CN105837397A - Method for synthesizing perfluoroalkyl ethylene - Google Patents
Method for synthesizing perfluoroalkyl ethylene Download PDFInfo
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- CN105837397A CN105837397A CN201610248223.9A CN201610248223A CN105837397A CN 105837397 A CN105837397 A CN 105837397A CN 201610248223 A CN201610248223 A CN 201610248223A CN 105837397 A CN105837397 A CN 105837397A
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- synthetic method
- ethylene
- perfluoro alkyl
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- transfer catalyst
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for synthesizing perfluoroalkyl ethylene. The method comprises the following steps: stirring and mixing perfluoroalkyl ethyl iodide and an inorganic base solution, adding a phase transfer catalyst, stirring and heating, performing elimination reaction at 0-100 DEG C, after the reaction is completed, cooling the reaction liquid to the room temperature, leaving to stand and layer, separating the liquid, and washing the organic phase at a lower layer, thereby obtaining the product perfluoroalkyl ethylene. The method is simple in operation process, gentle in reaction condition, simple in product purification, free of organic solvent, and low in cost and safe and environmentally friendly as the phase transfer catalyst can be recycled.
Description
Technical field
The present invention relates to a kind of organic synthesis method, particularly relate to the synthesis side of a kind of perfluoro alkyl ethylene
Method.
Background technology
(formula is CF to perfluoro alkyl ethylene3(CF2)nCH=CH2, the wherein integer between n=0-19) and it is system
Standby perfluoralkyl surfactant and the important intermediate of perfluoroalkyl resin, owing on its molecule, fluorine atom is unique
Physical characteristic so that it is there is excellent water and oil-resistant, thermostability, oxidative resistance, weatherability and chemistry steady
Qualitative and be widely used in the fields such as building coating, textile finishing and optical communication.
The method one of the synthesizing perfluoroalkyl ethylene commonly used at present is with inorganic by perfluor alkyl ethide iodine
Aqueous alkali reacts, and for improving reaction efficiency, adds substantial amounts of cosolvent in system, and reaction is washed after terminating and removed
Go salt by-product, finally give perfluoro alkyl ethylene.In the method, owing to adding the raising of a large amount of cosolvents
Biphase contacting efficiency, then can cause a large amount of losses of solvent in post processing water-washing process, be unfavorable for environment and life
Produce.
Method two is with alcoholic solvent, the inorganic base of perfluor alkyl ethide iodine with excess to be formed organic alkali solution react,
After heated and stirred back flow reaction a period of time, the method distilled by decompression obtains perfluoro alkyl ethylene.Above-mentioned side
In method, use the alcoholic solvent of excess to prepare organic alkali solution with inorganic base, and post-reaction treatment needs distillation
Removing alcoholic solvent, the method for decompression distillation then adds equipment energy consumption, and it is unfavorable all to cause actual production, and makes
Productivity declines.
Summary of the invention
The problem existed for prior art, the invention reside in the synthetic method providing a kind of perfluoro alkyl ethylene,
The method reaction condition gentleness is easily controlled, and uses phase transfer catalyst to improve reaction efficiency, it is to avoid to use organic
Solvent, and product postprocessing is simply effective, energy efficient and cost.
Technical scheme is as follows:
Perfluor alkyl ethide iodine is stirred with the aqueous solution of inorganic base and mixes, add phase transfer catalyst, stirring
Heating, carries out elimination reaction at 0 DEG C～100 DEG C, and the response time is 1～48 hour, after reaction terminates, instead
Answering liquid to be cooled to room temperature stratification, separatory takes off a layer organic facies, is washed with deionized 1-5 all over to colourless
Bright, obtain the perfluoro alkyl ethylene that product of formula (I) represents；
Wherein, perfluor alkyl ethide iodine is 1:1～1:50 with the mol ratio of inorganic base；
Perfluor alkyl ethide iodine is 1:0.1～1:100 with the phase transfer catalyst mol ratio of addition；
The formula of described perfluoro alkyl ethylene is CF3(CF2)nCH=CH2(I), wherein between n=0-19
Integer；The formula of described perfluor alkyl ethide iodine is CF3(CF2)nCH2CH2I (II), wherein n=0-19 it
Between integer.
Inorganic base in above-mentioned reactions steps is sodium hydroxide, potassium hydroxide, barium hydroxide, sodium carbonate, carbonic acid
Hydrogen sodium, sodium phosphate, dibastic sodium phosphate, sodium hypochlorite, sodium hypobromite, potassium carbonate, potassium bicarbonate, potassium phosphate,
One or more in potassium hydrogen phosphate, postassium hypochlorite, potassium hypobromite, ammonia are with the mixture of arbitrary proportion.
Phase transfer catalyst in reactions steps is tetrabutyl ammonium bromide, triethyl group cetyl ammonium bromide, three second
Base Benzylphosphonium Bromide ammonium, bromination triethyl group cetyl phosphine, tetraphenylarsonium chloride base phosphine, trialkylamine, 18-crown-6,
One or more in PEG-4000, Polyethylene Glycol-600, PEG-8 00, PEG-6000 are appointed
The mixture of meaning ratio.
As preferably:
The reaction temperature of described elimination reaction is 0 DEG C～80 DEG C, and the response time is 8～24 hours；
Described perfluor alkyl ethide iodine is 1:1～1:10 with the mol ratio of inorganic base；
Described perfluor alkyl ethide iodine is 10:1～0.1:1 with the mol ratio of phase transfer catalyst；
Described inorganic base is selected from any one in sodium hydroxide, potassium bicarbonate, sodium bicarbonate, ammonia；
Described phase transfer catalyst is in tetrabutyl ammonium bromide, PEG-4000, Polyethylene Glycol-600
Any one.
Further: it is any one that described phase transfer catalyst is selected from tetrabutyl ammonium bromide, PEG-4000
Kind.
Compared with prior art, the invention have the benefit that the present invention use the aqueous solution of inorganic base directly with
Perfluor alkyl ethide Iod R, generates corresponding perfluoro alkyl ethylene, and the present invention need not add organic solvent, keeps away
Exempt from product postprocessing massive laundering and the tedious steps of decompression distillation, improve by adding phase transfer catalyst
Biphase contacting efficiency, thus improve reaction efficiency, during phase transfer catalyst remains in reaction vessel after reaction
Recycling, present invention process method operating process is simple, and reaction condition is gentle, and purification of products is simple, it is to avoid
Using solvent, phase transfer catalyst can be recycled simultaneously, cost-effective, safety and environmental protection.
Detailed description of the invention
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1
1.49g (0.037mol) sodium hydroxide adds in single port flask with 20.28g (1.13mol) deionized water
Stirring and dissolving, continuously adds 2.3g (0.00575mol) PEG-4000 and 9.99g (0.021mol) is complete
Fluorine hexyl ethyl iodide, stirring reaction 6 hours, stratification at 40 DEG C, share under deionized water 15ml washing
Layer organic facies 3 times.
Obtaining perfluorohexyl ethylene 7.05g, productivity is 96.5%.
Embodiment 2
6.22g (0.05mol) 28% ammonia, 1.49g (0.00462mol) tetrabutyl bromine is added in reaction bulb
Change ammonium and 9.95g (0.02mol) perfluoro hexyl ethyl iodide, stirring reaction 24 hours at 20 DEG C, stratification,
Share deionized water 15ml and wash lower floor's organic facies 3 times.
Obtaining perfluorohexyl ethylene 6.55g, productivity is 94.2%.
Embodiment 3
In reaction bulb add 3.01g (0.036mol) sodium bicarbonate, 7.5g (0.42mol) deionized water,
1.54g (0.00478mol) tetrabutyl ammonium bromide and 10.01g (0.021mol) perfluoro hexyl ethyl iodide, 20 DEG C
Lower stirring reaction 24 hours, stratification, share deionized water 15ml and wash lower floor's organic facies 3 times.
Obtaining perfluorohexyl ethylene 7.13g, productivity is 97.6%.
Embodiment 4
In reaction bulb add 3.50g (0.035mol) potassium bicarbonate, 7.01g (0.39mol) deionized water,
1.5g (0.00466mol) tetrabutyl ammonium bromide and 10.03g (0.021mol) perfluoro hexyl ethyl iodide, 20 DEG C
Lower stirring reaction 24 hours, stratification, share deionized water 15ml and wash lower floor's organic facies 3 times.
Obtaining perfluorohexyl ethylene 6.80g, productivity is 93.2%.
Claims (9)
1. the synthetic method of a perfluoro alkyl ethylene, it is characterised in that: employing following steps:
Perfluor alkyl ethide iodine is stirred with the aqueous solution of inorganic base and mixes, add phase transfer catalyst, stirring
Heating, carries out elimination reaction at 0 DEG C～100 DEG C, and the response time is 1～48 hour, after reaction terminates, instead
Answering liquid to be cooled to room temperature stratification, separatory takes off a layer organic facies, is washed with deionized 1-5 all over to colourless
Bright, obtain the perfluoro alkyl ethylene that product of formula (I) represents；
Wherein, perfluor alkyl ethide iodine is 1:1～1:50 with the mol ratio of inorganic base；
Perfluor alkyl ethide iodine is 1:0.1～1:100 with the phase transfer catalyst mol ratio of addition；
The formula of described perfluoro alkyl ethylene is CF3(CF2)nCH=CH2(I), wherein between n=0-19
Integer；The formula of described perfluor alkyl ethide iodine is CF3(CF2)nCH2CH2I (II), wherein n=0-19 it
Between integer.
The synthetic method of a kind of perfluoro alkyl ethylene the most according to claim 1, it is characterised in that: institute
The perfluor alkyl ethide iodine stated is 1:1～1:10 with the mol ratio of inorganic base.
The synthetic method of a kind of perfluoro alkyl ethylene the most according to claim 1, it is characterised in that: institute
The perfluor alkyl ethide iodine stated is 10:1～0.1:1 with the mol ratio of phase transfer catalyst.
The synthetic method of a kind of perfluoro alkyl ethylene the most according to claim 1, it is characterised in that: institute
The inorganic base stated is sodium hydroxide, potassium hydroxide, barium hydroxide, sodium carbonate, sodium bicarbonate, sodium phosphate, phosphorus
Acid hydrogen sodium, sodium hypochlorite, sodium hypobromite, potassium carbonate, potassium bicarbonate, potassium phosphate, potassium hydrogen phosphate, hypochlorous acid
One or more in potassium, potassium hypobromite, ammonia are with the mixture of arbitrary proportion.
The synthetic method of a kind of perfluoro alkyl ethylene the most according to claim 4, it is characterised in that: institute
The inorganic base stated is selected from any one in sodium hydroxide, potassium bicarbonate, sodium bicarbonate, ammonia.
The synthetic method of a kind of perfluoro alkyl ethylene the most according to claim 1, it is characterised in that: institute
The phase transfer catalyst stated be tetrabutyl ammonium bromide, triethyl group cetyl ammonium bromide, triethylbenzyl ammonium bromide,
Bromination triethyl group cetyl phosphine, tetraphenylarsonium chloride base phosphine, trialkylamine, 18-crown-6, PEG-4000, poly-
The mixture of one or more arbitrary proportions in ethylene glycol-600, PEG-8 00, PEG-6000.
The synthetic method of a kind of perfluoro alkyl ethylene the most according to claim 6, it is characterised in that: institute
It is any one that the phase transfer catalyst stated is selected from tetrabutyl ammonium bromide, PEG-4000, Polyethylene Glycol-600
Kind.
The synthetic method of a kind of perfluoro alkyl ethylene the most according to claim 7, it is characterised in that: institute
The phase transfer catalyst stated is selected from any one in tetrabutyl ammonium bromide, PEG-4000.
The synthetic method of a kind of perfluoro alkyl ethylene the most according to claim 1, it is characterised in that: institute
The reaction temperature stating elimination reaction is 0 DEG C～80 DEG C, and the response time is 8～24 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610248223.9A CN105837397A (en) | 2016-04-19 | 2016-04-19 | Method for synthesizing perfluoroalkyl ethylene |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610248223.9A CN105837397A (en) | 2016-04-19 | 2016-04-19 | Method for synthesizing perfluoroalkyl ethylene |
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| CN105837397A true CN105837397A (en) | 2016-08-10 |
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| CN201610248223.9A Pending CN105837397A (en) | 2016-04-19 | 2016-04-19 | Method for synthesizing perfluoroalkyl ethylene |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114516781A (en) * | 2022-03-17 | 2022-05-20 | 山东大学 | Preparation method of perfluorooctyl ethyl iodide and perfluorooctyl ethylene |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1589248A (en) * | 2001-09-25 | 2005-03-02 | 霍尼韦尔国际公司 | Process for producing fluoroolefins |
| CN101565350A (en) * | 2009-06-05 | 2009-10-28 | 山东中氟化工科技有限公司 | Method for preparing perfluoro alkyl ethylene |
| CN100589248C (en) * | 2007-11-14 | 2010-02-10 | 北京芯技佳易微电子科技有限公司 | A programmable non volatile memory unit, array and its making method |
| US20120175137A1 (en) * | 2005-11-10 | 2012-07-12 | E. I. Du Pont De Nemours And Company Chemtura Corporation | Fire extinguishing agents, methods for preventing and/or extinguishing combustion, fire extinguishing systems, and production processes |
-
2016
- 2016-04-19 CN CN201610248223.9A patent/CN105837397A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1589248A (en) * | 2001-09-25 | 2005-03-02 | 霍尼韦尔国际公司 | Process for producing fluoroolefins |
| US20120175137A1 (en) * | 2005-11-10 | 2012-07-12 | E. I. Du Pont De Nemours And Company Chemtura Corporation | Fire extinguishing agents, methods for preventing and/or extinguishing combustion, fire extinguishing systems, and production processes |
| CN100589248C (en) * | 2007-11-14 | 2010-02-10 | 北京芯技佳易微电子科技有限公司 | A programmable non volatile memory unit, array and its making method |
| CN101565350A (en) * | 2009-06-05 | 2009-10-28 | 山东中氟化工科技有限公司 | Method for preparing perfluoro alkyl ethylene |
Non-Patent Citations (1)
| Title |
|---|
| B. AM6DURI等: "Synthesis and properties of fluorosilicon-containing polybutadienes by hydrosilylation of fluorinated hydrogenosilanes.Part 1. Preparation of the silylation agents", 《JOURNAL OF FLUORINE CHEMISTRY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114516781A (en) * | 2022-03-17 | 2022-05-20 | 山东大学 | Preparation method of perfluorooctyl ethyl iodide and perfluorooctyl ethylene |
| CN114516781B (en) * | 2022-03-17 | 2023-09-19 | 山东大学 | Preparation method of perfluorooctyl ethyl iodide and perfluorooctyl ethylene |
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