CN107761130B - The electrochemical fluorination preparation method of hydrofluoroether - Google Patents
The electrochemical fluorination preparation method of hydrofluoroether Download PDFInfo
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- CN107761130B CN107761130B CN201710935666.XA CN201710935666A CN107761130B CN 107761130 B CN107761130 B CN 107761130B CN 201710935666 A CN201710935666 A CN 201710935666A CN 107761130 B CN107761130 B CN 107761130B
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/27—Halogenation
- C25B3/28—Fluorination
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/04—Saturated ethers
- C07C43/12—Saturated ethers containing halogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/04—Saturated ethers
- C07C43/12—Saturated ethers containing halogen
- C07C43/123—Saturated ethers containing halogen both carbon chains are substituted by halogen atoms
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Abstract
The present invention relates to a kind of preparation methods of hydrofluoroether, and in particular to a kind of electrochemical fluorination preparation method of hydrofluoroether.Chloroether class compound, fluorination reagent and aprotic solvent are added in fluorination electrolytic cell and are fluorinated, the hydrofluoroether product for being free of chlorine, fluorination reagent Et are generated3N-3HF.Aprotic solvent is dimethyl sulfoxide, Et3Concentration range of the N-3HF in dimethyl sulfoxide is 10-15mol/L, and the electrode voltage of fluorination electrolytic cell is controlled in 3.5V.Use Et3N-3HF, selection fluorination performance is fabulous, and product impurity is less, and purity is higher, and yield is higher at a high selectivity, adds aprotic solvent, has preferable influence to the electric conductivity of solution at electrolysis initial stage.A variety of Hydrofluoroether compounds such as perfluoro-ethyl methyl ether can be prepared by primary raw material of chloroether in the present invention, and react alternative raising, and target product is up to 99.9% in product obtained after post-processing.
Description
Technical field
The present invention relates to a kind of preparation methods of hydrofluoroether, and in particular to a kind of electrochemical fluorination preparation side of hydrofluoroether
Method.
Background technique
Fluorine-containing chemical shows that many advantages, such as partially fluorinated or whole fluorinated organic compounds have uniqueness
The performances such as insulating properties, hydro-oleophobicity and high temperature resistant, so fluorochemical is very commercially valuable chemical substance, mesh
Preceding its has important and special purposes in fields such as medicine, new material, pesticides.And hydrofluoroether class is a kind of partially fluorinated fluorine-containing
Compound can be used as cleaning agent, foaming agent, refrigerant etc..
The method for preparing hydrofluoroether is more, and the addition etc. of alkylation, Fluorine containing olefine and alcohol including carboxyl compound is above-mentioned
There is the drawbacks of in terms of raw material in terms of preparing low boiling point hydrofluoroether in method.
Electrochemical fluorination includes at present using wide Simons electrochemical fluorination, such as United States Patent (USP)
SimonsECF method is reported in US2519983.But the fluoride of this method preparation uses often along with many side reactions
When pure hydrogen fluoride solution is fluorinated product, do not have selectively, under same concentrations and voltage conditions, all chlorine in matrix
It is all replaced by fluorine atoms with hydrogen atom.
The fluorination reagent that people and then searching react more mild carries out another electrochemical fluorination as electrolyte, should
Method is that Schmidt is proposed the 1950s, and the later period passes through the continuous exploration of people, realizes the exchange of fluorine halogen atom
Reaction, such as the reports such as Sanit-Jalmes in 2006 use triethylamine three (hydrogen fluoride) (Et3N-3HF) can be chosen property
Ring group hydrogen fluorine thioether substance is made in exchange chloride for fluoride, and target product is aromatic compound, and boiling point is generally greater than 100
DEG C, but yield is very low, is usually no more than 10%.
Summary of the invention
In view of the deficiencies of the prior art, the object of the present invention is to provide a kind of electrochemical fluorination preparation method of hydrofluoroether,
Product impurity is few, purity is high, high income, and reaction alternative is high, and the ratio of target product may be up in product obtained
99%.
The electrochemical fluorination preparation method of hydrofluoroether of the present invention, by chloroether class compound, fluorination reagent and non-
Proton solvent is added in fluorination electrolytic cell and is fluorinated, and generates the hydrofluoroether product for being free of chlorine, fluorination reagent Et3N-3HF。
Chloroether class compound of the present invention, in the group of ehter bond both ends, one end be free from fluorine or chlorine, part it is fluorine-containing or
The alkyl of chlorine, the other end are complete fluorine-containing or chlorine groups, the fluorinated product that the present invention available in this way is intentionally got contains
Fluoroalkyl alkyl ether.
Chloroether class compound is CFxClyHz-(CFpClq)m-O-(CH2)n-CH3, in formula, x, y, z is 0 to 3 integer, q
It is 1 or 2, p is 0 or 1, and m is 0 to 3 integer, and n is 0 to 2 integer.
Preferably, chloroether class compound is CFCl2CF2-O-CH3、CFCl2CF2-O-CH2CH3、CF3CFHCFCl-O-CH3
Or CF3CFHCFCl-O-CH2CH3。
Hydrofluoroether product without chlorine is CFxHz-(CFp)m-O-(CH2)n-CX3, in formula, x, y, z is 0 to 3 integer, q
It is 1 or 2, p is 0 or 1, and m is 0 to 3 integer, and n is 0 to 2 integer, and X is hydrogen or fluorine atom, when X is fluorine atom, z+n ≠
0。
Preferably, the hydrofluoroether product without chlorine is CF3CF2-O-CH3、CF3CF2-O-CH2CH3、CF3CFHCF2-O-CH3、
CF3CFHCF2-O-CH2CF3Or CF3CFHCF2-O-CH2CH3。
Being fluorinated temperature range is 20-60 DEG C, and the fluorination time is 2-10h.
Fluorination reagent used in the present invention is triethylamine-hydrogen fluoride (Et3N-3HF), initial fluorination reagent application is most universal
Be fluorine gas, but high reaction activity possessed by it, lack selectivity and toxicity etc. and cause the application risk higher, and make
Use narrow range.Later people have developed novel fluorination reagent, O-F and N-F reagent is still deposited although risk decreases
In certain limitation.Its reactivity is set to become more mild and easily operated, Et using triethylamine-hydrogen fluoride3N-3HF
With mild and effective reactivity, good regioselectivity and lesser corrosivity, and it is quality-high and inexpensive.
Matrix of the invention has insulating properties, and Et3The viscosity of N-3HF solution is larger, and pure Et3N3HF solution phase
Fluorination performance under the conditions of is slightly excessively high, and the present invention adds suitable highly polar aprotic solvent in the electrolytic solution, has reached drop
Low Et3N-3HF solution viscosity improves the effect of the conductivity of solution, because such solvent can reduce the energy of reaction transition state
It building, stablizes reaction intermediate, be conducive to the speed for accelerating reaction, aprotic solvent is preferably dimethyl sulfoxide in the present invention,
Dimethyl sulfoxide has preferable influence to the electric conductivity of solution at electrolysis initial stage, but the addition of dimethyl sulfoxide is unfavorable for being fluorinated
The progress of reaction, as a result the chlorine atom in matrix cannot be fully substituted, so needing to control the additional amount of dimethyl sulfoxide, be measured
It is excessive, it may result in electrode surface in the regulation of electrolysis and polymerization reaction occur and forms the polymer film less than point, prevent
The further progress of electrode reaction, so in the present invention, Et3Concentration range of the N-3HF in dimethyl sulfoxide is 10-
15mol/L。
Et3N-3HF and dimethyl sulfoxide form electrolyte, Et3Concentration range of the N-3HF in dimethyl sulfoxide is 10-
15mol/L.The concentration range of chloroether class compound in the electrolytic solution is 0.1-10mol/L.
The electrode voltage of fluorination electrolytic cell is controlled in 3.0-4.5V, preferably 3.5V.In the excessively high then methyl of electrode voltage
Hydrogen can partially be replaced, and electrode voltage is too low, and chlorine atom cannot be fully substituted, and the present invention controls the electricity of fluorination electrolytic cell
Pole tension is controlled in 3.5V, ideal substitution product can be obtained, and yield is higher.
Reaction condition of the present invention is more mild, and current strength is moderate, will not generally decompose in fluorination reaction process
Or synthetic reaction, it also avoids to generate the fluorinated product for containing carbon atom more less than matrix or more.On the other hand, it reacts
Fluorine can add in degree of unsaturation first when any degree of unsaturation generated in the process reacts, institute's base in the process of the present invention
The generation of this avoidable alkene ether impurity.
The invention belongs to selective fluorination, electrode voltage control is in 3.5V, by coordination electrode control of Electric potentials size of current,
The conditions such as the concentration of fluorination reagent influence the hydrogen atom in matrix above carbon skeleton by the electrochemical fluorination process, make
A degree of integrality will at least be kept in above-mentioned fluorinated product by obtaining these groups.And chlorine whole in matrix passes through fluorine halogen
Atom exchange reaction is fully completed fluorine substitution, so that fluorine-containing alkyl-alkyl ether be made.
The electrochemical fluorination electrolytic cell (referred to as " fluorination electrolytic cell ") that fluorination process of the invention can carry out can be electricity
Common electrochemical fluorination electrolytic cell known to electrochemical fluorination reaction field.Fluorination electrolytic cell used in the present invention is by some slots
Body component is constituted, and the groove body can be equipped with reaction solution including one and can be impregnated in the reaction solution, for leading in reaction solution
Enter the electrode reaction container of electric current, material is usually carbon steel.The electrode of electrolytic cell used in small laboratory or pilot scale generally uses
The platinized platinum of teflon-coated.And in biggish design scale, fluorination electrolytic cell includes one and is constituted and hanged by carbon steel
The floating groove body for having electrode block, electrode block include cathode electrode plate and anode electrode plate, and cathode electrode plate is usually closed by iron, nickel or nickel
Gold is made, and anode electrode plate is usually made of nickel, and the electrode plate is impregnated in reaction solution, applies voltage, electricity to the electrode
Stream flows through reaction solution in slot.Under pressurized circulation, reaction solution generates flowing, flows over the surface of anode and cathode.Refer generally to list
Grade flow cell channel (there is single anode and a single cathode) or ambipolar flow cell channel.
Has many advantages, such as good insulating, volatile, non-combustible according to the hydrofluoroether that the method for the present invention produces, it is possible to make
It is used for foaming agent, cleaning agent, solvent etc., for example, being used as the precision cleaning or gold of the electronic product of circuit board, electric motor
Belong to solvent for cleaning；As the foaming agent for preparing polyurethane foam insulation material；As the work in refrigeration machine or refrigerant condenser
Make fluid, heat transfer agent or coolant, the cold and hot working medium in semiconductor manufacturing industry production process；It is prepared as electronic component
The retarder thinner etc. of the functional liquids such as anti-fingerprint liquid, waterproof coating used in process.
In conclusion the invention has the following advantages that
(1) Et is used3N-3HF, selection fluorination performance is fabulous, and product impurity is less, and purity is higher, receives at a high selectivity
Rate is higher, adds aprotic solvent, has preferable influence to the electric conductivity of solution at electrolysis initial stage.
(2) a variety of Hydrofluoroether compounds such as perfluoro-ethyl methyl ether can be prepared by primary raw material of chloroether in the present invention,
And alternative raising is reacted, the ratio of target product may be up to 99% in product obtained, through washing, extraction, rectifying
The product of 99.9% or more purity can be obtained.
Specific embodiment
Below with reference to embodiment, the present invention will be further described.
Embodiment 1
1mol/L Et3The dimethyl sulfoxide electrolytic solution of N3HF is as electrolyte, CFCl2-CF2-O-CH3In electrolyte
In concentration be 1mol/L, the 1L electrolyte for containing product is added in 2.5L electrochemical fluorination electrolytic cell.The electrochemistry
Fluorination electrolytic cell equipment is placed in parallel by about 2 square decimeters of a pair of of platinum electrode slice, keeps potentiostatic deposition, and electric current is adjusted to
50mA, electrode potential are set as 3.5V, and reaction temperature is 25 DEG C, carry out under the normal pressure that nitrogen protection is formed.After the completion of electrolysis, in electricity
It solves and 500ml water is added in liquid, then extracted 5 times using ether, ether is taken mutually to be dried with anhydrous sodium sulfate, decompression filters
To filtrate, as product, takes micro progress chlorine element and fluorine element to test, be as a result listed in table 1.
Embodiment 2-7
It is tested using method same as Example 1, but changes Et in electrolyte3The concentration and electrode of N3HF
Voltage, condition and result are listed in table 1.
Embodiment 8-9
It is tested using method same as Example 1, but feed change type, condition and result are listed in table 1, it is real
It applies example 8 and uses raw material CFCl2-CFCl-O-CH3, embodiment 9 is using raw material CHCl2-CF2-O-CH3。
Comparative example 1
By CFCl2-CF2-O-CH3Be dissolved in anhydrous hydrogen fluoride, using Simons method a 2.5L electrochemistry
Implement the experiment in electrolytic cell, electrolytic cell is additionally provided with one -35 DEG C of overhead condensation other than equipped with anodic-cathodic piece
Device, pressure 0.2MPa 25 DEG C of temperature, keep constant voltage 3.0V, slowly heat up after being electrolysed the regular hour, remove HF, flow into
HF collecting tank, remaining fluorinated product liquid flow through the HF that one is filled with sodium fluoride particle after 60 DEG C of gasifications and remove column, to remove
Micro HF therein is remained, then again by a pipe equipped with fluorination silver catalyst, to remove issuable OF2,
Condensation obtains Product liquid, tests chlorinity and fluorine content.As a result it is listed in table 1.
Table 1
As seen from the results in Table 1:
Et3Concentration of the N3HF in dimethyl sulfoxide can just obtain target product until becoming 10mol/L.And electrode
Ideal substitution product can be obtained in 3.5V for voltage control.
Gas-chromatography and gas chromatography mass spectrometry data show, obtained target product CF3-CF2-O-CH3Ratio in the product can
Reach 99%, purity, which can be obtained, after washing, organic solvent extraction and rectifying can reach 99.9% or more product.
Claims (6)
1. a kind of electrochemical fluorination preparation method of hydrofluoroether, it is characterised in that: by chloroether class compound, fluorination reagent and non-
Proton solvent is added in fluorination electrolytic cell and is fluorinated, and generates the hydrofluoroether product for being free of chlorine；
Fluorination reagent is Et3N-3HF, aprotic solvent are dimethyl sulfoxide, Et3N-3HF and dimethyl sulfoxide form electrolyte,
Et3Concentration range of the N-3HF in dimethyl sulfoxide is 10-15mol/L；
The chloroether class compound is CFxClyHz-(CFpClq)m-O-(CH2)n-CH3, in formula, x, y, z is 0 to 3 integer, q
It is 1 or 2, p is 0 or 1, and m is 0 to 3 integer, and n is 0 to 2 integer；
The hydrofluoroether product without chlorine is CFxHz-(CFp)m-O-(CH2)n-CX3, in formula, x, y, z is 0 to 3 integer, and q is
1 or 2, p are 0 or 1, and m is 0 to 3 integer, and n is 0 to 2 integer, and X is hydrogen.
2. the electrochemical fluorination preparation method of hydrofluoroether according to claim 1, it is characterised in that: chloroether class compound
For CFCl2CF2-O-CH3、CFCl2CF2-O-CH2CH3、CF3CFHCFCl-O-CH3Or CF3CFHCFCl-O-CH2CH3。
3. the electrochemical fluorination preparation method of hydrofluoroether according to claim 1, it is characterised in that: the hydrofluoroether without chlorine
Product is CF3CF2-O-CH3、CF3CF2-O-CH2CH3、CF3CFHCF2-O-CH3Or CF3CFHCF2-O-CH2CH3。
4. the electrochemical fluorination preparation method of hydrofluoroether according to claim 1, it is characterised in that: being fluorinated temperature range is
20-60 DEG C, the fluorination time is 2-10h.
5. the electrochemical fluorination preparation method of hydrofluoroether according to claim 1, it is characterised in that: chloroether class compound
Concentration range in the electrolytic solution is 0.1-10mol/L.
6. the electrochemical fluorination preparation method of hydrofluoroether according to claim 1, it is characterised in that: the electricity of fluorination electrolytic cell
Pole tension control range is in 3.5V.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3884775A (en) * | 1972-06-14 | 1975-05-20 | Agency Ind Science Techn | Electrolytic process for production of chlorofluorinated ethers |
| RU2221765C1 (en) * | 2002-07-08 | 2004-01-20 | Федеральное государственное унитарное предприятие Российский научный центр "Прикладная химия" | Perfluorinated organic compound production process |
| CN101302621A (en) * | 2008-07-02 | 2008-11-12 | 南开大学 | Electrochemical synthesis method of fluorinated glyoxaline |
| CN102596930A (en) * | 2009-10-21 | 2012-07-18 | 苏威氟有限公司 | Method for the manufacture of fluorinated ethylene carbonates |
| CN103739450A (en) * | 2013-12-30 | 2014-04-23 | 山东华夏神舟新材料有限公司 | Preparation method of hydrofluoroether |
-
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- 2017-10-10 CN CN201710935666.XA patent/CN107761130B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3884775A (en) * | 1972-06-14 | 1975-05-20 | Agency Ind Science Techn | Electrolytic process for production of chlorofluorinated ethers |
| RU2221765C1 (en) * | 2002-07-08 | 2004-01-20 | Федеральное государственное унитарное предприятие Российский научный центр "Прикладная химия" | Perfluorinated organic compound production process |
| CN101302621A (en) * | 2008-07-02 | 2008-11-12 | 南开大学 | Electrochemical synthesis method of fluorinated glyoxaline |
| CN102596930A (en) * | 2009-10-21 | 2012-07-18 | 苏威氟有限公司 | Method for the manufacture of fluorinated ethylene carbonates |
| CN103739450A (en) * | 2013-12-30 | 2014-04-23 | 山东华夏神舟新材料有限公司 | Preparation method of hydrofluoroether |
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