CN101891761A - Phase transfer catalyzed method for synthesizing triethyl phosphate - Google Patents
Phase transfer catalyzed method for synthesizing triethyl phosphate Download PDFInfo
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Abstract
本发明涉及一种相转移催化合成磷酸三乙酯的方法。是以磷酸二乙酯钠盐为原料，加入相转移催化剂，在有机溶剂和水体系中加入乙基化试剂，生成的磷酸三乙酯，经分离提纯得到成品。本发明与现有技术相比，所用的催化剂成本较低，采用有机溶剂和水作为混合溶剂，有机溶剂可以循环使用，对环境友好，降低了合成成本，不仅对磷酸二乙酯钠盐进行了再利用，将废弃物转化为具有实用价值的有机磷资源，减少了环境污染，而且为磷酸三乙酯的工业生产提供了新的途径。该方法不仅具有反应步骤少，操作简便，收率高，产品纯度高，易于工业化生产，而且减少了荧光增白剂生产过程中的副产物磷酸二乙酯钠盐的环境污染。The invention relates to a method for synthesizing triethyl phosphate by phase transfer catalysis. Diethyl phosphate sodium salt is used as raw material, phase transfer catalyst is added, and ethylating reagent is added to the organic solvent and water system to form triethyl phosphate, which is separated and purified to obtain the finished product. Compared with the prior art, the present invention has lower catalyst cost, adopts organic solvent and water as the mixed solvent, and the organic solvent can be recycled, which is environmentally friendly and reduces the synthesis cost. Reusing wastes into organic phosphorus resources with practical value reduces environmental pollution and provides a new way for the industrial production of triethyl phosphate. The method not only has the advantages of fewer reaction steps, simple operation, high yield, high product purity and easy industrial production, but also reduces the environmental pollution of the by-product diethyl phosphate sodium salt in the production process of the fluorescent whitening agent.
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, relative 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 is very extensive.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, defoamer, the dyeing auxiliary of acetate fiber, the production of luminescent lamp glass paint etc.The present synthetic two lines that mainly contain of the preparation triethyl phosphate of report both at home and abroad.Article one, being the U.S.6673955 report, is phosphorus esterification reagent with the phosphorus oxychloride, obtains compound with ethanol synthesis again, and this synthetic 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 by 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, obtains triethyl phosphate with hydrogen peroxide oxidation under alkaline condition.The deficiency of this synthetic 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
Purpose of the present invention just is to provide a kind of method of catalytically synthesizing triethyl phosphate by phase transfer at above-mentioned the deficiencies in the prior art.
The objective of the invention is to be achieved through the following technical solutions:
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 that reflux exchanger, feed hopper, whipping appts and thermometer 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 twice back again with water and wash once, use anhydrous magnesium sulfate drying at last with saturated sodium-chloride with saturated sodium bicarbonate;
F, revolve and steam solvent and obtain triethyl phosphate crude product, yellow transparent liquid;
G, get pure triethyl phosphate, colourless transparent liquid through underpressure distillation again.
The objective of the invention is to be achieved through the following technical solutions:
Organic solvent comprises toluene, dimethylbenzene, chlorobenzene, acetonitrile or methyl iso-butyl ketone (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, adopt 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 provide new approach for the industrial production of triethyl phosphate.It is few that this method not only has reactions steps, easy and simple to handle, the yield height, and the product purity height 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
Be described in further detail 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, add ethylization reagent (is example with the ethyl sulfate) in organic solvent and aqueous systems, 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, it is as a nucleophilic reagent then, is carried to enter in the organic phase by phase-transfer catalyst and carries out nucleophilic substitution reaction with ethyl sulfate.
Reaction formula is as follows:
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 as benzyltriethylammoinium chloride, cetyl trimethylammonium bromide, Tetrabutyl amonium bromide etc.; The concrete organic solvent of using comprises toluene, dimethylbenzene, chlorobenzene, acetonitrile, methyl iso-butyl ketone (MIBK) etc.Wherein Zui Jia 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 crude product.
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 join reflux exchanger are housed, feed hopper, in the reactor of whipping appts and thermometer, heated and stirred makes p diethylaminobenzoic acid ester sodium salt and Tetrabutyl amonium bromide dissolving, be 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, washing twice back again with water washes once with saturated sodium-chloride, anhydrous magnesium sulfate drying revolves the steaming solvent at last and obtains triethyl phosphate crude product, 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 dimethylbenzene 500ml and water 80ml, join reflux exchanger is housed, feed hopper, in the reactor of whipping appts and thermometer, 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, washing twice back again with water washes once with saturated sodium-chloride, anhydrous magnesium sulfate drying revolves the steaming solvent at last and obtains triethyl phosphate crude product, yellow transparent liquid, yield is 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 reflux exchanger is housed, feed hopper, in the reactor of whipping appts and thermometer, 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, washing twice back again with water washes once with saturated sodium-chloride, anhydrous magnesium sulfate drying revolves the steaming solvent at last and obtains triethyl phosphate crude product, yellow transparent liquid, yield is 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 methyl iso-butyl ketone (MIBK) 800ml and water 120ml, join reflux exchanger is housed, feed hopper, in the reactor of whipping appts and thermometer, 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, washing twice back again with water washes once with saturated sodium-chloride, anhydrous magnesium sulfate drying revolves the steaming solvent at last and obtains triethyl phosphate crude product, 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 (3)
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, 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 that reflux exchanger, feed hopper, whipping appts and thermometer 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 twice back again with water and wash once, use anhydrous magnesium sulfate drying at last with saturated sodium-chloride with saturated sodium bicarbonate;
F, revolve and steam solvent and obtain triethyl phosphate crude product, 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 comprises toluene, dimethylbenzene, chlorobenzene, acetonitrile or methyl iso-butyl ketone (MIBK).
3. according to the method for the said catalytically synthesizing triethyl phosphate by phase transfer of claim 1, it is characterized in that described phase-transfer catalyst is benzyltriethylammoinium chloride, cetyl trimethylammonium bromide or Tetrabutyl amonium bromide.
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| CN101891761B CN101891761B (en) | 2012-07-04 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN113292597A (en) * | 2021-06-25 | 2021-08-24 | 浙江宏达化学制品有限公司 | Preparation method of phosphate compound |
| CN116143830A (en) * | 2023-02-22 | 2023-05-23 | 李效军 | A kind of method of synthesizing trialkyl phosphate by dialkyl phosphate |
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 |
|---|
| 《European Journal of Chemistry》 20110630 Na Ge et al Novelties of solid-liquid phase transfer catalyzed synthesis of benzyl diethyl phosphate from the sodium salt of diethyl phosphate 第269-271页 1-3 第2卷, 第2期 2 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN113292597A (en) * | 2021-06-25 | 2021-08-24 | 浙江宏达化学制品有限公司 | Preparation method of phosphate compound |
| CN116143830A (en) * | 2023-02-22 | 2023-05-23 | 李效军 | A kind of method of synthesizing trialkyl phosphate by dialkyl phosphate |
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| CN101891761B (en) | 2012-07-04 |
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