CN109232167A - A kind of preparation process of perfluorobutadiene - Google Patents
A kind of preparation process of perfluorobutadiene Download PDFInfo
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- CN109232167A CN109232167A CN201811313308.6A CN201811313308A CN109232167A CN 109232167 A CN109232167 A CN 109232167A CN 201811313308 A CN201811313308 A CN 201811313308A CN 109232167 A CN109232167 A CN 109232167A
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- perfluorobutadiene
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- lda
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic System
- C07F3/06—Zinc compounds
Abstract
The invention discloses a kind of preparation processes of perfluorobutadiene; include the following steps: step (1), under nitrogen protection; tetrahydrofuran and anhydrous zinc chloride are added in flask; reduce by 10 DEG C of temperature; a certain amount of tetrafluoroethane is slowly added dropwise; then it adds LDA (diisopropylamine lithium), it is after reaction stirring a period of time, mixture is cooling；Step (2) vacuumizes system, then is slowly added into molysite or mantoquita, keeps temperature-resistant in adition process；After charging, temperature is increased, is stirred continuously reaction, generates perfluorobutadiene；Finished product perfluorobutadiene is collected by trap cooling.Raw material of the invention is tetrafluoroethane, and cheap and be easy to get, reaction condition is simple.
Description
Technical field
The present invention relates to a kind of preparation processes of perfluorobutadiene, especially with tetrafluoroethane (hfc-134a) for raw material system
The method of standby perfluorobutadiene.
Background technique
Perfluorobutadiene (also known as hexachlorobutadiene), because its tool is there are two double bond, often by as preparing a variety of fluorine-containing high scores
A kind of monomer of elastic material.Last decade, hexachlorobutadiene (C4F6Or HFBD) application focus primarily upon semiconductor product
Plasma medium etching processing techniques on.With traditional plasma etching gas CF4、C2F6、C3F8、c-C4F6And NF3It compares,
C4F6With faster etch-rate, high etching selectivity and high-aspect-ratio.And the service life of C4F6 in an atmosphere it is shorter (<
1d), the GWP value and above-mentioned conventional etch gas phase for making it are free of chlorine than negligible, and in molecule to earth atmosphere
Ozone layer inertia is also presented.Therefore C4F6 is that a kind of greenhouse effects are extremely low, environmentally protective efficient dry etching gas, is had wide
Wealthy market prospects.
The synthesis of perfluorobutadiene at present mainly has following several routes: (1) be saturated fluorine halogen butane slough halogen atom or
Hydrogen halides；(2) trifluoroethane metal alkyl halides are coupled certainly；(3) in the presence of Grignard Reagent, α, ω-dihalo- perfluorinated butane
Defluorinate halogen.Furthermore researcher also resets isomerization, perfluor adipic acid sodium pyrolytic at high temperature using hexafluoro cyclobutane
The methods of synthesis, but these methods are because of the lower and less use of yield.A kind of new perfluorobutadiene is prepared it is therefore desirable to develop
Method.
Summary of the invention
Goal of the invention: the object of the present invention is to provide a kind of preparation processes of perfluorobutadiene, and the technique is with tetrafluoroethane
For raw material, product selectivity is high, is easily isolated and purifies, realizes the industrialized production of perfluorobutadiene.
A kind of technical solution: preparation process of perfluorobutadiene, comprising the following steps:
Tetrahydrofuran and anhydrous zinc chloride are added in flask for step (1), under nitrogen protection, reduce by 10 DEG C of temperature, slowly
Slowly a certain amount of tetrafluoroethane is added dropwise, then adds LDA (diisopropylamine lithium), after reaction stirring a period of time, will mix
Object is cooling；
Step (2) vacuumizes system, then is slowly added into molysite or mantoquita, keeps temperature-resistant in adition process；Charging
After, temperature is increased, reaction is stirred continuously, generates perfluorobutadiene；Finished product perfluorobutadiene is collected by trap cooling.
As optimization: adding reaction temperature when tetrafluoroethane and LDA in the step (1) is 10-15 DEG C.
As optimization: being reacted 0.5-3 hours after adding LDA in the step (1), reaction temperature is 10-30 DEG C.
As optimization: tetrafluoroethane and the molar ratio of anhydrous zinc chloride are 0.5:1-4:1 in the step (1)；Tetrafluoro second
The mass ratio of alkane and tetrahydrofuran is 1:5-1:20；The mol ratio of anhydrous zinc chloride and LDA are 1:1-1:6.
As optimization: the reaction need to collect product perfluorobutadiene under the conditions of certain vacuum, and vacuum degree is
100mmHg。
As optimization: when molysite or mantoquita being added in the step (2), reaction temperature is -5-5 DEG C.
As optimization: molysite or mantoquita are FeCl in the step (2)3、FeBr3、CuBr2、Cu(OAc)2、Cu(OTf)2。
As optimization: after the completion of all feeding in the step (2), increasing temperature to 30-50 DEG C.
As optimization: the collection of product carries out in the cold well that dry ice-propanone is bathed in the step (2).
The utility model has the advantages that the present invention with tetrafluoroethane (HFC-134a) be raw material, in polar solvent, highly basic effect under,
Trifluorovinyl zinc chloride is obtained with metal chloride；Again using molysite or mantoquita as catalyst, in aprotic polar solvent, three
Fluoride-based zinc chloride, which reacts, generates perfluorobutadiene.Raw material of the invention is tetrafluoroethane, cheap and be easy to get, instead
Answer condition simple.
Detailed description of the invention
Fig. 1 is technological process of production schematic diagram of the invention.
Specific implementation method
The present invention is further explained in the light of specific embodiments.
Specific embodiment 1
(1) under nitrogen protection, tetrahydrofuran and anhydrous zinc chloride are added into 100ml flask, flask temperature is cooling
To 10 DEG C, keeps temperature-resistant, tetrafluoroethane and LDA (diisopropylamine lithium) is added.LDA add after increase temperature to 10 DEG C,
It is stirred to react 0.5 hour.Tetrafluoroethane and anhydrous zinc chloride the marking mol ratio of addition are 0.5:1；Tetrafluoroethane and tetrahydro
The mass ratio of furans is 1:5.The mol ratio of anhydrous zinc chloride and LDA are 1:2.
(2) system is vacuumized (100 millimetres of mercury), reaction mixture is then cooled to -5 DEG C, is slowly added into molysite
Or mantoquita, it keeps in the process temperature-resistant.Temperature is increased after charging to 30 DEG C, is stirred to react 2 hours.Pass through dry ice-the third
The cold well of ketone bath collects product perfluorobutadiene.
Specific example 2
(1) under nitrogen protection, tetrahydrofuran and anhydrous zinc chloride are added into 100ml flask, flask temperature is cooling
To 10 DEG C, keeps temperature-resistant, tetrafluoroethane and LDA (diisopropylamine lithium) is added.LDA add after increase temperature to 15 DEG C,
It is stirred to react 1 hour.Tetrafluoroethane and anhydrous zinc chloride the marking mol ratio of addition are 1.5:1；Tetrafluoroethane and tetrahydro furan
The mass ratio muttered is 1:15.The mol ratio of anhydrous zinc chloride and LDA are 1:3.
(2) system is vacuumized (100 millimetres of mercury), reaction mixture is then cooled to -1 DEG C, is slowly added into molysite
Or mantoquita, it keeps in the process temperature-resistant.Temperature is increased after charging to 35 DEG C, is stirred to react 2 hours.Pass through dry ice-the third
The cold well of ketone bath collects product perfluorobutadiene.
Specific example 3
(1) under nitrogen protection, tetrahydrofuran and anhydrous zinc chloride are added into 100ml flask, flask temperature is cooling
To 15 DEG C, keeps temperature-resistant, tetrafluoroethane and LDA (diisopropylamine lithium) is added.LDA add after increase temperature to 20 DEG C,
It is stirred to react 2 hours.Tetrafluoroethane and anhydrous zinc chloride the marking mol ratio of addition are 2.5:1；Tetrafluoroethane and tetrahydro furan
The mass ratio muttered is 1:20.The mol ratio of anhydrous zinc chloride and LDA are 1:5.
(2) system is vacuumized (100 millimetres of mercury), reaction mixture is then cooled to 2 DEG C, be slowly added into molysite or
Mantoquita is kept temperature-resistant in the process.Temperature is increased after charging to 45 DEG C, is stirred to react 2 hours.Pass through dry ice-propanone
The cold well of bath collects product perfluorobutadiene.
Specific example 4
(1) under nitrogen protection, tetrahydrofuran and anhydrous zinc chloride are added into 100ml flask, flask temperature is cooling
To 15 DEG C, keeps temperature-resistant, tetrafluoroethane and LDA (diisopropylamine lithium) is added.LDA add after increase temperature to 30 DEG C,
It is stirred to react 3 hours.Tetrafluoroethane and anhydrous zinc chloride the marking mol ratio of addition are 4:1；Tetrafluoroethane and tetrahydrofuran
Mass ratio be 1:20.The mol ratio of anhydrous zinc chloride and LDA are 1:6.
(2) system is vacuumized (100 millimetres of mercury), reaction mixture is then cooled to 5 DEG C, be slowly added into molysite or
Mantoquita is kept temperature-resistant in the process.Temperature is increased after charging to 50 DEG C, is stirred to react 2 hours.Pass through dry ice-propanone
The cold well of bath collects product perfluorobutadiene.
Claims (9)
1. a kind of preparation process of perfluorobutadiene, it is characterised in that: the following steps are included:
Tetrahydrofuran and anhydrous zinc chloride are added in flask for step (1), under nitrogen protection, reduce by 10 DEG C of temperature, slowly drip
Add a certain amount of tetrafluoroethane, then adds LDA (diisopropylamine lithium), it is after reaction stirring a period of time, mixture is cold
But；
Step (2) vacuumizes system, then is slowly added into molysite or mantoquita, keeps temperature-resistant in adition process；Charging finishes
Afterwards, temperature is increased, reaction is stirred continuously, generates perfluorobutadiene；Finished product perfluorobutadiene is collected by trap cooling.
2. the preparation process of perfluorobutadiene described in accordance with the claim 1, it is characterised in that: add tetrafluoro in the step (1)
Ethane is 10-15 DEG C with reaction temperature when LDA.
3. the preparation process of perfluorobutadiene described in accordance with the claim 1, it is characterised in that: add LDA in the step (1)
It reacts 0.5-3 hours afterwards, reaction temperature is 10-30 DEG C.
4. the preparation process of perfluorobutadiene described in accordance with the claim 1, it is characterised in that: tetrafluoro second in the step (1)
The molar ratio of alkane and anhydrous zinc chloride is 0.5:1-4:1；The mass ratio of tetrafluoroethane and tetrahydrofuran is 1:5-1:20；Anhydrous chlorine
The mol ratio for changing zinc and LDA is 1:1-1:6.
5. the preparation process of perfluorobutadiene described in accordance with the claim 1, it is characterised in that: the reaction need to be in certain vacuum
Under the conditions of collect product perfluorobutadiene, vacuum degree 100mmHg.
6. the preparation process of perfluorobutadiene described in accordance with the claim 1, it is characterised in that: iron is added in the step (2)
When salt or mantoquita, reaction temperature is -5-5 DEG C.
7. the preparation process of perfluorobutadiene described in accordance with the claim 1, it is characterised in that: in the step (2) molysite or
Mantoquita is FeCl3、FeBr3、CuBr2、Cu(OAc)2、Cu(OTf)2。
8. the preparation process of perfluorobutadiene described in accordance with the claim 1, it is characterised in that: all add in the step (2)
After the completion of material, temperature is increased to 30-50 DEG C.
9. the preparation process of perfluorobutadiene described in accordance with the claim 1, it is characterised in that: product in the step (2)
Collection carries out in the cold well that dry ice-propanone is bathed.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109806858A (en) * | 2019-02-18 | 2019-05-28 | 南通宝凯化工有限公司 | A kind of preparation method of catalysts for gas phase fluorination |
| CN115903705A (en) * | 2022-11-30 | 2023-04-04 | 福建省杭氟电子材料有限公司 | Production management control system for preparing electronic grade hexafluobutadiene |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101525267A (en) * | 2009-04-24 | 2009-09-09 | 河南工业大学 | Method for preparing hexachlorobutadiene |
| CN101774884A (en) * | 2010-01-14 | 2010-07-14 | 天津大学 | Preparation method of hexachlorobutadiene |
| CN102399128A (en) * | 2011-11-09 | 2012-04-04 | 常熟三爱富中昊化工新材料有限公司 | Method for preparing hexafluorobutadiene-1,3 |
| CN104829415A (en) * | 2015-04-03 | 2015-08-12 | 北京宇极科技发展有限公司 | Method for synthesizing hexafluoro-1,3-butadiene |
| CN105272818A (en) * | 2015-11-19 | 2016-01-27 | 北京宇极科技发展有限公司 | New method for preparing hexafluorobutadiene |
-
2018
- 2018-11-06 CN CN201811313308.6A patent/CN109232167A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101525267A (en) * | 2009-04-24 | 2009-09-09 | 河南工业大学 | Method for preparing hexachlorobutadiene |
| CN101774884A (en) * | 2010-01-14 | 2010-07-14 | 天津大学 | Preparation method of hexachlorobutadiene |
| CN102399128A (en) * | 2011-11-09 | 2012-04-04 | 常熟三爱富中昊化工新材料有限公司 | Method for preparing hexafluorobutadiene-1,3 |
| CN104829415A (en) * | 2015-04-03 | 2015-08-12 | 北京宇极科技发展有限公司 | Method for synthesizing hexafluoro-1,3-butadiene |
| CN105272818A (en) * | 2015-11-19 | 2016-01-27 | 北京宇极科技发展有限公司 | New method for preparing hexafluorobutadiene |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109806858A (en) * | 2019-02-18 | 2019-05-28 | 南通宝凯化工有限公司 | A kind of preparation method of catalysts for gas phase fluorination |
| CN115903705A (en) * | 2022-11-30 | 2023-04-04 | 福建省杭氟电子材料有限公司 | Production management control system for preparing electronic grade hexafluobutadiene |
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Address after: 226000 Nantong Qidong Economic Development Zone Jiangsu fine chemical industry concentrated area Applicant after: Nantong baokai Pharmaceutical Co., Ltd Address before: 226000 Nantong Qidong Economic Development Zone Jiangsu fine chemical industry concentrated area Applicant before: Nantong Baokai Chemical Co.,Ltd. |
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Application publication date: 20190118 |