CN106279290B - A kind of oxa- short-chain perfluoroaldyl vinyl ethers and preparation method thereof - Google Patents
A kind of oxa- short-chain perfluoroaldyl vinyl ethers and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of oxa- short-chain perfluoroaldyl vinyl ethers and preparation method thereof.The oxa- short-chain perfluoroaldyl vinyl ethers is refered in particular to such as flowering structure: CF3O(CF2O)nCF2CF2OCF=CF2, wherein n=0 or 1.Preparation method of the present invention utilizes the intermediate acyl fluorides CF of oneself synthesis3OCF2CFO and CF3OCF2OCF2CFO further studies the addition reaction of they and HFPO and subsequent at salt and decarboxylic reaction, it was found that more efficient synthetic technological condition, it is possible thereby to low cost and a large amount of synthesis oxa- short-chain perfluoroaldyl vinyl ethers CF3OCF2CF2OCF=CF2And CF3OCF2OCF2CF2OCF=CF2, this important raw material is provided to synthesize extraordinary fluoropolymer.
Description
Technical field:
The present invention relates to a kind of oxa- short-chain perfluoroaldyl vinyl ethers and preparation method thereof.
Background technique:
Short-chain perfluoroaldyl vinyl ethers compound refers to that general formula is
RfOCF=CF2
Wherein Rf=CF3(CF2)m, m=1-6
Compound；Actually obtain more application is substantially limited to m=1-3 perfluoroalkyl base vinyl ethers, such as perfluor first
Base vinyl ethers (abbreviation PMVE), perfluoroethylvinyl ether (abbreviation PEVE), perfluoropropylvinylether (abbreviation PPVE),
The important monomer for copolymerization some special fluoroplastics and fluorubber, for example, PMVE and tetrafluoroethene copolymerization is available can
Fusible fluoroplastic PFA, PMVE and tetrafluoroethene, inclined fluorine second can be obtained in fusibleness fluoroplastics MFA, PPVE and tetrafluoroethene copolymerization
Inclined fluoroether rubber can be obtained in alkene, cross-linking monomer copolymerization, and perfluoroelastomers can be obtained in PMVE and tetrafluoroethene, cross-linking monomer copolymerization,
PEVE and tetrafluoroethene, hexafluoropropene copolymerization can obtain modified perfluoroethylene-propylene, etc., these short-chain perfluoroaldyl vinyl
Ether plays an important role in Organic fluoride industry.
The research of synthesis and the application of oxa- short-chain perfluoroaldyl vinyl ethers is than later, but their special oxa- knot
Structure makes it with special application value, such as common perfluoroelastomers glass transition temperature with higher, and is being copolymerized
When be added part oxa- short-chain perfluoroaldyl vinyl ethers after, the glass transition temperature of obtained modification perfluoroelastomers obviously drops
It is low, so that it can also be able to maintain good elasticity at lower temperatures.
The study on the synthesis of oxa- short-chain perfluoroaldyl vinyl ethers is less.DuPont Resnick is special in the U.S.
In benefit 3692843 and 3817960, a kind of CF is described3OCF2OCF2The mixture of CFO and CF2ClCFCl2 is in diethylene glycol two
CF is obtained with HFPO addition under cesium fluoride catalysis in methyl ether3OCF2CF2OCF(CF3) CFO, then in diethylene glycol dimethyl ether
With Na2CO3Reaction obtains CF3OCF2OCF2CF2OCF=CF2Method；Baranova is in Zhurnal Organicheskoi
In Khimii 1972,8 (9), 790-793, a kind of CF is described3OCF2CFO and HFPO is being fluorinated in diethylene glycol dimethyl ether
Caesium is catalyzed lower addition and obtains CF3OCF2CF2OCF(CF3) CFO, then obtained with NaOH reactant aqueous solution at salt and then decarboxylation
CF3OCF2CF2OCF=CF2Method；Thereafter pass through nearly 30 years quiet periods, Minnesota Mining and Manufacturing Company Worm etc. is in WO2001046107
In describe a kind of CH3OCH2CH2OCH(CH3)COOCH3It is fluorinated to obtain CF through fluorine gas3OCF2CF2OCF(CF3)CO2CH3And then exist
CF is produced at salt, by salt decarboxylation with KOH in methanol3OCF2CF2OCF=CF2Method；Chinese Yang Xiao is bravely equal in Chinese patent
In CN101376621 and Synthetic Communication 2012,42 (7), 959-966, one kind is described
CH3OCH2OCH2CH2OH reacts to obtain CH with HFPO3OCH2CH2OCF(CF3)CO2CH2CH2OCH2OCH3, ester exchange reaction is at first
Ester CH3OCH2CH2OCF(CF3)CO2CH3, fluorine gas is fluorinated to obtain CF3OCF2CF2OCF(CF3)CO2CH3, by CF3OCF2CF2OCF
(CF3)CO2CH3CF is obtained at salt, decarboxylation with KOH in methyl alcohol3OCF2OCF2OCF2CF2OCF=CF2Method.
In the above synthetic method, rear three documents then use hydrocarbon intermediate more simple and easy to get, but use is difficult to adjust
The fluorine gas flaorination process of control and the fluorine gas of strong oxidizing property, so that its synthesis process is complicated, dangerous and yield is very low, in current item
Economic industrialized production is difficult to realize under part.
The synthesis of first three document is needed using intermediate acyl fluorides CF3OCF2CFO and CF3OCF2OCF2CFO, the two acyl fluorides
Synthesize is usually TFE or HFP high temperature gas phase oxidation or the hydrocarbon electrolysis containing methoxy ethyl in pervious document
What fluoride process obtained, these synthetic methods are complicated and need special consersion unit, and yield is very low, and later researcher is caused to turn
To the direct fluorine gas flaorination process of research.
The present invention utilizes the intermediate acyl fluorides CF of oneself synthesis3OCF2CFO and CF3OCF2OCF2CFO further studies it
With the addition reaction of HFPO and subsequent at salt and decarboxylic reaction, it was found that more efficient synthetic technological condition, it is possible thereby to low
Cost and a large amount of synthesis oxa- short-chain perfluoroaldyl vinyl ethers CF3OCF2CF2OCF=CF2And CF3OCF2OCF2CF2OCF=
CF2, this important raw material is provided to synthesize extraordinary fluoropolymer.
Summary of the invention:
It is a primary object of the present invention to provide a kind of simplicity and it is easy to industrialized synthesis oxa- short-chain perfluoroaldyl second
The method of alkene ether.
The specific technical solution of the present invention is as follows:
A kind of oxa- short-chain perfluoroaldyl vinyl ethers, has the following structure:
CF3O(CF2O)nCF2CF2OCF=CF2
Wherein, n=0 or 1.
The invention also discloses preparation methods comprising following steps:
(1) acyl fluorides CF3O(CF2O)nCF2CFO and hexafluoropropylene oxide (english abbreviation: HFPO, EINECS accession number: 207-
Addition reaction 050-4) occurs, obtains addition product acyl fluorides CF3O(CF2O)nCF2CF2OCF(CF3)CFO；
(2) addition product acyl fluorides CF3O(CF2O)nCF2CF2OCF(CF3) CFO reacted with alkali carbonate, produced
Object CF3O(CF2O)nCF2CF2OCF=CF2。
Preferably, step (1) carries out in the presence of being etherified the mixed solvent of polyol solvent and nitrile solvents.
Preferably, step (1) carries out under the catalysis of alkali metal fluoride.
Specifically, the preparation method of the oxa- short-chain perfluoroaldyl vinyl ethers includes the following steps:
(1)CF3O(CF2O)nCF2CFO is in the in the mixed solvent for being etherified polyol solvent and nitrile solvents, in alkali metal fluosilicate
It under the catalysis of compound, is reacted with HFPO, obtains addition product acyl fluorides CF3O(CF2O)nCF2CF2OCF(CF3)CFO；
(2) addition product acyl fluorides CF obtained in step (1)3O(CF2O)nCF2CF2OCF(CF3) CFO and alkali carbonate
It is reacted, obtains product CF through high temperature decarboxylation3O(CF2O)nCF2CF2OCF=CF2。
In step (1), the alkali metal fluoride refers to CsF or KF, preferably KF, the alkali metal fluoride with
CF3O(CF2O)nCF2The molar ratio of CFO is 0.01:-0.2:1, preferably 0.05:1-0.15:1；The etherificate polyol solvent
Refer to glycol dimethyl ether, ethylene glycol diethyl ether, three methyl ether of glycerine, three ether of glycerine, diethylene glycol dimethyl ether, diethyl two
One of diethylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, tetraethyleneglycol dimethyl ether, tetraethylene glycol diethyl ether
Or a variety of mixtures, preferably diethylene glycol dimethyl ether or diethyl diethylene glycol dimethyl ether and tetraethyleneglycol dimethyl ether molar ratio 1:2~
The mixture of 2:1, the etherificate polyol solvent and CF3O(CF2O)nCF2The molar ratio of CFO is 1:1-50:1, preferably 5:1-
10:1；The nitrile solvents refer to one of acetonitrile, propionitrile, malononitrile, succinonitrile, glutaronitrile, adiponitrile or a variety of, preferably
For succinonitrile, the nitrile solvents and CF3O(CF2O)nCF2The molar ratio of CFO is 0.5:1-25:1, preferably 2:1-5:1；Instead
Answer object HFPO and CF3O(CF2O)nCF2The molar ratio of CFO is 0.5:1-2.5:1, preferably 0.9:1-1.2:1；Reaction temperature be-
40 to 30 degrees Celsius, preferably -20 to -5 degrees Celsius.
In step (1), specifically one with stirring and temperature control equipment reactor in, by alkali metal fluoride with
Etherificate polyol solvent is mixed with nitrile solvents, and raw material CF is added3O(CF2O)nCF2CFO cools down reaction mixture under stiring
To set temperature, it is then passed through HFPO gas under stiring, while being adjusted according to the temperature conditions of reactant to protect
Temperature of charge is held within positive and negative 5 DEG C of set temperature；After having led to HFPO, continues to keep temperature of charge and stir 2 hours,
Then stop stirring, allow reactant to warm naturally to room temperature, reactant will be layered；Lower layer's reactant is separated, rectifying is carried out, obtains
To addition product acyl fluorides CF3O(CF2O)nCF2CF2OCF(CF3)CFO。
In step (2), alkali carbonate refers to Carbon Dioxide lithium, natrium carbonicum calcinatum, Anhydrous potassium carbonate, Carbon Dioxide
Caesium, preferably one or both of natrium carbonicum calcinatum and Anhydrous potassium carbonate, more preferably natrium carbonicum calcinatum and Anhydrous potassium carbonate
The mixture of molar ratio 1:2~2:1, alkali carbonate and CF3O(CF2O)nCF2CF2OCF(CF3) CFO mole ratio be 1:
1-10:1, preferably 2:1-5:1；Reaction temperature is 100 to 300 degrees Celsius, preferably 150 to 230 degrees Celsius.
In step (2), specifically in a reactor with stirring and temperature control equipment, alkali metal carbonic acid is added
Salt；Then addition product acyl fluorides CF is added dropwise into alkali carbonate under stiring3O(CF2O)nCF2CF2OCF(CF3) CFO, at this time
The temperature of reactant does not change substantially；Add addition product acyl fluorides CF3O(CF2O)nCF2CF2OCF(CF3) continue to stir after CFO
It 1 hour, then heats to set temperature and is kept for 4 hours, the gas that reaction generates is drawn out to the receiving for having condenser
In slot, the liquid under condensation is received；After reacting and finishing receiving, obtained liquid washing, dry and rectifying will be received, produced
Product CF3O(CF2O)nCF2CF2OCF=CF2。
The present invention uses CF3OCF2CFO and CF3OCF2OCF2CFO is anti-with the addition reaction and decarboxylation of HFPO by them
It answers, synthesizes oxa- short-chain perfluoroaldyl vinyl ethers CF3OCF2CF2OCF=CF2And CF3OCF2OCF2CF2OCF=CF2, reaction height
Effect, environmental protection more safer than the technique that fluorine gas fluoride process synthesizes same oxa- short-chain perfluoroaldyl vinyl ethers, it is easier to carry out
Industrialized production, cost are lower.
The present invention is carried out the addition reaction of HFPO using mixed solvent, adds into pair in product by optimization reaction condition
Product is reduced；Addition product acyl fluorides is directly reacted into salt and decarboxylation with alkali carbonate, it is complete efficiently to obtain the short chain of product oxa-
Vinyl ethers.
Specific embodiment
Embodiment 1
In dry 2 liters of stainless steel autoclaves with stirring and temperature control device, it is separately added into diethylene glycol diformazan
1005 grams of ether (7.5 moles), 120 grams of succinonitrile (1.5 moles), 5 grams of KF (0.086 mole), are stirred, are then added 273
Gram raw material CF3OCF2Temperature in reaction kettle is cooled to -20 degrees Celsius by CFO (1.5 moles), logical cooling medium.Lasting stirring and logical cooling
Medium is passed through HFPO gas, and reactant can be observed and slightly heat up, and increases the flow of cooling medium at this time to keep temperature not surpass
Cross -15 DEG C；It is common enter HFPO266 grams (1.6 moles).After having led to HFPO, continue to keep temperature of charge and stirring 2 hours, so
Stop stirring afterwards, reactant is allowed to warm naturally to room temperature, reactant is layered after standing；Separate lower layer's reactant, gas-chromatography point
Analysis is known wherein containing CF3OCF2CFO 1.45%, CF3OCF2CF2OCF(CF3) CFO 97.29%, CF3OCF2CF2OCF(CF3)
CF2OCF(CF3) CFO 1.26%.Rectifying is carried out to lower layer's product, obtains addition product acyl fluorides CF3OCF2CF2OCF(CF3) CFO production
478 grams of product (controlling and receiving purity greater than 99.0%).
Embodiment 2
In dry 10 liters of stainless steel autoclaves with stirring and temperature control device, it is separately added into diethylene glycol diformazan
3350 grams of ether (25 moles), 1000 grams of succinonitrile (12.5 moles), 20 grams of KF (0.345 mole), are stirred, are then added
620 grams of raw material CF3OCF2OCF2Temperature in reaction kettle is cooled to -15 degrees Celsius by CFO (2.5 moles), logical cooling medium.Lasting stirring
With logical cooling medium, it is passed through HFPO gas, reactant can be observed and slightly heat up, increases the flow of cooling medium at this time to keep
Temperature is no more than -10 DEG C；It is common enter 420 grams of HFPO (2.53 moles).After having led to HFPO, continues to keep temperature of charge and stir
It mixes 2 hours, then stops stirring, reactant is allowed to warm naturally to room temperature, reactant is layered after standing；Lower layer's reactant is separated,
Gas chromatographic analysis is known wherein containing CF3OCF2OCF2CFO 0.77%, CF3OCF2OCF2CF2OCF(CF3) CFO 97.32%,
CF3OCF2OCF2CF2OCF(CF3)CF2OCF(CF3) CFO 1.91%.Rectifying is carried out to lower layer's product, obtains addition product acyl fluorides
CF3OCF2OCF2CF2OCF(CF3) 954 grams of CFO product (controlling and receiving purity greater than 99.0%).
Embodiment 3
According to method described in embodiment 1, " 1005 grams of diethylene glycol dimethyl ether (7.5 moles) " are replaced with into " tetrem two
1665 grams of diethylene glycol dimethyl ether (7.5 moles) ".Lower layer's reactant is separated after reaction, gas chromatographic analysis is known wherein containing CF3OCF2CFO
1.85%, CF3OCF2CF2OCF(CF3) CFO 96.57%, CF3OCF2CF2OCF(CF3)CF2OCF(CF3) CFO 1.58%.It is right
Lower layer's product carries out rectifying, obtains addition product acyl fluorides CF3OCF2CF2OCF(CF3) CFO product (controls and receives purity to be greater than
99.0%) 470 grams.
Embodiment 4
According to method described in embodiment 1, " 1005 grams of diethylene glycol dimethyl ether (7.5 moles) " are replaced with into " diethyl two
The mixture of 502.5 grams of diethylene glycol dimethyl ether (3.25 moles) and 721.5 grams of tetraglyme (3.25 moles) ".It is separated after reaction
Lower layer's reactant, gas chromatographic analysis are known wherein containing CF3OCF2CFO 0.95%, CF3OCF2CF2OCF(CF3) CFO 98.35%,
CF3OCF2CF2OCF(CF3)CF2OCF(CF3) CFO 0.81%.Rectifying is carried out to lower layer's product, obtains addition product acyl fluorides
CF3OCF2CF2OCF(CF3) 482 grams of CFO product (controlling and receiving purity greater than 99.0%).
Embodiment 5
In 2 liters of stainless steel autoclaves with frame type agitating blade and temperature control device, 800 grams of Anhydrous potassium carbonates are added；So
The addition product acyl fluorides CF that embodiment 4 obtains is added dropwise into autoclave under stiring afterwards3OCF2CF2OCF(CF3) CFO, it is added altogether
1000 grams, observe that the temperature and pressure in autoclave does not change substantially.Continue stirring 1 hour, it is Celsius to then heat to 175
Degree keeps temperature and stirring 4 hours, and the pressure that can be observed in autoclave persistently increases；The gas that reaction generates is drawn out to
In one dump tank with condenser, the liquid under condensation is received；After reacting and finishing receiving, the liquid for receiving and obtaining is taken out,
It is dry through washing, anhydrous sodium sulfate, 734 grams of organic liquid are obtained, gas chromatographic analysis knows it containing CF3OCF2CF2OCF=
CF298.13%, contain CF3OCF2CF2OCHFCF31.87%.Rectifying is carried out to it, obtains 99.0% or more purity
CF3OCF2CF2OCF=CF2689 grams of product.
Embodiment 6
1000 grams of Anhydrous potassium carbonates are replaced with 1000 grams of natrium carbonicum calcinatums by 5 the method for embodiment simultaneously.It finally obtains
844 grams of organic liquid, gas chromatographic analysis knows it containing CF3OCF2OCF2CF2OCF=CF298.89%, contain
CF3OCF2OCF2CF2OCHFCF31.11%.
Embodiment 7
1000 grams of Anhydrous potassium carbonates are replaced with 568 grams of Anhydrous potassium carbonates and 432 grams of nothings by 5 the method for embodiment simultaneously
Aqueous sodium carbonate.844 grams of organic liquid are finally obtained, gas chromatographic analysis knows it containing CF3OCF2OCF2CF2OCF=CF2
99.66%, contain CF3OCF2OCF2CF2OCHFCF30.34%.
Embodiment 8
In 2 liters of stainless steel autoclaves with frame type agitating blade and temperature control device, 1000 grams of Anhydrous potassium carbonates are added；So
The addition product acyl fluorides CF that embodiment 2 obtains is added dropwise into autoclave under stiring afterwards3OCF2OCF2CF2OCF(CF3) CFO, it is added altogether
1100 grams, the temperature and pressure during this in autoclave does not change substantially.Continue stirring 1 hour, then heats to 210 and take the photograph
Family name's degree keeps temperature and stirring 4 hours, and the pressure that can be observed in autoclave persistently increases；The gas that reaction is generated is drawn
Into a dump tank with condenser, the liquid under condensation is received；After reacting and finishing receiving, the liquid for receiving and obtaining is taken out
Body, it is dry through washing, anhydrous sodium sulfate, 844 grams of organic liquid are obtained, gas chromatographic analysis knows it containing CF3OCF2OCF2CF2OCF
=CF299.17%, contain CF3OCF2OCF2CF2OCHFCF30.83%, the product of the purity can be used directly.
Claims (6)
1. the preparation method of oxa- short-chain perfluoroaldyl vinyl ethers, which comprises the steps of:
(1) acyl fluorides CF3O(CF2O)nCF2Addition reaction occurs for CFO and hexafluoropropylene oxide, obtains addition product acyl fluorides CF3O(CF2O)nCF2CF2OCF(CF3)CFO；
(2) addition product acyl fluorides CF3O(CF2O)nCF2CF2OCF(CF3) CFO reacted with alkali carbonate, obtain product CF3O
(CF2O)nCF2CF2OCF=CF2；
Step (1) addition reaction carries out in the presence of being etherified the mixed solvent of polyol solvent and nitrile solvents；
Step (1) described addition reaction carries out under the catalysis of alkali metal fluoride；
Wherein, n=0 or 1；
Step (1) reactant hexafluoropropylene oxide and CF3O(CF2O)nCF2The molar ratio of CFO is 0.9:1-1.2:1；
Step (1) reaction temperature be -20 to -5 degrees Celsius.
2. preparation method as described in claim 1, it is characterised in that: the alkali metal fluoride is selected from CsF or KF.
3. preparation method as described in claim 1, it is characterised in that: the etherificate polyol solvent is selected from glycol dinitrate
Ether, ethylene glycol diethyl ether, three methyl ether of glycerine, three ether of glycerine, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, three second
One of glycol dimethyl ether, triethylene glycol diethyl ether, tetraethyleneglycol dimethyl ether, tetraethylene glycol diethyl ether or a variety of mixing
Object.
4. preparation method as described in claim 1, it is characterised in that: the nitrile solvents be selected from acetonitrile, propionitrile, malononitrile,
One of succinonitrile, glutaronitrile, adiponitrile are a variety of.
5. preparation method as described in claim 1, it is characterised in that: the alkali carbonate is selected from Carbon Dioxide lithium, nothing
Aqueous sodium carbonate, Anhydrous potassium carbonate, Carbon Dioxide caesium.
6. preparation method as described in claim 1, it is characterised in that: the reaction temperature of step (2) described reaction arrives for 100
300 degrees Celsius.
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| US3291843A (en) * | 1963-10-08 | 1966-12-13 | Du Pont | Fluorinated vinyl ethers and their preparation |
| US3321532A (en) * | 1963-10-08 | 1967-05-23 | Du Pont | Fluorocarbon ethers |
| US3817960A (en) * | 1971-03-29 | 1974-06-18 | Du Pont | Polymers of perfluorovinyl ethers |
| CN105061659A (en) * | 2015-07-31 | 2015-11-18 | 深圳诚立胜新材料科技有限公司 | Fluorine-containing material preparation method, and application of fluorine-containing material prepared through using method |
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| US3114778A (en) * | 1963-12-17 | Fluorinated vinyl ethers and their | ||
| US3132123A (en) * | 1960-11-25 | 1964-05-05 | Du Pont | Polymers of perfluoroalkoxy perfluorovinyl ethers |
| US3291843A (en) * | 1963-10-08 | 1966-12-13 | Du Pont | Fluorinated vinyl ethers and their preparation |
| US3321532A (en) * | 1963-10-08 | 1967-05-23 | Du Pont | Fluorocarbon ethers |
| US3250808A (en) * | 1963-10-31 | 1966-05-10 | Du Pont | Fluorocarbon ethers derived from hexafluoropropylene epoxide |
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