CN85104673A - The production process of tributyl phosphate - Google Patents
The production process of tributyl phosphate Download PDFInfo
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- CN85104673A CN85104673A CN 85104673 CN85104673A CN85104673A CN 85104673 A CN85104673 A CN 85104673A CN 85104673 CN85104673 CN 85104673 CN 85104673 A CN85104673 A CN 85104673A CN 85104673 A CN85104673 A CN 85104673A
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- CN
- China
- Prior art keywords
- butanols
- tributyl phosphate
- phosphorus oxychloride
- reaction
- aqueous sodium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Abstract
Adopt high butanols/phosphorus oxychloride than the preparation tributyl phosphate, its yield can reach 90%.Aftertreatment adopts yellow soda ash or sodium hydroxide to neutralize, and solution loss butanols when having avoided washing with big water gaging has also been avoided to the corrosion of equipment with to the pollution of environment.
Description
The invention belongs to the production method of organic synthesis product tributyl phosphate.
In the past by butanols and phosphorus oxychloride direct reaction prepare tributyl phosphate method (U.S.P.2,426,691(1947); 3,053,875(1960); 3,801,683(1974)) wherein, the mol ratio of butanols and phosphorus oxychloride is lower, so esterification is difficult for carrying out fully, have more monoesters and diester to exist, so productive rate is generally below 80%.In order to remove the by product (hydrogenchloride) in the reaction process, mostly adopt the decompression degassing, steam or the method for massive laundering with excessive butanols.Its shortcoming is, because hydrogenchloride tends to be dissolved in and forms constant boiling mixture in the butanols, and therefore can not be by thoroughly removing in the reaction mixture.And in the presence of hydrogenchloride, distill, have and following pay reaction and cause the reduction of tributyl phosphate productive rate.
And the method for massive laundering, the dissolving butanols is too much, causes raw material consumption excessive, and can not thoroughly remove hydrogen chloride gas.In last handling process,, also be well-known to the corrosion of equipment with to the pollution of environment in the distillation that has in the presence of the hydrogenchloride.
The objective of the invention is with butanols and phosphorus oxychloride is raw material, and a yield height is provided, harmless to equipment, but the method for environmentally safe ， And suitability for industrialized production tributyl phosphate.
It is 7～12/1 that the present invention has adopted the mol ratio of butanols and phosphorus oxychloride, temperature of reaction is at 20～60 ℃, reaction pressure is in 300～700mmHg(gauge pressure), reaction times is 3～5 hours, in and the time can add less water with solid sodium carbonate, 40%～60% aqueous sodium carbonate or carry out with 20～40% aqueous sodium hydroxide solutions, neutral temperature is at 20～70 ℃.
The present inventor finds to adopt high butanols/phosphorus oxychloride than preparing tributyl phosphate and using solid sodium carbonate, aqueous sodium carbonate or aqueous sodium hydroxide solution carry out in the by product hydrogenchloride and the time productive rate of tributyl phosphate is brought up to about 90%, And and having solved to problems such as equipment corrosion and contaminate environment.
Example 1:
With 1295g(17.5mol) butanols place three mouthfuls of three liters to burn and, remain on 25～60 ℃, the 600mmHg(gauge pressure) pressure, stir and drip 384g(2.5mol down) phosphorus oxychloride, drip the back 25～60 ℃ of insulations 3 hours, add 500ml water and 440g sodium phosphate then, neutral temperature remains on 25～60 ℃, the elimination solid salt is told organic phase, in 70～80mmHg(gauge pressure) steam excessive butanols under the pressure, thick ester is washed with equal-volume, under 3～4mmHg pressure, 138～40 ℃ steam product 580g, yield 91.8%.
Example 2:
With 1295g(17.5mol) butanols places three mouthfuls of three liters to burn and remains on 30～60 ℃, the 600mmHg(gauge pressure) pressure, stir and drip 384g(2.5mol down) phosphorus oxychloride, after the dropping, 25～60 ℃ of insulations 3 hours, be neutralized to PH7～8 with 40% aqueous sodium carbonate then, tell organic phase, decompression steams excessive butanols, and thick ester is washed with equal-volume, under 5～8mmHg pressure, steam product 574g, yield 90.7% then.
Example 3:
React by example 1 with reclaiming butanols, get tributyl phosphate 570g, yield 90.2%.
Example 4:
React by example 1, neutral temperature remains on 55 ℃, gets tributyl phosphate 567g, yield 90.0%.
Example 5:
React by example 1, neutralize, get tributyl phosphate 565g, yield 89.6% with 24% aqueous sodium hydroxide solution.
Example 6:
In the 300 liter enamel reaction stills, put into the 60.00Kg butanols, in the 700mmHg(gauge pressure) pressure, 25～60 ℃, stir down, drip the 19.25Kg phosphorus oxychloride, drip back insulation 4 hours, add 25Kg water and 22Kg yellow soda ash, neutral temperature remains on 25～60 ℃, solids removed by filtration salt, tell organic phase, decompression steams excessive butanols, and thick ester is washed with equal-volume, decompression steams tributyl phosphate 28.0Kg, yield 88.5%.
Claims (3)
1, a kind ofly prepare the method for tributyl phosphate by butanols and phosphorus oxychloride reaction, the mol ratio that the invention is characterized in butanols and phosphorus oxychloride is 7～12: 1 ， And and under mild conditions, neutralizes the hydrogenchloride that produces in the reaction with alkali.
2, according to claim 1, the alkali of its neutralization usefulness can be solid sodium carbonate, 40～60% aqueous sodium carbonates or 20～40% aqueous sodium hydroxide solutions.
3, according to claim 1, wherein temperature of reaction is 20～60 ℃, and neutral temperature is 20～70 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85104673A CN85104673B (en) | 1985-06-14 | 1985-06-14 | Process for production of tributyl phosphate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85104673A CN85104673B (en) | 1985-06-14 | 1985-06-14 | Process for production of tributyl phosphate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85104673A true CN85104673A (en) | 1987-01-21 |
| CN85104673B CN85104673B (en) | 1987-07-22 |
Family
ID=4793988
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN85104673A Expired CN85104673B (en) | 1985-06-14 | 1985-06-14 | Process for production of tributyl phosphate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN85104673B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100343261C (en) * | 2003-11-14 | 2007-10-17 | 无锡市红星化工厂 | High purity tributyl phosphate production method |
| CN101993454A (en) * | 2010-11-01 | 2011-03-30 | 江西科技师范学院 | Method for synthesizing tributyl phosphate by sodium formate acid-binding method |
| CN102040622A (en) * | 2011-01-25 | 2011-05-04 | 洛阳市中达化工有限公司 | Method for synthesizing tributyl phosphate |
| CN102351896A (en) * | 2011-08-25 | 2012-02-15 | 周滢 | Method for producing dibutyl phosphate by comprehensively using three wastes in production process |
| CN104211727A (en) * | 2014-08-01 | 2014-12-17 | 洛阳市三诺化工有限公司 | Preparation method of tributyl phosphate |
| CN107793446A (en) * | 2016-08-31 | 2018-03-13 | 天津市科密欧化学试剂有限公司 | A kind of purification process of SILVER REAGENT tributyl phosphate |
| CN110452263A (en) * | 2019-08-23 | 2019-11-15 | 三门峡中达化工有限公司 | A kind of method that pyridine catalyzes and synthesizes TRI N BUTYL PHOSPHATE |
-
1985
- 1985-06-14 CN CN85104673A patent/CN85104673B/en not_active Expired
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100343261C (en) * | 2003-11-14 | 2007-10-17 | 无锡市红星化工厂 | High purity tributyl phosphate production method |
| CN101993454A (en) * | 2010-11-01 | 2011-03-30 | 江西科技师范学院 | Method for synthesizing tributyl phosphate by sodium formate acid-binding method |
| CN101993454B (en) * | 2010-11-01 | 2011-11-16 | 江西科技师范学院 | Method for synthesizing tributyl phosphate by sodium formate acid-binding method |
| CN102040622A (en) * | 2011-01-25 | 2011-05-04 | 洛阳市中达化工有限公司 | Method for synthesizing tributyl phosphate |
| CN102040622B (en) * | 2011-01-25 | 2012-08-22 | 洛阳市中达化工有限公司 | Method for synthesizing tributyl phosphate |
| CN102351896A (en) * | 2011-08-25 | 2012-02-15 | 周滢 | Method for producing dibutyl phosphate by comprehensively using three wastes in production process |
| CN102351896B (en) * | 2011-08-25 | 2013-09-04 | 周滢 | Method for producing dibutyl phosphate by comprehensively using three wastes in production process |
| CN104211727A (en) * | 2014-08-01 | 2014-12-17 | 洛阳市三诺化工有限公司 | Preparation method of tributyl phosphate |
| CN107793446A (en) * | 2016-08-31 | 2018-03-13 | 天津市科密欧化学试剂有限公司 | A kind of purification process of SILVER REAGENT tributyl phosphate |
| CN110452263A (en) * | 2019-08-23 | 2019-11-15 | 三门峡中达化工有限公司 | A kind of method that pyridine catalyzes and synthesizes TRI N BUTYL PHOSPHATE |
Also Published As
| Publication number | Publication date |
|---|---|
| CN85104673B (en) | 1987-07-22 |
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