CN102702035A - Method for continuously preparing fluorinated vinyl ether - Google Patents
Method for continuously preparing fluorinated vinyl ether Download PDFInfo
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- CN102702035A CN102702035A CN2012101932540A CN201210193254A CN102702035A CN 102702035 A CN102702035 A CN 102702035A CN 2012101932540 A CN2012101932540 A CN 2012101932540A CN 201210193254 A CN201210193254 A CN 201210193254A CN 102702035 A CN102702035 A CN 102702035A
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- vinyl ether
- fluorinated vinyl
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Abstract
The invention discloses a method for continuously preparing fluorinated vinyl ether. Anhydrous carbonate and 2-alkoxy propionyl fluoride are continuously added to a twin-screw extruder according to a molar ratio of 2 to 10:1, are subjected to a salt-forming reaction at a salt-forming section of the twin-screw extruder, and subjected to a decarboxylation reaction at a decarboxylation section to obtain the fluorinated vinyl ether, wherein the starting temperature of the salt-forming section is 60 to 90 DEG C, the final temperature is 180 to 204 DEG C, the temperature is increasingly distributed at a gradient of 0 to 30 DEG C/10cm along with the direction of travel of the materials, the temperature of the decarboxylation section is 180 to 320 DEG C, and the total residence time of the salt-forming reaction and the decarboxylationreaction is 2 to 8min by controlling the extrusion rate of the twin-screw extruder. The method provided by the invention has the advantages of short process flow, continuous operation, good reaction mass transfer and heat transfer, high reaction conversion rate and the like, and the conversion rate is up to 88.2%.
Description
Technical field
The present invention relates to the preparation method of fluorinated vinyl ether, particularly a kind of method of utilizing twin screw extruder to prepare fluorinated vinyl ether continuously.
Background technology
Fluorinated ethylene base ether is the important comonomer of organic fluorine material, and main effect is to be incorporated into the functional groups chain in the polymkeric substance, improves or strengthen the performance of some aspect of polymkeric substance.
According to bibliographical information, the fluorinated vinyl ether synthetic technology mainly contains following two kinds at present:
1) directly salify, decarboxylic reaction obtain fluorinated vinyl ether in fixed-bed reactor, tubular reactor or fluidized-bed to make 2-alkoxypropionyl fluoride and carbonate.Such technology is earlier carbonate to be placed reactor drum; Add the reaction of 2-alkoxypropionyl fluoride again; Like Chinese patent publication number CN101213168A, open day on July 2nd, 2008, denomination of invention: the preparation method of fluorinated vinyl ether; This application case discloses a kind of method for preparing fluorinated vinyl ether in the following manner, and said mode is: 2-alkoxypropionyl fluoride and metal carbonate are reacted in temperature is higher than the agitated bed reactor of decarboxylation temperature of intermediate carboxylate.Said method is under the condition that does not have solvent, to implement.This invents described method, can obtain highly purified fluorinated vinyl ether with high-throughout mode.Weak point is to realize the continuously feeding of carbonate; The mass transfer of temperature controlling, reaction, the difficulty of conducting heat, reaction product in time spreads out of than difficulty, and reaction heat can not effectively shift; Side reactions such as disproportionation reaction make to be prone to take place, and cause that reaction yield is low, the not high shortcoming of selectivity.
Earlier the 2-alkoxypropionyl fluoride is accomplished under the temperature of the decomposition temperature that is lower than its salt-forming reaction thing with metal carbonate and mixed salify, the elevated temperature decarboxylic reaction produces fluorinated vinyl ether again.Like Chinese patent publication number CN1520393A, open day on August 11st, 2004, denomination of invention: the preparation method of fluorinated vinyl ether, this invention provide through simple operations from have ester group as the hydroxy-acid group precursor, or as the SO of sulfonic acid group precursor
2The acid fluoride of F is made the method for fluorinated vinyl ether with high yield.Weak point is to exist operation steps many, can not continuous production etc. shortcoming, simultaneously because the existence of solvent also exists side reaction to increase phenomenons such as (for example, the HF affixtures of fluorinated vinyl ether).
Summary of the invention
The present invention is directed to the weak point of prior art, provide that a kind of technology is simple, yield is high, cost is low, the continuous preparation method of the fluorinated vinyl ether of energy-conserving and environment-protective.
In order to solve the problems of the technologies described above; The technical scheme that the present invention adopts is: a kind of continuous preparation method of fluorinated vinyl ether; Be that 2~10:1 adds anhydrous carbonate and 2-alkoxypropionyl fluoride continuously to twin screw extruder in molar ratio; Through twin screw extruder salify section be carried out to reactant salt, the decarboxylation section is carried out decarboxylic reaction and is obtained fluorinated vinyl ether, said salify section starting temperature is 60~90 ℃, terminal temperature is 180~204 ℃; And the gradient rising that is 20~30 ℃/10cm with the material direct of travel distributes; Decarboxylation section temperature is 180~320 ℃, and through control twin screw extruder rate of extrusion, the total residence time that makes salt-forming reaction and decarboxylic reaction is 2~8min.
Further:
Described carbonate is yellow soda ash or salt of wormwood.
Described 2-alkoxypropionyl fluoride is by general formula X-(O-Y)
a-O-CF (CF
3) COF representes, wherein, it is 1 to 3 C that X is selected from n
nF
2n+1Or FSO
2(C
2F
4); It is 1 to 3 C that Y is selected to p
PF
2PA is 0 to 2.
Described 2-alkoxypropionyl fluoride is selected from FSO
2CF
2CF
2OCF (CF
3) CF
2OCF (CF
3) COF, FSO
2CF
2CF
2OCF (CF
3) COF, FSO
2CF
2CF
2(OCF (CF
3) CF
2)
2OCF (CF
3) COF, CF
3CF
2CF
2OCF (CF
3) COF, CF
3OCF (CF
3) a kind of among the COF.
Described salify segment length is 40~55cm, and all the other are the decarboxylation section.
The mol ratio of described 2-alkoxypropionyl fluoride and anhydrous carbonate is 3~8:1.
Described salify section starting temperature is 70~80 ℃, and terminal temperature is 190~200 ℃, and is the gradient rising distribution of 25 ℃/10cm with the material direct of travel.
Described decarboxylation temperature is 190~270 ℃.
The total residence time of described salt-forming reaction and decarboxylic reaction is 3~6min.
The present invention utilizes twin screw extruder to be salify, decarboxylic reaction device; 2-alkoxypropionyl fluoride and anhydrous carbonate are raw material; With solid continuous charging device control carbonate feed rate; With microprocessor pump drive control 2-alkoxypropionyl fluoride feed rate, shear the mixing of accomplishing anhydrous metal carbonate and 2-alkoxypropionyl fluoride through the rotation of screw rod, and realize that continuous decarboxylic reaction prepares fluorinated vinyl ether.
Among the present invention, the salt-forming reaction of 2-alkoxypropionyl fluoride and carbonate is carried out in the salify section of twin screw extruder, and decarboxylic reaction carries out in the decarboxylation section of twin screw extruder; Said salify section is meant that temperature on the twin screw extruder is 60~204 ℃ interval, and the decarboxylation section is meant that temperature is in 180~320 ℃ interval; Described salify segment length is 40~55cm, and all the other are the decarboxylation section.
The kind of carbonate is different, causes carbonate different with the organic carboxyl acid salify thing that the reaction of 2-alkoxypropionyl fluoride obtains.Usually the sylvite of organic carboxyl acid is solid-state under decarboxylation temperature, and the sodium salt of organic carboxyl acid is the heavy-gravity fused solution under decarboxylation temperature.Organic carboxylate is more or less freely in solid-state following decarboxylation meeting, and under molten state, can have more serious mass transfer problem, thereby causes the side reaction aggravation, reduces reaction preference.But because the purity of salt of wormwood is often lower than yellow soda ash, and price wants high, makes to utilize salt of wormwood to substitute yellow soda ash also and may not be certain to produce better economy.In the present invention, owing to adopted twin screw extruder, make its heat transfer, mass-transfer performance obtain tangible improvement, so carbonate both can select salt of wormwood, also can select yellow soda ash as reactor drum with good cutting performance.
Salt-forming reaction need provide certain energy, and temperature is low excessively, can cause salt-forming reaction speed slow, makes that the length of salify section is very long, or the prolongation of salify required time, even salt-forming reaction can't be carried out; Temperature is too high then may to be caused the vaporization of 2-alkoxypropionyl fluoride or can cause the limit to become the phenomenon of Yanbian decarboxylation to take place, and causes that the material contact is inhomogeneous, makes salify incomplete, reduces product yield; The salify temperature raises the major cause that distributes for can make the 2-alkoxypropionyl fluoride under lower temperature, accomplish salt-forming reaction in gradient with the material direct of travel, makes material accomplish warm simultaneously, so that descend to go on foot decarboxylic reaction.Therefore, it is 60~90 ℃ that the present invention selects salify section starting temperature, is preferably 70~80 ℃; Terminal temperature is 180~204 ℃, is preferably 190~200 ℃; And be 20~30 ℃/10cm with the material direct of travel, the gradient that is preferably 25 ℃/10cm raises and distributes.
Decarboxylation temperature is low, can make decarboxylic reaction speed slow, makes that the length of decarboxylation section is very long, maybe need prolong the reaction times; Decarboxylation temperature is low excessively, also can cause decarboxylic reaction to carry out smoothly; And decarboxylation temperature is too high, then can cause side reactions such as disproportionation reaction, causes reaction preference to descend, problems such as the difficult control of reaction.Therefore, the present invention selects the temperature of decarboxylation section at 180~320 ℃, preferred 190~270 ℃.
The residence time of material in twin screw extruder is too short, and decarboxylation is incomplete, causes the transformation efficiency of 2-alkoxypropionyl fluoride low; Reaction time is oversize, be prone to take place side reactions such as material pyrolytic decomposition, and reaction efficiency is lower.Therefore, the total residence time that the present invention is chosen to reactant salt and decarboxylic reaction is 2~8min, is preferably 3~6min.
The mol ratio of 2-alkoxypropionyl fluoride and anhydrous carbonate is low more, and then the salify transformation efficiency of 2-alkoxypropionyl fluoride is high more, and the selectivity of 2-alkoxypropionyl fluoride is also high more.But mol ratio is low excessively, can cause the waste of carbonate, causes the increase of cost and the increase of useless solid amount.So it is 2~10:1 that the present invention selects not have the mol ratio of 2-alkoxypropionyl fluoride and anhydrous carbonate, preferred 3~8:1.
In addition, the moisture content in the material carbon hydrochlorate also is one of important factor that influences decarboxylic reaction.Because the existence of moisture content causes the generation of side reaction easily, generates hydrogenous by product, polymer properties descends when causing the follow-up polymerization of fluorinated vinyl ether.Therefore to select anhydrous carbonate be raw material in the present invention.
Advantage of the present invention is: make that the salt-forming reaction of anhydrous carbonate and 2-alkoxypropionyl fluoride and the decarboxylic reaction of salt thereof are carried out in twin screw extruder continuously; Effectively solve mass transfer, the heat transfer problem in the reaction, improved the transformation efficiency and the reaction preference of reaction.It is short to have technical process, but operate continuously reaction mass transfer, conduct heat, the reaction conversion ratio advantages of higher, transformation efficiency is up to 88.2%.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
As shown in the figure: 1 is solid feed inlet, and 2 is the liquid charging opening, and 3 is the salify section, and 4 are the decarboxylation section.
Embodiment
Below through accompanying drawing and embodiment the present invention is further elaborated, but the present invention is not limited to described embodiment.
CTE-SC-25 type twin screw extruder (the screw diameter 25mm that the present invention uses Nanjing Pohle agate mechanical means ltd to produce; Length-to-diameter ratio 48), CTE-SC-25 type twin screw extruder mainly comprises drive-motor, shaft coupling, wheel casing, solid charging system, mixing and conveying system, exhaust system, screw rod, machine barrel and machine barrel well heater outward etc.; For being applicable to this technology, the present invention has increased the liquid charging opening newly to the twin screw extruder of purchasing.
Embodiment 1
Utilize solid continuous charging device to add soda ash light continuously, utilize microprocessor pump drive to add FSO continuously simultaneously to the liquid charging opening 2 of twin screw extruder to the solid feed inlet 1 of twin screw extruder
2CF
2CF
2OCF (CF
3) CF
2OCF (CF
3) COF; The length of salify section 3 is 48cm, and all the other are decarboxylation section 4; The starting temperature of control salify section 3 is 60 ℃, and terminal temperature is 204 ℃, and is the gradient rising of 30 ℃/10cm with the material direct of travel; The minimum temperature of control decarboxylation section 4 is 204 ℃, and top temperature is 230 ℃; Control FSO
2CF
2CF
2OCF (CF
3) CF
2OCF (CF
3) raw materials components mole ratio of COF and yellow soda ash is 8:1; Through control twin screw extruder rate of extrusion, the total residence time that makes salt-forming reaction and decarboxylic reaction is 6min, condensation and collection FSO
2CF
2CF
2OCF (CF
3) CF
2-OCF=CF
2, based on FSO
2CF
2CF
2OCF (CF
3) CF
2OCF (CF
3) yield of COF is 77.3%.
Utilize solid continuous charging device to add Anhydrous potassium carbonate continuously, utilize microprocessor pump drive to add FSO continuously simultaneously to the liquid charging opening 2 of twin screw extruder to the solid feed inlet 1 of twin screw extruder
2CF
2CF
2OCF (CF
3) COF; The length of salify section 3 is 45cm, and all the other are decarboxylation section 4; The starting temperature of control salify section 3 is 90 ℃, and terminal temperature is 180 ℃, and is the gradient rising of 20 ℃/10cm with the material direct of travel; The minimum temperature of control decarboxylation section 4 is 180 ℃, and top temperature is 300 ℃; Control FSO
2CF
2CF
2OCF (CF
3) COF and salt of wormwood raw materials components mole ratio be 10:1; Through control twin screw extruder rate of extrusion, the total residence time that makes salt-forming reaction and decarboxylic reaction is 2min, condensation and collection bullion FSO
2CF
2CF
2OCF=CF
2, based on FSO
2CF
2CF
2OCF (CF
3) yield of COF is 83.7%.
Utilize solid continuous charging device to add Anhydrous potassium carbonate continuously, utilize microprocessor pump drive to add FSO continuously simultaneously to the liquid charging opening 2 of twin screw extruder to the solid feed inlet 1 of twin screw extruder
2CF
2CF
2(OCF (CF
3) CF
2)
2OCF (CF
3) COF; The length of salify section 3 is 50cm, and all the other are decarboxylation section 4; The starting temperature of control salify section 3 is 90 ℃, and terminal temperature is 190 ℃, and is the gradient rising of 20 ℃/10cm with the material direct of travel; The minimum temperature of control decarboxylation section 4 is 190 ℃, and top temperature is 230 ℃, control FSO
2CF
2CF
2(OCF (CF
3) CF
2)
2OCF (CF
3) COF and Anhydrous potassium carbonate raw materials components mole ratio be 3:1; Through control twin screw extruder rate of extrusion, the total residence time that makes salt-forming reaction and decarboxylic reaction is 3min, condensation and collection bullion FSO
2CF
2CF
2(OCF (CF
3) CF
2)
2OCF=CF
2, based on FSO
2CF
2CF
2(OCF (CF
3) CF
2)
2OCF (CF
3) yield of COF is 78.6%.
Embodiment 4
Utilize solid continuous charging device to add soda ash light continuously, utilize microprocessor pump drive to add CF continuously simultaneously to the liquid charging opening 2 of twin screw extruder to the solid feed inlet 1 of twin screw extruder
3CF
2CF
2OCF (CF
3) COF; The length of salify section 3 is 45cm, and all the other are decarboxylation section 4; The starting temperature of control salify section 3 is 90 ℃, and terminal temperature is 180 ℃, and is the gradient rising of 20 ℃/10cm with the material direct of travel; The minimum temperature of control decarboxylation section 4 is 180 ℃, and top temperature is 270 ℃; Control CF
3CF
2CF
2OCF (CF
3) COF and soda ash light raw materials components mole ratio be 2:1; Through control twin screw extruder rate of extrusion, the total residence time that makes salt-forming reaction and decarboxylic reaction is 5min, condensation and collection bullion CF
3CF
2CF
2OCF=CF
2, based on CF
3CF
2CF
2OCF (CF
3) the COF yield is 72.9%.
Embodiment 5
Utilize solid continuous charging device to add soda ash light continuously, utilize microprocessor pump drive to add CF continuously simultaneously to the liquid charging opening 2 of twin screw extruder to the solid feed inlet 1 of twin screw extruder
3OCF (CF
3) COF; The length of salify section 3 is 48cm, and all the other are decarboxylation section 4; The starting temperature of control salify section 3 is 60 ℃, and terminal temperature is 204 ℃, and is the gradient rising of 30 ℃/10cm with the material direct of travel; The minimum temperature of control decarboxylation section 4 is 204 ℃, and top temperature is 250 ℃; Control CF
3OCF (CF
3) COF and soda ash light raw materials components mole ratio be 6:1; Through control twin screw extruder rate of extrusion, the total residence time that makes salt-forming reaction and decarboxylic reaction is 8min, condensation and collection bullion CF
3OCF=CF
2, based on CF
3OCF (CF
3) yield of COF is 88.2%.
Claims (9)
1. the continuous preparation method of a fluorinated vinyl ether; It is characterized in that being that 2~10:1 adds anhydrous carbonate and 2-alkoxypropionyl fluoride continuously to twin screw extruder in molar ratio; Through twin screw extruder salify section be carried out to reactant salt, the decarboxylation section is carried out decarboxylic reaction and is obtained fluorinated vinyl ether, said salify section starting temperature is 60~90 ℃, terminal temperature is 180~204 ℃; And the gradient rising that is 20~30 ℃/10cm with the material direct of travel distributes; Decarboxylation section temperature is 180~320 ℃, and through control twin screw extruder rate of extrusion, the total residence time that makes salt-forming reaction and decarboxylic reaction is 2~8min.
2. the continuous preparation method of fluorinated vinyl ether according to claim 1 is characterized in that described carbonate is yellow soda ash or salt of wormwood.
3. the continuous preparation method of fluorinated vinyl ether according to claim 1 is characterized in that described 2-alkoxypropionyl fluoride is by general formula X-(O-Y)
a-O-CF (CF
3) COF representes, wherein, it is 1 to 3 C that X is selected from n
nF
2n+1Or FSO
2(C
2F
4); It is 1 to 3 C that Y is selected to p
PF
2PA is 0 to 2.
4. the continuous preparation method of fluorinated vinyl ether according to claim 3 is characterized in that described 2-alkoxypropionyl fluoride is selected from FSO
2CF
2CF
2OCF (CF
3) CF
2OCF (CF
3) COF, FSO
2CF
2CF
2OCF (CF
3) COF, FSO
2CF
2CF
2(OCF (CF
3) CF
2)
2OCF (CF
3) COF, CF
3CF
2CF
2OCF (CF
3) COF, CF
3OCF (CF
3) a kind of among the COF.
5. the continuous preparation method of fluorinated vinyl ether according to claim 1 is characterized in that described salify segment length is 40~55cm, and all the other are the decarboxylation section.
6. the continuous preparation method of fluorinated vinyl ether according to claim 1, the mol ratio that it is characterized in that said 2-alkoxypropionyl fluoride and anhydrous carbonate is 3~8:1.
7. the continuous preparation method of fluorinated vinyl ether according to claim 1 is characterized in that described salify section starting temperature is 70~80 ℃, and terminal temperature is 190~200 ℃, and is the gradient rising distribution of 25 ℃/10cm with the material direct of travel.
8. the continuous preparation method of fluorinated vinyl ether according to claim 1 is characterized in that described decarboxylation temperature is 190~270 ℃.
9. the continuous preparation method of fluorinated vinyl ether according to claim 1, the total residence time that it is characterized in that described salt-forming reaction and decarboxylic reaction is 3~6min.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20220005775A (en) * | 2020-07-07 | 2022-01-14 | 한국화학연구원 | Method for preparing perfluoropropyl vinyl ether with high conversion rate |
CN114917855A (en) * | 2022-05-25 | 2022-08-19 | 金华永和氟化工有限公司 | Reaction system and method for continuously preparing perfluoroalkyl vinyl ether |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6114441A (en) * | 1997-07-25 | 2000-09-05 | E. I. Du Pont De Nemours And Company | Blends of grafted fluoropolymer and polyester |
CN1520393A (en) * | 2001-06-29 | 2004-08-11 | ������������ʽ���� | Process for producing fluorinated vinyl ether |
CN101213168A (en) * | 2005-06-30 | 2008-07-02 | 3M创新有限公司 | Method of making fluorinated vinyl ethers |
-
2012
- 2012-06-08 CN CN2012101932540A patent/CN102702035B/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6114441A (en) * | 1997-07-25 | 2000-09-05 | E. I. Du Pont De Nemours And Company | Blends of grafted fluoropolymer and polyester |
CN1520393A (en) * | 2001-06-29 | 2004-08-11 | ������������ʽ���� | Process for producing fluorinated vinyl ether |
CN101213168A (en) * | 2005-06-30 | 2008-07-02 | 3M创新有限公司 | Method of making fluorinated vinyl ethers |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20220005775A (en) * | 2020-07-07 | 2022-01-14 | 한국화학연구원 | Method for preparing perfluoropropyl vinyl ether with high conversion rate |
KR102477300B1 (en) | 2020-07-07 | 2022-12-13 | 한국화학연구원 | Method for preparing perfluoropropyl vinyl ether with high conversion rate |
CN114917855A (en) * | 2022-05-25 | 2022-08-19 | 金华永和氟化工有限公司 | Reaction system and method for continuously preparing perfluoroalkyl vinyl ether |
CN114917855B (en) * | 2022-05-25 | 2024-03-12 | 金华永和氟化工有限公司 | Reaction system and method for continuously preparing perfluoroalkyl vinyl ether |
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