene, acetonitrile or MIBK.
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| CN2010102296238A CN101891761B (en) | 2010-07-19 | 2010-07-19 | Method for catalytically synthesizing triethyl phosphate by phase transfer |
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| CN101891761B true CN101891761B (en) | 2012-07-04 |
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| CN109928993A (en) * | 2019-04-17 | 2019-06-25 | 沈阳新纪化学有限公司 | A kind of commercial recovery method that the fluorescent whitening agent kettle of phosphorous diethyl phthalate is residual |
| CN113292597B (en) * | 2021-06-25 | 2023-03-24 | 浙江宏达化学制品有限公司 | Method for preparing triethyl phosphate compound by recovering sodium diethylphosphate and ethyl chloride |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3976619A (en) * | 1972-12-26 | 1976-08-24 | Monsanto Company | Flame retardant polymers containing phosphates |
| US6673955B2 (en) * | 2001-11-27 | 2004-01-06 | Bayer Aktiengesellschaft | Preparation of triethyl phosphate |
| CN101941988A (en) * | 2010-03-04 | 2011-01-12 | 浙江医药股份有限公司维生素厂 | Process for preparing triethyl phosphate by utilizing sodium diethyl phosphate |
-
2010
- 2010-07-19 CN CN2010102296238A patent/CN101891761B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3976619A (en) * | 1972-12-26 | 1976-08-24 | Monsanto Company | Flame retardant polymers containing phosphates |
| US6673955B2 (en) * | 2001-11-27 | 2004-01-06 | Bayer Aktiengesellschaft | Preparation of triethyl phosphate |
| CN101941988A (en) * | 2010-03-04 | 2011-01-12 | 浙江医药股份有限公司维生素厂 | Process for preparing triethyl phosphate by utilizing sodium diethyl phosphate |
Non-Patent Citations (1)
| Title |
|---|
| Na Ge et al.Novelties of solid-liquid phase transfer catalyzed synthesis of benzyl diethyl phosphate from the sodium salt of diethyl phosphate.《European Journal of Chemistry》.2011,第2卷(第2期),第269-271页. * |
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