CN105837473A - Preparing process of tetrabutyl urea - Google Patents
Preparing process of tetrabutyl urea Download PDFInfo
- Publication number
- CN105837473A CN105837473A CN201610276960.XA CN201610276960A CN105837473A CN 105837473 A CN105837473 A CN 105837473A CN 201610276960 A CN201610276960 A CN 201610276960A CN 105837473 A CN105837473 A CN 105837473A
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- Prior art keywords
- trichloromethyl
- preparation technology
- tetrabutyl urea
- double
- butylamine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C273/02—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of urea, its salts, complexes or addition compounds
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- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparing method of tetrabutyl urea .Di-n-butylamine, bis(trichloromethyl)carbonate, liquid caustic soda and pure water serve as raw materials of the preparing process .The preparing process includes the steps that bis(trichloromethyl)carbonate is pulverized and mixed with pure water, the mixture of bis(trichloromethyl)carbonate and pure water is added into a certain amount of liquid caustic soda, the liquid-solid mixture is added into di-n-butylamine under sufficient stirring, a crude tetrabutyl urea product is obtained through stirring heating and reflux, and the crude product is rectified to obtain a final product .Organic solvent is avoided, and solvent recovering cost and purification difficulty are reduced; phosgene is not used as a raw material, and the synthesis process is safe and free of risks; as liquid caustic soda is adopted, chlorine hydride gas is avoided .
Description
Technical field
The present invention relates to the preparation technology of a kind of tetrabutyl urea, especially a kind of employing di-n-butylamine, double (trichloromethyls)
The tetrabutyl urea technique of carbonic ester, liquid caustic soda and pure water preparation.
Technical background
Tetrabutyl urea (is called for short TBU), and for transparent or the most yellowish liquid, viscosity is slightly big than water, and molecular formula is
C17H36N20；It is the organic synthesis intermediate that purposes is wider, it is possible to as vitochemical solvent, extractant and catalyst, especially
It it is the solvent being used as hydrogen peroxide production process in a large number.The hydrogen anthraquinone solvent being mainly used in hydrogen dioxide solution production by anthraquinone process new technology.
Relative to conventional solvent trioctyl phosphate, the dissolubility with hydrogen anthraquinone is big；H2O2Partition coefficient in biphase is big；The tetrabutyl
The advantages such as urea is big with water density difference, surface tension is big.
The synthetic method of tetrabutyl urea has phosgenation and non-phosgene；Wherein non-phosgene is due to condition harshness, can implement
Property little, it is impossible to as a kind of industrial preparative method.Phosgenation is divided into phosgenation, Diphosgene, triphosgene.Phosgenation is phosphinylidyne
Chlorine method, Diphosgene is trichloromethyl chloroformate method, and triphosgene is double (trichloromethyl) carbonic acid ester process.
Phosgene has another name called phosgene, high poison, and chemical reactivity is higher, has aggressive after meeting water.Such as Publication No.
CN102702029A discloses the patent of invention of one " preparation technology of tetrabutyl urea ", and this technique uses phosgene as former
Material, uses fully closed reaction unit, and equipment requirements is high, is not allow for least bit leakage.And involved by this technique
Reaction be gas liquid reaction, the contact area of gas-liquid is little, causes the response time long, and this patent short reaction time is 5 hours.By
There is unreacted phosgene in reactor top, after reaction, need the toxic gas displacing in reactor.This invention is mentioned instead
Need after should static 30 minutes, but undeclared reason.The technique that this patent is used, not only dangerous big, high to equipment requirements, instead
Answer speed the slowest.
Surpalite is the another name of trichloromethyl chloroformate, colourless liquid, and irritant abnormal smells from the patient is insoluble in water, can make other
The solvent of toxic agent.Surpalite is a kind of ASPHYX, i.e. causes damage the lung tissue of human body, causes blood plasma to penetrate into alveolar and draws
Play pulmonary edema, so that alveolar gas exchange is obstructed, body anoxia and death by suffocation.Surpalite in World War I once by as biochemistry
Weapon.So the case using surpalite to prepare tetrabutyl urea there is no.
Triphosgene, also known as solid phosgene, is the another name of double (trichloromethyl) carbonic ester.The micro-poison of triphosgene, stability is relatively strong,
Only have a small amount of decomposition when boiling point, generate trichloromethyl chloroformate and phosgene.Use triphosgene as tetrabutyl urea raw materials for production
Case a lot, but all have employed organic solvent and dissolve.As Publication No. CN1394852A discloses one " four fourths
The preparation method of base urea " patent of invention, the method use organic solvent as the carrier of double (trichloromethyl) carbonic ester, the most molten
Solution drips again, and recycling design during reaction, and the process of recycling design adds energy consumption and the time of reaction.And
And this invention uses nitrogen displacement method to displace the hydrogen chloride gas that reaction generates, create substantial amounts of hydrogen chloride emission.Use
Solvent dissolves double (trichloromethyl) carbonic ester, can not be kept completely separate when separating, can carry out the impact in band purity.
East China University of Science Industrial Catalysis institute Cui Li duty, Liu Chunshan et al. send out in " fine-chemical intermediate " magazine
The article of table one summary property, entitled " synthetic method of tetrabutyl urea ", it is mentioned that single phosgenation, Diphosgene, three
Phosgenation.Wherein single phosgenation has reaction very acutely, and more difficult control during a large amount of preparation is also deposited on lock out operation simultaneously
In shortcomings such as certain difficulties.Diphosgene has highly volatile, has asphyxiating, the shortcomings such as toxicity is stronger.Though triphosgene
Do not mention shortcoming, but have in existing technique, be required for solvent and dissolve triphosgene.
Summary of the invention
For solving when phosgenation prepares tetrabutyl urea the high request to equipment, the response time is the slowest, needs standing etc. after reaction
Problem, course of reaction need to cool down and avoid the potential threat that personnel and surrounding enviroment are brought by severe toxicity raw material；For solving triphosgene
Energy consumption that when method prepares tetrabutyl urea, solvent recovery is brought, time increase, and solvent is on problems such as the impacts of purity；The present invention carries
Preparation technology for a kind of tetrabutyl urea.
For achieving the above object, the technical scheme that the present invention takes is: the preparation technology of a kind of tetrabutyl urea, raw material bag
Include: di-n-butylamine, double (trichloromethyl) carbonic ester, liquid caustic soda, pure water.Its processing step is as follows:
(1) double (trichloromethyl) carbonic esters of general pulverize and mix with pure water, add in a certain amount of liquid caustic soda；
(2) mixed solidliquid mixture is dripped under well-beaten state in entrance di-n-butylamine；
(3), after dripping, stirring heats up and refluxes and can obtain tetrabutyl urea crude product；
(4) crude product can obtain final products through rectification.
Double (trichloromethyl) carbonic esters and di-n-butylamine in described technique, sodium hydroxide mol ratio is 1: 6.3 ~ 8: 7 ~ 10；
Step (1) described alkali liquor, its concentration is 15%-31%；
Step (3) described temperature rising reflux step, its temperature can be 60-108 DEG C, and the response time is 30min-12 hour, reaction pressure
Power is room temperature.
Vacuum 0.1MPa-0.096MPa during step (4) described rectification, temperature is 200 DEG C-330 DEG C；
Compared with prior art, the present invention has the advantages that.
1, the present invention does not use phosgene as raw material, so the highest to equipment requirements, need not from raw material to production
The most airtight, can atmospheric operation.And stable under double (trichloromethyl) carbonic ester room temperature, toxicity is less, reduce wanting of equipment
Ask, reduce the harm to operator and surrounding enviroment.
2, di-n-butylamine of the present invention directly contacts with double (trichloromethyl) carbonic esters, accelerates response speed, adds anti-
Answer efficiency, reduce the response time.
3, the present invention does not use organic solvent to dissolve double (trichloromethyl) carbonic ester, it is not necessary to solvent recovery,
Separate also without to solvent during rectification, reduce energy consumption, add product purity.
4, the present invention uses liquid caustic soda to be neutralized the hydrogen chloride produced in course of reaction, will not produce hydrogen chloride emission,
Decrease the pollution to air.
Detailed description of the invention
Embodiment 1
(1) take double (trichloromethyl) carbonic ester of 100g, ground and mix with 213g pure water, grinding particle diameter unrestricted.
(2) mixture of double (trichloromethyl) carbonic esters with water is completely added in the liquid caustic soda of 340g industry 31%, and fills
Divide mixing.
(3) mixed liquor is sufficiently stirred for so that double (trichloromethyl) evengranular distribution of carbonic ester is in the liquid phase.
(4) solidliquid mixture after above-mentioned being uniformly distributed is dripped in entrance 265g di-n-butylamine, control dropping temperature and exist
Less than 70 DEG C.
(5) after dropping, being warming up to 108 DEG C, backflow now occur, temperature no longer raises.Keep with this understanding stirring
Mix reaction 30 minutes, prepare tetrabutyl urea crude product.
(6) tetrabutyl urea crude product is at normal pressure 0.1MPa, still temperature 320 DEG C, and the part taking meteorological temperature more than 315 DEG C cools down
After, retortable obtain tetrabutyl urea finished product；Preparing tetrabutyl urea product purity after testing is 99.78%.
Embodiment 2
(1) take double (trichloromethyl) carbonic ester of 100g, ground and mix with 100g pure water, grinding particle diameter unrestricted.
(2) mixture of double (trichloromethyl) carbonic esters with water is completely added in the liquid caustic soda of 350g industry 31%, and fills
Divide mixing.
(3) mixed liquor is sufficiently stirred for so that double (trichloromethyl) evengranular distribution of carbonic ester is in the liquid phase.
(4) solidliquid mixture after above-mentioned being uniformly distributed is dripped in entrance 270g di-n-butylamine, control dropping temperature and exist
Less than 70 DEG C.
(5) after dropping, it is warming up to 90 DEG C, does not now have backflow, keep temperature constant.Keep with this understanding
Stirring reaction 2 hours, prepares tetrabutyl urea crude product.
(6) tetrabutyl urea crude product is at vacuum-0.096MPa, still temperature 210 DEG C, takes the portion of meteorological temperature more than 200 DEG C
After point cooling, retortable obtain tetrabutyl urea finished product；Preparing tetrabutyl urea product purity after testing is 99.82%.
Embodiment 3
(1) take double (trichloromethyl) carbonic ester of 100g, ground and mix with 50g pure water, grinding particle diameter unrestricted.
(2) mixture of double (trichloromethyl) carbonic esters with water is completely added in the liquid caustic soda of 400g industry 31%, and fills
Divide mixing.
(3) mixed liquor is sufficiently stirred for so that double (trichloromethyl) evengranular distribution of carbonic ester is in the liquid phase.
(4) solidliquid mixture after above-mentioned being uniformly distributed is dripped in entrance 280g di-n-butylamine, control dropping temperature and exist
Less than 70 DEG C.
(5) after dropping, it is warming up to 60 DEG C, does not now have backflow, keep temperature constant.Keep with this understanding
Stirring reaction 12 hours, prepares tetrabutyl urea crude product.
(6) tetrabutyl urea crude product is at vacuum-0.092MPa, still temperature 220 DEG C, takes the portion of meteorological temperature more than 210 DEG C
After point cooling, retortable obtain tetrabutyl urea finished product；Preparing tetrabutyl urea product purity after testing is 99.70%.
The analysis method of tetrabutyl urea prepared by above-described embodiment:
Use chromatographic, the neutral capillary column of employing, capillary column specification 0.25 μm, 30 meters.Analytical tool condition
Temperature of vaporization chamber: 220 DEG C, detector temperature: 250 DEG C, post case temperature: 195 DEG C, decay: 1, sensitivity: 4.
Tetrabutyl urea sample: without preparing sample, direct injected.Take 0.2 microlitre (1 little lattice) sample size.
Claims (7)
1. a preparation technology for tetrabutyl urea, the raw material of described preparation technology be di-n-butylamine, double (trichloromethyl) carbonic ester,
Liquid caustic soda and pure water；The step of described preparation technology is to pulverize double (trichloromethyl) carbonic ester to mix with pure water, adds certain
In the liquid caustic soda of amount, entering in di-n-butylamine by liquid-solid mixture dropping under well-beaten state, stirring heats up and refluxes and obtains
Obtaining tetrabutyl urea crude product, crude product prepares final products through rectification.
The preparation technology of a kind of tetrabutyl urea the most as claimed in claim 1, described double (trichloromethyl) carbonic esters, di-n-butylamine and
The mol ratio of sodium hydroxide is 1: 6 ~ 8: 7 ~ 10.
The preparation technology of a kind of tetrabutyl urea the most as claimed in claim 1, the concentration of described liquid caustic soda is 15%-31%.
The preparation technology of a kind of tetrabutyl urea the most as claimed in claim 1, the reaction temperature of described preparation technology is 60-108 DEG C,
Response time is 0.5-12 hour, and reaction pressure is normal pressure.
The preparation technology of a kind of tetrabutyl urea the most as claimed in claim 1, the vacuum of described rectification be 0.1MPa-
0.096MPa, temperature is 200 DEG C-320 DEG C.
The preparation technology of a kind of tetrabutyl urea the most as claimed in claim 1, the particle diameter that described double (trichloromethyl) carbonic esters pulverize
It is less than the caliber of dropping equipment outlet.
The preparation technology of a kind of tetrabutyl urea the most as claimed in claim 1, described alkali liquor and double (trichloromethyl) carbonic esters be
During under well-beaten state, dropping enters di-n-butylamine.
Priority Applications (1)
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| CN201610276960.XA CN105837473A (en) | 2016-04-29 | 2016-04-29 | Preparing process of tetrabutyl urea |
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| CN201610276960.XA CN105837473A (en) | 2016-04-29 | 2016-04-29 | Preparing process of tetrabutyl urea |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106380426A (en) * | 2016-08-18 | 2017-02-08 | 黎明化工研究设计院有限责任公司 | Method for preparation of 1, 1, 3, 3-tetrabutylurea by aqueous phase process |
| CN106478461A (en) * | 2016-08-18 | 2017-03-08 | 黎明化工研究设计院有限责任公司 | A kind of method that Ethanol Method prepares tetrabutyl urea |
| CN106831493A (en) * | 2017-02-08 | 2017-06-13 | 湖南国发精细化工科技有限公司 | The synthetic method of tetrabutyl urea |
| CN108329238A (en) * | 2018-02-05 | 2018-07-27 | 黎明化工研究设计院有限责任公司 | A kind of method that Aqueous phase prepares tetrabutyl urea |
| CN108727226A (en) * | 2018-06-01 | 2018-11-02 | 黎明化工研究设计院有限责任公司 | The minimizing technology of dibutyl amine in a kind of tetrabutyl urea |
Citations (5)
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| CN1394852A (en) * | 2002-06-06 | 2003-02-05 | 中外合资湖州吉昌化学有限公司 | Preparation method of tetrabutyl urea |
| WO2004007436A1 (en) * | 2002-07-10 | 2004-01-22 | Basf Aktiengesellschaft | Method for the continuous production of tetra-substituted ureas |
| CN101333176A (en) * | 2008-05-30 | 2008-12-31 | 浙江工业大学 | Method for preparing substituent urea and co-producing hydrochloride of corresponding amines |
| CN102702029A (en) * | 2012-04-10 | 2012-10-03 | 重庆长风化学工业有限公司 | Preparation process for tetrabutyl urea |
| CN103193680A (en) * | 2013-04-03 | 2013-07-10 | 北京石油化工学院 | Preparation method of tetrabutyl urea |
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| CN1394852A (en) * | 2002-06-06 | 2003-02-05 | 中外合资湖州吉昌化学有限公司 | Preparation method of tetrabutyl urea |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106380426A (en) * | 2016-08-18 | 2017-02-08 | 黎明化工研究设计院有限责任公司 | Method for preparation of 1, 1, 3, 3-tetrabutylurea by aqueous phase process |
| CN106478461A (en) * | 2016-08-18 | 2017-03-08 | 黎明化工研究设计院有限责任公司 | A kind of method that Ethanol Method prepares tetrabutyl urea |
| CN106478461B (en) * | 2016-08-18 | 2018-03-09 | 黎明化工研究设计院有限责任公司 | A kind of method that Ethanol Method prepares tetrabutyl urea |
| CN106380426B (en) * | 2016-08-18 | 2018-03-09 | 黎明化工研究设计院有限责任公司 | A kind of method that Aqueous phase prepares tetrabutyl urea |
| CN106831493A (en) * | 2017-02-08 | 2017-06-13 | 湖南国发精细化工科技有限公司 | The synthetic method of tetrabutyl urea |
| CN108329238A (en) * | 2018-02-05 | 2018-07-27 | 黎明化工研究设计院有限责任公司 | A kind of method that Aqueous phase prepares tetrabutyl urea |
| CN108329238B (en) * | 2018-02-05 | 2020-10-16 | 黎明化工研究设计院有限责任公司 | Method for preparing tetrabutyl urea by aqueous phase method |
| CN108727226A (en) * | 2018-06-01 | 2018-11-02 | 黎明化工研究设计院有限责任公司 | The minimizing technology of dibutyl amine in a kind of tetrabutyl urea |
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Application publication date: 20160810 |