CN106518687A - Efficient preparation method of high-purity tetraethyl ammonium chloride - Google Patents
Efficient preparation method of high-purity tetraethyl ammonium chloride Download PDFInfo
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- CN106518687A CN106518687A CN201610813034.1A CN201610813034A CN106518687A CN 106518687 A CN106518687 A CN 106518687A CN 201610813034 A CN201610813034 A CN 201610813034A CN 106518687 A CN106518687 A CN 106518687A
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- purity
- etamon chloride
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
- C07C209/12—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of quaternary ammonium compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/86—Separation
Abstract
The invention discloses an efficient preparation method of high-purity tetraethyl ammonium chloride. Under the action of a polar solvent, triethylamine and chloroethane react while reaction temperature, pressure and time are controlled so as to prepare tetraethyl ammonium chloride; and the prepared tetraethyl ammonium chloride undergoes further cooling and separation so as to obtain the high-purity tetraethyl ammonium chloride product. The method has simple process, and purity of the product can reach 99% and above. In comparison with an existing method for production of tetraethyl ammonium chloride, the method of the invention has the following advantages: by increasing initial pressure of the reaction, reaction time is greatly shortened, and product purity is enhanced and production cost is reduced. Due to zero emission, low energy consumption and high productivity, the method is especially suitable for industrial production of tetraethyl ammonium chloride.
Description
Technical field
The present invention relates to quaterisation, belongs to organic compound synthetic technology, and in particular in certain polar solvent,
High-purity etamon chloride is prepared under certain temperature and pressure, by a certain proportion of triethylamine and chloroethanes reaction.
Background technology
Etamon chloride is mainly used as the template that agent, molecular sieve catalyst are facilitated in phase transfer, and is synthesis tetrem
The important intermediate of base ammonium hydroxide.
At present, the method for synthesizing etamon chloride mainly has following four：
A kind of method for preparing etamon chloride is described in CN1347872A patents.The method is by adding triethylamine, chlorine
Ethane, etamon chloride and acetone or acetonitrile solvent react prepared tetraethyl chlorination in 48 hours in autoclave, at 100 DEG C
Ammonium product.In the method, chloroethanes and triethylamine mole ratio are 2, substantial amounts of chloroethanes excess, and the time used is longer, Jing
Ji benefit is low, is not suitable for industrialized production.
A kind of method of synthesis etamon chloride is described in CN103377833A patents.The method is by adding three second
, in flask, heating stirring flows back, isothermal reaction 20-24 hours for amine, chloroethanes and benzene solvent.By the mixture of gained after reaction
Air-distillation, reclaims the chloroethanes of benzene and excess, is heated to 100 °C, the benzene and chloroethanes of remaining is removed under reduced pressure, tetraethyl is obtained
Ammonium chloride.It is long that the method equally exists the time used, the low shortcoming of business efficiency.The solvent benzol for being adopted in addition is good for people
Health hazard ratio is larger.
By adding triethylamine, chloroethanes, tetraethylammonium bromide and methanol solvate in high pressure in JP2004043382 patents
In kettle, react 8 hours at 100 DEG C, be 90% by the yield of liquid-phase chromatographic analysis product etamon chloride.Due to starting
Tetraethylammonium bromide is added, is caused the separation of subsequent product extremely difficult, and product etamon chloride is in the dissolving of methyl alcohol
Degree is big, increased the detached cost of subsequent product, is also not suitable for industrialized production.
Mention in US6444846B1 and adopt acetonitrile as solvents, with chloroethanes and triethylamine as raw material, 6 are reacted at 140 DEG C
Hour, etamon chloride product is obtained.But due to chloroethanes excessive 37% in the method, subsequently to excessive chloroethanes
Reclaiming needs substantial amounts of additional energy, does not meet the theory of current green chemical industry.
The content of the invention
The purpose of invention be for the yield existing for existing etamon chloride synthetic method it is low, purity is low, production
The shortcoming of cycle length, high cost, there is provided it is a kind of in high yield, high-purity, efficiently, the new side of etamon chloride synthesis of low cost
Method.
The new synthetic method of etamon chloride in the present invention, without the need for catalyst in whole production process, raw material chloroethanes
Without the need for substantial amounts of excess, react the mother liquor that Jing is filtered to isolate after terminating and do not need extra process make directly as solvent repetition
With by pressurizeing, the production time greatly shortens.The zero-emission during whole etamon chloride synthetic crystallization, is a kind of green
Environmentally friendly, with low cost high-purity etamon chloride practicality production method, has good prospects for commercial application.
For achieving the above object, the technical solution used in the present invention is as follows：
The new synthetic method of high-purity etamon chloride of the present invention, is carried out according to the following steps：（1）The triethylamine for taking proportional quantity is put
The solvent acetonitrile of respective amount in reactor, is added, chloroethanes gas is added under the conditions of low-temperature negative-pressure, is passed through nitrogen and is pressurized to
Certain pressure, reaction a period of time；（2）Material after reaction is terminated is placed in room temperature natural cooling crystallization, treats that temperature of charge drops
Mother liquor and product is separated to room temperature, and through vacuum drying, final products are highly purified etamon chloride to product；（3）Return
Mother liquor after receipts does not carry out extra process, in lower batch etamon chloride synthetic reaction is directly used as solvent, according to this, mother liquor
Recycled.
Pressurizeed using nitrogen in described synthetic method, partly in order to increase pressure is carried out beneficial to reaction, shorten anti-
Between seasonable；On the other hand it is, for the adverse effect for excluding oxygen to synthetic reaction etamon chloride product purity, to serve as one
Shielding gas is planted, the purity of product is improved.
The synthetic method of high-purity etamon chloride of the present invention has compared with the synthetic method of existing etamon chloride
Have the advantage that：
1）The present invention is shortened by the reaction time, so greatly improve in the industrial production production capacity, reducing energy consumption, reduce manually into
Sheet, reduction equipment etc. put into；
2）The present invention adopts properly mixed solvent, and dissolubility is good and product is molten in the solvent in a solvent to make reaction raw materials
Solution property is poor, it is ensured that in process of production, realizes reaction and crystallizes while carry out, and the material in subsequent reactions kettle also ten
Partial volume is easily released, highly beneficial for industrial continuous prodution；
3）Due to being circulated recycling to reaction dissolvent and a small amount of unreacted raw material in the present invention, it is achieved thereby that zero-emission
Put, and then whole production cost significantly reduces, and meet the theory of current green chemical industry.
Specific embodiment
The present invention is made with reference to embodiment and further being illustrated, but the present invention is not limited to these enforcements
Example.
Embodiment 1
40.2g triethylamines are weighed respectively, and 31.2g acetonitriles, 30.8g chloroethanes are added in the autoclave of 200ml；Use nitrogen
Gas is added to 2MPa, is warming up to 140 °C, the lower reaction of stirring 3 hours, and cooling, separation product finally give etamon chloride
63.9g, its yield are 97.1%, and quantitative analysis etamon chloride content is 99.5%.
Comparative example 1
40.2g triethylamines are weighed respectively, and 31.2g acetonitriles, 30.8g chloroethanes are added in the autoclave of 200ml；Heat up
To 140 °C, the lower reaction of stirring 3 hours, cooling, separation product finally give etamon chloride 53.0g, and its yield is
80.5%。
Embodiment 2
40.2g triethylamines are weighed respectively, and 31.2g acetonitriles, 35.9g chloroethanes are added in the autoclave of 200ml；Use nitrogen
Gas is added to 2MPa, is warming up to 140 °C, the lower reaction of stirring 1 hour, and cooling, separation product finally give etamon chloride
60.8g, its yield are 92.4%.
Embodiment 3
40.2g triethylamines are weighed respectively, and 31.2g acetonitriles, 35.9g chloroethanes are added in the autoclave of 200ml；Use nitrogen
Gas is added to 1MPa, is warming up to 140 °C, the lower reaction of stirring 4 hours, and cooling, separation product finally give etamon chloride
65.2g, its yield are 99.1%.
Embodiment 4
40.2g triethylamines are weighed respectively, and 31.2g acetonitriles, 35.9g chloroethanes are added in the autoclave of 200ml；Use nitrogen
Gas is added to 2MPa, is warming up to 140 °C, the lower reaction of stirring 2 hours, and cooling, separation product finally give etamon chloride
63.5g, its yield are 96.5%.
Embodiment 5
40.2g triethylamines are weighed respectively, and 31.2g acetonitriles, 28.2g chloroethanes are added in the autoclave of 200ml；Use nitrogen
Gas is added to 2MPa, is warming up to 140 °C, the lower reaction of stirring 3 hours, and cooling, separation product finally give etamon chloride
63.1g, its yield are 95.9%.
Claims (9)
1. a kind of high-efficiency synthesis method of high-purity etamon chloride, in being appropriate solvent, by triethylamine and chloroethanes one
Under fixed temperature and pressure, agent need not be facilitated, etamon chloride product is obtained by single step reaction.
2. characterized in that, the synthetic method is carried out according to the following steps：（1）The triethylamine for taking proportional quantity is placed in autoclave
In, the solvent of respective amount is added, under the conditions of low-temperature negative-pressure, the chloroethanes of respective amount is passed through, with gas pressurized to certain pressure
Afterwards, react 0.5 ~ 12 hour under certain reaction temperature；（2）After reaction terminates, room temperature is carried out to product in autoclave
Crystallisation by cooling, or be passed through cooling circulating water product cooling in autoclave is crystallized；Mother liquor and product is separated after the completion of crystallization
Product, finally give highly purified etamon chloride；（3）Mother liquor after recovery does not carry out extra process, is then used as lower batch
The solvent of etamon chloride synthetic reaction, according to this, recycles mother liquor.
3. the high-efficiency synthesis method of high-purity etamon chloride according to claim 1, it is characterised in that described is molten
Agent be methyl alcohol, ethanol, isopropanol, ethyl acetate, dimethyl carbonate, acetonitrile, acetone, one or more solvent in butanone it is mixed
Compound, if the weight ratio of the mixture of described solvent multi-solvents, solvent therein 1 and solvent 2 is 0.5 ~ 30:1, preferably
For 1 ~ 15:1.
4. the high-efficiency synthesis method of high-purity etamon chloride according to claim 1, it is characterised in that the gas
For nitrogen, carbon dioxide, inert gas and its mixture, preferably gas is nitrogen.
5. the high-efficiency synthesis method of high-purity etamon chloride according to claim 1, it is characterised in that described one
Fixed pressure is 0.5MPa ~ 20MPa, and preferably pressure is 1 ~ 5MPa.
6. the high-efficiency synthesis method of high-purity etamon chloride according to claim 1, it is characterised in that described chlorine
Ethane and triethylamine and mol ratio are 0.5 ~ 2.5:1, preferably 1.1 ~ 1.3:1.
7. the high-efficiency synthesis method of high-purity etamon chloride according to claim 1, it is characterised in that described is molten
Agent is 0.3 ~ 10 with the weight ratio of triethylamine:1, preferably 0.8 ~ 1.5:1.
8. the high-efficiency synthesis method of high-purity etamon chloride according to claim 1, it is characterised in that described is anti-
Temperature is answered to be 60 ~ 200 °C, preferably 100 ~ 150 °C.
9. the high-efficiency synthesis method of high-purity etamon chloride according to claim 1, it is characterised in that described is anti-
It is 0.5 ~ 12 hour, preferably 1 ~ 3.5 hour between seasonable.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108586261A (en) * | 2018-01-20 | 2018-09-28 | 盐城泛安化学有限公司 | A kind of preparation method of high-purity etamon chloride |
| CN113846337A (en) * | 2021-09-17 | 2021-12-28 | 镇江润晶高纯化工科技股份有限公司 | Method for preparing high-purity tetraethylammonium hydroxide through continuous electrolysis |
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| JP2000212132A (en) * | 1999-01-18 | 2000-08-02 | Sumitomo Seika Chem Co Ltd | Production of quaternary tetraethylammonium chloride |
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| WO2002085786A1 (en) * | 2001-04-19 | 2002-10-31 | Lithdyne International | Process for preparing tetrafluoroborate salt and intermediates thereof |
| JP2004010570A (en) * | 2002-06-10 | 2004-01-15 | Tosoh Corp | Method for producing quaternary halogenated ammonium salt |
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| CN102060701A (en) * | 2010-12-27 | 2011-05-18 | 营口市风光化工有限公司 | Method for synthesizing beta-(3,5-di-tert-butyl-4-hydroxyphenyl)methyl propionate |
| CN103159746A (en) * | 2011-12-12 | 2013-06-19 | 山东新时代药业有限公司 | Industrial tegafur synthesizing method |
| CN104163763A (en) * | 2014-07-14 | 2014-11-26 | 安徽奔马先端科技有限公司 | New synthesis method of high purity quaternary ammonium salt |
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2016
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| WO2002085786A1 (en) * | 2001-04-19 | 2002-10-31 | Lithdyne International | Process for preparing tetrafluoroborate salt and intermediates thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108586261A (en) * | 2018-01-20 | 2018-09-28 | 盐城泛安化学有限公司 | A kind of preparation method of high-purity etamon chloride |
| CN113846337A (en) * | 2021-09-17 | 2021-12-28 | 镇江润晶高纯化工科技股份有限公司 | Method for preparing high-purity tetraethylammonium hydroxide through continuous electrolysis |
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Application publication date: 20170322 |