CN101698644B - Method for efficiently preparing trifluroethyl vinyl ether without solvent - Google Patents
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Abstract
The invention discloses a method for preparing fluoride-containing trifluroethyl vinyl ethers, which is characterized by carrying out bulk reaction on a fluoride-containing straight chain or branched chain acyl fluoride compound and trifluoroethylene sulfate in the presence of a catalyst and forming a product with a general formula shown in the formula (I). The high-temperature cracking route is avoided and no organic solvent is used in the process of reaction, a trifluroethyl vinyl ether monitor is efficiently prepared through bulk addition reaction and a high purity trifluroethyl vinyl ether monitor can be obtained at high yield through rectification, namely CF2=CF-O-Rf (I).
Description
Technical field
The invention belongs to fluorine-containing fine chemicals field, the preparation method who relates to a class fluroxene, such fluroxene is widely used in synthetic fluoro-resin with proton exchange function, the film product application of such fluoro-resin preparation is played the transmission proton and is stoped the dual function of hydroxyl radical free radical from the backmigration of cathode compartment anode chamber in chlorine industry electrolyzer composite membrane barrier film.
Background technology
After the seventies in 20th century, ion-exchange membrane electrolysis was applied in chlorine industry, this technology had just become the developing direction of chlorine industry old factory technological transformation and newly-built electrolyzer.Using exchange membrane containing fluorine in electrolyzer is technique known at present.This class ionic membrane have bonding negatively charged ion and with its bonded positively charged ion, can carry out cationic exchange.Ionic membrane is divided into cathode compartment and anolyte compartment to battery or electrolyzer, and ion can optionally pass through.Facts have proved, contain ion-exchange group, especially the exchange membrane containing fluorine that contains sulfonic group and carboxylic acid group is more suitable for being used as the cluster ion exchange membrane of chlor-alkali electrolytic cells owing to its chemically-resistant degradation property, the fluorine-containing carboxylic layer exchange membrane of cathode compartment one side mainly rises and stops the backmigration of hydroxyl negatively charged ion to enter the anolyte compartment, in case the backmigration of hydroxyl negatively charged ion enters the anolyte compartment, the current efficiency of chlorine and caustic soda will descend greatly.
Present technique known: the preparation that preparation contains the ion exchange fluoro resin of carboxyl (perhaps subsequent disposal can be converted to carboxyl) is to adopt the fluorine-containing alkene ether monomer and the tetrafluoroethylene monomer that contain carboxyl (perhaps subsequent disposal can be converted to carboxyl) to carry out copolymerization, the wherein employed fluorine-containing alkene ether monomer that contains carboxyl (perhaps subsequent disposal can be converted to carboxyl) be can synthetic ion-exchange resin the most critical raw material.United States Patent (USP) U.S.4281092 has described the preparation of the alkyl alkene ether monomer that contains carboxyl in detail, and the generation portion of containing of the two keys of its end group adopts the mode of Pintsch process to carry out.
Summary of the invention
At the deficiencies in the prior art, the invention provides the preparation method of fluorine alkene ether, this method is avoided the Pintsch process route, high conversion prepare the fluorine-containing alkene ether monomer that contains carboxyl (perhaps aftertreatment can be converted into carboxyl), acyl fluorides monomer and the addition reaction of trifluoro vinyl sulfuric ester that has ester group end group (can be converted into carboxyl after the processing) adopted in this invention, do not add any organic solvent in the reaction process, two kinds of reaction liquid mass polymerizations, directly prepare fluorine-containing alkene ether monomer, these fluorine-containing alkene ether monomers are separated to obtain highly purified monomer by rectifying column.Can be applicable to polyreaction, prepare the resin that meets the demands.
Technical scheme of the present invention is as follows:
The preparation method of fluorine alkene ether, this method comprises that fluorine-containing straight or branched acyl fluorides compound supports under the fluoride salt catalyst action and the addition reaction of trifluoro vinyl sulfuric ester body at gac, keep temperature of reaction at 0～100 ℃, form product with the general formula shown in the formula (I).
CF
2＝CF-O-R
f (I)
In the formula: R
fFor having the monomer of structure shown in the following general formula:
R=-COOCH
3Perhaps-OCH
3
In the formula: the integer of the integer of a=1～3, b=0～3.Preferred b=0 or 1; The integer of a=1-3.
Described fluorine-containing straight or branched acyl fluorides structural general formula is:
R=-COOCH
3Perhaps-OCH
3The integer of the integer of a=1～3, b=0～3.
The general structure of described trifluoro vinyl sulfuric ester is:
The described preparation method who contains fluroxene, concrete reaction formula general formula is as follows:
R=-COOCH
3Perhaps-OCH
3
In the following formula-CH
3Can be replaced by alkyl, substituted alkyl, phenyl or substituted-phenyl.The alkyl or the substituted alkyl of preferred 1～20 carbon atom of described alkyl or substituted alkyl.With the containing fluroxene and can use method of the present invention preparation of similar of the present invention.
The above-mentioned described preparation method who contains fluroxene, the reaction molar ratio that is perfluor straight or branched acyl fluorides compound and trifluoro vinyl sulfuric ester is (1-1.1): 1, adopting gac to support fluoride salt in the reaction process is catalyzer, the body addition reaction under the solvent-free existence.By rectifying separation purifying functional fluorine-bearing alkene ether monomer.
The above-mentioned described gac that adopts in reaction process supports basic metal and fluoridizes salt, and basic metal is fluoridized salt and is selected from one or several mixture in cesium fluoride, Potassium monofluoride, the Sodium Fluoride.Also can use other carriers to replace gac, described carrier includes but not limited to aluminum oxide, silica gel, float stone and/or diatomite.Its preparation method and gac of the present invention support basic metal and fluoridize salt seemingly.
The Preparation of catalysts method is: alkaline metal fluoride cpd is dissolved in the deionized water, be mixed with saturated aqueous solution, dry activated carbon is added the solution that absorbs preparation in the entry, remove by filter redundant moisture thereafter, fluoridize the gac of salt and place 200-450 ℃ retort furnace internal heating drying treatment having absorbed basic metal, treatment time is 12～72h, after disposing, moves in the drying plant and stores for future use.Gac supports and contains basic metal in the fluoride salt catalyzer and fluoridize the mole total amount of salt at 0.01-5mol/g.
The above-mentioned described preparation method who contains fluroxene is to keep temperature of reaction at 0～100 ℃, and preferable reaction temperature is 10～50 ℃ and reacts.
The preparation method of described fluorine alkene ether of the present invention, avoid adopting the Pintsch process route, employed trifluoro vinyl sulfuric ester can be to prepare up to the yield more than 95%, the directly body addition reaction under catalyst action of various functional acyl fluorides monomers and trifluoro vinyl sulfuric ester is adopted in this invention, under the solvent-free existence, directly body addition, prepare various functional fluorine-bearing alkene ether monomers, these functional fluorine-bearing alkene ether monomers are separated to obtain highly purified monomer by rectifying column.With this monomer and tetrafluoroethylene copolymerization, be and have functional resin.
Body addition reaction of the present invention belongs to the inside group permutoid reaction of two kinds of fluid molecules under catalyst action, product remains liquid, the problem that does not exist system viscosity to increase, do not adopt any organic solvent in the system, effectively improved the utilization ratio of conversion unit, improve product purity, avoided separating environmental pollution, the elimination recovery energy dissipation problem that organic solvent caused that the organic solvent lock causes.
Embodiment
The present invention is described by the following examples, but does not limit the present invention.
The trifluoro vinyl sulfuric ester that the present invention is adopted in building-up process can prepare according to techniques well known, and the preparation method that the present invention recommends is referring to Angew.Chem.internat.Edit.Vol.11 (1972) No.7,590.
All kinds of acyl fluorides raw materials with function end group with the reaction of trifluoro vinyl sulfuric ester that the present invention is adopted in building-up process can be bought and obtain, and also can prepare by approach well known, and the preparation method the present invention that can Gong select for use will describe by embodiment.
The methoxyl group tetrafluoro methyl propionate (molecular formula: CH that the present invention is adopted in building-up process
3OCF
2CF
2COOCH
3) raw material can buy and obtain, and also can prepare by approach well known, the preparation method that the present invention recommends is referring to United States Patent (USP) U.S.Pat.2988537.
The basic metal that the present invention is adopted in building-up process is fluoridized salt (cesium fluoride, Potassium monofluoride, Sodium Fluoride) and gac and all can be bought and obtain.
Embodiment 1: Preparation of catalysts
In disposing the 250ml wide-necked bottle of stirring rake, add in the 50g deionized water and the 200g cesium fluoride, be stirred to whole dissolvings, mix, the 10g dry activated carbon is added in the above-mentioned solution, after fully mixing absorption 30min-1hr, remove by filter redundant moisture, the gac that has absorbed cesium fluoride is placed 400 ℃ retort furnace internal heating drying treatment, the treatment time is 48hr, after disposing, move in the drying plant and store for future use.Know that after tested cesium fluoride all is carried in the gac, the ratio of cesium fluoride in gac is: 0.132mol/g.
Embodiment 2: the preparation of mixed catalyst
In disposing the 500ml wide-necked bottle of stirring rake, add in the 100g deionized water, the 100g cesium fluoride, 50g Potassium monofluoride and 2g Sodium Fluoride are stirred to whole dissolvings, mix, and the 10g dry activated carbon is added in the above-mentioned solution, after fully mixing absorption 30min-1hr, remove by filter redundant moisture, the gac that has absorbed fluoride salt is placed 300 ℃ retort furnace internal heating drying treatment, the treatment time is 60hr, after disposing, move in the drying plant and store for future use.Know that after tested fluoride salt all is carried in the gac, the ratio of fluoride salt in gac is: 0.157mol/g.
Embodiment 3:
The circulation cooling/heating systems to be equipped with, temperature controlling system, the 10L stainless steel autoclave of charging system is cleaned and thorough drying, in still, add and support the cesium fluoride catalyzer by the 110g Preparation of Activated Carbon, wherein the molar content of cesium fluoride in gac is 0.15mol/g, reactor vacuumized thereafter, inflated with nitrogen displacement three times, until Control for Oxygen Content below 10ppm, be evacuated to-0.1MPa, in system, add trifluoro vinyl sulfuric ester 2940g, stir temperature control at 10 ℃, slowly drip the fluorine-containing propionyl fluoride of 3-methoxycarbonyl (molecular formula: CH by charging system
3OOCCF
2COF) 2340g, controlled temperature remain between 10 ± 1 ℃ and get final product, and after dropwising, constant temperature stirred after two hours, stop to stir, and cooling is directly put into rectifying tower by filtration unit with the water white transparency material and carried out the rectifying purifies and separates.
Product yield is more than 90%, the product after the separation the capillary chromatographic column build-in test as a result purity more than 99.9%, molecular composition C
6H
3F
7O
3, test through ultimate analysis: the carbon percentage composition is 28.14%, the protium percentage composition is 1.18%, oxygen element content 18.74%; In the IR spectrogram: 1782cm
-1For in the ester group-C=O vibration; 1842cm
-1For-CF=CF
2Vibration causes; Product boiling point normal pressure is down for 47-52 ℃.Be a=1 of the present invention, b=0, R=-COOCH
3The time compound.
Embodiment 4:
The circulation cooling/heating systems to be equipped with, temperature controlling system, the 10L stainless steel autoclave of charging system is cleaned and thorough drying, in still, add 70g and support the Potassium monofluoride catalyzer by Preparation of Activated Carbon, wherein the molar content of Potassium monofluoride in gac is 0.26mol/g, reactor vacuumized thereafter, inflated with nitrogen displacement three times, until Control for Oxygen Content below 10ppm, be evacuated to-0.1MPa, in system, add trifluoro vinyl sulfuric ester 2950g, stir temperature control at 15 ℃, slowly drip the fluorine-containing butyryl fluorine (molecular formula: CH of 4-methoxycarbonyl by charging system
3OOCCF
2CF
2COF) 3090g, controlled temperature remain between 15 ± 1 ℃ and get final product, and after dropwising, constant temperature stirred after two hours, stop to stir, and cooling is directly put into rectifying tower by filtration unit with the water white transparency material and carried out the rectifying purifies and separates.
Product yield is more than 88%, the product after the separation the capillary chromatographic column build-in test as a result purity more than 99.9%, molecular composition C
7H
3F
9O
3, test through ultimate analysis: the carbon percentage composition is 27.47%, the protium percentage composition is 0.99%, oxygen element content 15.68%; In the IR spectrogram: 1782cm
-1For in the ester group-C=O vibration; 1842cm
-1For-CF=CF
2Vibration causes; Product boiling point normal pressure is down for 59-65 ℃.Be a=2 of the present invention, b=0, R=-COOCH
3The time compound.
Embodiment 5:
The circulation cooling/heating systems to be equipped with, temperature controlling system, the 10L stainless steel autoclave of charging system is cleaned and thorough drying, in still, add the support cesium fluoride of 85g by Preparation of Activated Carbon, the Potassium monofluoride mixed catalyst, wherein cesium fluoride and Potassium monofluoride total molar content in gac is 0.18mol/g, reactor vacuumized thereafter, inflated with nitrogen displacement three times, until Control for Oxygen Content below 10ppm, be evacuated to-0.1MPa, in system, add trifluoro vinyl sulfuric ester 1960g, stir temperature control at 20 ℃, slowly drip the fluorine-containing propoxy-propionyl fluoride (molecular formula: CH of 6-methoxycarbonyl by charging system
3OOCCF
2CF
2OCF (CF
3) COF) 3230g, controlled temperature remains between 20 ± 1 ℃ and gets final product, and after dropwising, constant temperature stirred after two hours, stopped to stir, and cooling is directly put into rectifying tower by filtration unit with the water white transparency material and is carried out the rectifying purifies and separates.
Total yield of products is more than 85%, the product after the separation the capillary chromatographic column build-in test as a result purity more than 99.9%, molecular composition C
9H
3F
13O
4, test through ultimate analysis: the carbon percentage composition is 25.61%, the protium percentage composition is 0.72%, oxygen element content 15.16%; In the IR spectrogram: 1782cm
-1For in the ester group-C=O vibration; 1842cm
-1For-CF=CF
2Vibration causes; 1200cm
-1And 1148cm
-1Two absorptions the strongest are caused by the CF vibration; 984cm
-1Be CF
3Vibration causes; Product boiling point normal pressure is down for 150-154 ℃.Be a=1 of the present invention, b=1, R=-COOCH
3The time compound.
Embodiment 6:
The circulation cooling/heating systems to be equipped with, temperature controlling system, the 10L stainless steel autoclave of charging system is cleaned and thorough drying, in still, add the cesium fluoride that supports by the 75g Preparation of Activated Carbon, Potassium monofluoride, the mixed catalyst of Sodium Fluoride, cesium fluoride wherein, Potassium monofluoride and Sodium Fluoride total molar content in gac is 0.25mol/g, reactor vacuumized thereafter, inflated with nitrogen displacement three times, until Control for Oxygen Content below 10ppm, be evacuated to-0.1MPa, in system, add trifluoro vinyl sulfuric ester 2950g, stir temperature control at 15 ℃, slowly drip the fluorine-containing valeryl fluorine (molecular formula: CH of 4-methoxycarbonyl by charging system
3OOCCF
2CF
2CF
2COF) 3860g, controlled temperature remain between 15 ± 1 ℃ and get final product, and after dropwising, constant temperature stirred after two hours, stop to stir, and cooling is directly put into rectifying tower by filtration unit with the water white transparency material and carried out the rectifying purifies and separates.
Product yield is more than 85%, the product after the separation the capillary chromatographic column build-in test as a result purity more than 99.9%, molecular composition C
8H
3F
11O
3, test through ultimate analysis: the carbon percentage composition is 26.98%, the protium percentage composition is 0.85%, oxygen element content 13.48%; In the IR spectrogram: 1782cm
-1For in the ester group-C=O vibration; 1842cm
-1For-CF=CF
2Vibration causes; Product boiling point normal pressure is down for 76-80 ℃.Be a=3 of the present invention, b=0, R=-COOCH
3The time compound.
Embodiment 7:
The circulation cooling/heating systems to be equipped with, temperature controlling system, the 10L stainless steel autoclave of charging system is cleaned and thorough drying, in still, add and support the cesium fluoride catalyzer by the 170g Preparation of Activated Carbon, wherein cesium fluoride total molar content in gac is 0.12mol/g, reactor vacuumized thereafter, inflated with nitrogen displacement three times, until Control for Oxygen Content below 10ppm, be evacuated to-0.1MPa, in system, add trifluoro vinyl sulfuric ester 3540g, stir temperature control at 15 ℃, slowly drip the fluorine-containing valeryl fluorine (molecular formula: CH of 4-methoxycarbonyl by charging system
3OOCCF
2CF
2CF
2COF) 4620g, controlled temperature remain between 15 ± 1 ℃ and get final product, and after dropwising, constant temperature stirred after two hours, stop to stir, and cooling is directly put into rectifying tower by filtration unit with the water white transparency material and carried out the rectifying purifies and separates.
Product yield is more than 86%, the product after the separation the capillary chromatographic column build-in test as a result purity more than 99.9%, molecular composition C
8H
3F
11O
3, test through ultimate analysis: the carbon percentage composition is 26.98%, the protium percentage composition is 0.85%, oxygen element content 13.48%; In the IR spectrogram: 1782cm
-1For in the ester group-C=O vibration; 1842cm
-1For-CF=CF
2Vibration causes; Product boiling point normal pressure is down for 76-80 ℃.Be a=3 of the present invention, b=0, R=-COOCH
3The time compound.
Embodiment 8:
The circulation cooling/heating systems to be equipped with, temperature controlling system, the 10L stainless steel autoclave of charging system is cleaned and thorough drying, in still, add and support the cesium fluoride catalyzer by the 170g Preparation of Activated Carbon, wherein cesium fluoride total molar content in gac is 0.12mol/g, reactor vacuumized thereafter, inflated with nitrogen displacement three times, until Control for Oxygen Content below 10ppm, be evacuated to-0.1MPa, in system, add trifluoro vinyl sulfuric ester 3540g, stir temperature control at 15 ℃, slowly drip 3-methoxyl group perfluoro-propionyl fluoride (molecular formula: CH by charging system
3OCF
2CF
2COF) 3210g, controlled temperature remain between 15 ± 1 ℃ and get final product, and after dropwising, constant temperature stirred after two hours, stop to stir, and cooling is directly put into rectifying tower by filtration unit with the water white transparency material and carried out the rectifying purifies and separates.
Product yield is more than 90%, the product after the separation the capillary chromatographic column build-in test as a result purity more than 99.9%, molecular composition C
6H
3F
9O
2, test through ultimate analysis: the carbon percentage composition is 25.92%, the protium percentage composition is 1.09%, oxygen element content 11.51%; In the IR spectrogram: 1842cm
-1For-CF=CF
2Vibration causes; 2960cm
-1For-CH
3The antisymmetric stretching vibration absorption peak, 2875cm
-1For-CH
3The symmetrical stretching vibration absorption peak; Product boiling point normal pressure is down for 46-48 ℃.Be a=2 of the present invention, b=0, R=-OCH
3The time compound.
Claims (7)
1. the preparation method of a class fluroxene, this method comprises that fluorine-containing straight or branched acyl fluorides compound and trifluoro vinyl sulfuric ester support basic metal at gac and fluoridize bulk reaction in the presence of the salt, keep temperature of reaction at 0～100 ℃, form as shown in the formula the product shown in (I):
CF
2＝CF-O-R
f (I)
Wherein: R
fFor having the monomer of structure shown in the following general formula:
R=-COOCH
3Perhaps-OCH
3
In the formula: the integer of the integer of a=1～3, b=0～3;
Described fluorine-containing straight or branched acyl fluorides structural general formula is:
R=-COOCH
3Perhaps-OCH
3, the integer of the integer of a=1～3, b=0～3 wherein;
The structural formula of described trifluoro vinyl sulfuric ester is:
Basic metal is fluoridized salt and is selected from one or several mixture in cesium fluoride, Potassium monofluoride, the Sodium Fluoride.
2. the preparation method of fluroxene as claimed in claim 1 is characterized in that general formula R
fDescribed in b=0 or 1 in the structure; The integer of a=1～3.
3. the preparation method of fluroxene as claimed in claim 1, it is characterized in that, gac supports basic metal and fluoridizes the preparation method of salt and be: alkaline metal fluoride cpd is dissolved in the deionized water, be mixed with saturated aqueous solution, dry activated carbon is added the solution that absorbs preparation in the entry, remove by filter redundant moisture thereafter, fluoridize the gac of salt and place 200-450 ℃ retort furnace internal heating drying treatment having absorbed basic metal, treatment time is 12-72h, after disposing, move in the drying plant and store for future use.
4. the preparation method of fluroxene as claimed in claim 1 is characterized in that gac supports basic metal and fluoridizes and contain basic metal in the salt and fluoridize the mole total amount of salt at 0.01-5mol/g.
5. as the preparation method of claim 1 or 4 described fluroxenes, it is characterized in that gac supports basic metal and fluoridizes and contain basic metal in the salt and fluoridize the mole total amount of salt at 0.1-0.5mol/g.
6. the preparation method of fluroxene as claimed in claim 1 is characterized in that described perfluor straight or branched acyl fluorides compound and trifluoro vinyl sulfuric ester support basic metal at gac and fluoridize in the presence of the salt, the solution bulk reaction, and temperature of reaction is 10-50 ℃.
7. the preparation method of fluroxene as claimed in claim 1 is characterized in that the reaction molar ratio of described perfluor straight or branched acyl fluorides compound and trifluoro vinyl sulfuric ester is (1-1.1): 1, and by rectifying separation purifying functional fluorine-bearing alkene ether monomer.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4281092A (en) * | 1978-11-30 | 1981-07-28 | E. I. Du Pont De Nemours And Company | Vulcanizable fluorinated copolymers |
| CN1520393A (en) * | 2001-06-29 | 2004-08-11 | ������������ʽ���� | Process for producing fluorinated vinyl ether |
-
2009
- 2009-10-26 CN CN200910229448XA patent/CN101698644B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4281092A (en) * | 1978-11-30 | 1981-07-28 | E. I. Du Pont De Nemours And Company | Vulcanizable fluorinated copolymers |
| CN1520393A (en) * | 2001-06-29 | 2004-08-11 | ������������ʽ���� | Process for producing fluorinated vinyl ether |
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