CN1318366C - Trifluoro methyl-1, 1, 2-trifluoro-1, 2-dichloro-ethyl ether dechlorination reaction process - Google Patents
Trifluoro methyl-1, 1, 2-trifluoro-1, 2-dichloro-ethyl ether dechlorination reaction process Download PDFInfo
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Abstract
The present invention discloses a technological method for the preparation of perfluoro-(methyl vinyl) ether from trifluoromethyl-1, 1, 2-trifluoro-1, 2-dichloro-ethyl ether through dechlorination reactions. In the method, dimethylformamide is adopted as a solvent, or that iodine is added as an activator, and the raw monomers of the gas-phase perfluoro-(methyl vinyl) ether, which flow out of a reflux condenser, are collected in a dry icy-cold trap at-78 DEG C. The solvent system of the present invention ensures that a certain reaction rate of the dechlorination reaction can be kept from beginning to end without the activation of zinc powder and the dehydration pretreatment of the solvent, and thus, the present invention has the advantages of greatly shortened reaction time, simplified process flow and reduced production cost. In addition, the reaction yield of the present invention can reach 90 to 95%.
Description
Technical field:
The present invention relates to a kind of preparation method of fluorine cpd, concrete, the present invention relates to a kind of by Trifluoromethyl-1,1,2-three fluoro-1,2-two chloro-ethyl ether (CF
3OCClFCClF
2) by dechlorination reaction, preparation perfluor (methyl ethylene) ether (CF
3OCF=CF
2) processing method.
Background technology:
Trifluoromethyl-1,1,2-three fluoro-1,2-two chloro-ethyl ethers are particular compound very, it is by fluorine oxygen base trifluoromethane (CF
3OF) with 1,2-two chloro-1,2-difluoroethylene (CClF=CClF) makes through the gas phase addition reaction.Nineteen sixty-five, W.S.Durrell etc. are at J.Poly.Sci.Vol3, No12, and put down in writing in 4065 (1965) documents: this compound carries out dechlorination reaction with zinc powder in the presence of solvent, can make the most important monomer of extraordinary fluoropolymer---perfluor (methyl ethylene) ether.And solvent is selected for use and is strong polar organic solvent---dimethyl sulfoxide (DMSO) [molecular formula: (CH
3)
2SO is called for short DMSO], its chemical equation is as follows:
CF
3OCClFCClF
2+Zn-→CF
3OCF＝CF
2+ZnCl
2
In the above-mentioned document, this reaction not only narration is simple, and its productive rate only is 59.3% through adjusting.We find under study for action, according to this method, if with the zinc powder activation, simultaneously solvent DMSO is carried out processed, productive rate can be brought up to 60～80%.But, the poor repeatability of this method productive rate, its major cause is: the raw material Trifluoromethyl-1 of adding, 1,2-three fluoro-1,2-two chloro-ethyl ethers reduce gradually in reaction late phase reaction speed, even stop, and each test, speed of response is slowed down and opportunity of stopping is not quite similar again, so productive rate is low and poor repeatability; Dechlorination research to the DSMO solvent system is also found, not good as " addition " reaction, Trifluoromethyl-1 in the gained dechlorination raw material, 1, the dechlorination reaction situation was very poor when 2-three fluoro-1,2-Dichloroethyl ether content were low, as adopt rectifying, dechlorination raw material after the purification can improve reaction, but because the loss of rectifying, overall yield does not improve.Illustrate that this solvent system only is feasible, but be not preferable.As use the strong inadequately solvent of common polarity instead, effect is poorer, almost dechlorination reaction can not take place.
Summary of the invention:
The present invention is intended to overcome above-mentioned defective, seek a kind of new solvent system, this solvent embodies can make Trifluoromethyl-1, and 1,2-three fluoro-1, the dechlorination reaction of 2-two chloro-ethyl ethers and zinc powder carries out more thoroughly, the reactive behavior of system still can keep in the later stage, even also can handle some dechlorination raw material of content difference, finally realized high reaction yield, also save the activation of zinc powder and the dehydration pre-treatment of solvent simultaneously, thereby simplified technical process greatly.
Order of the present invention is to realize by implementing following technical scheme:
Trifluoromethyl-1,1,2-three fluoro-1,2-two chloro-ethyl ether dechlorination reaction process is characterized in that comprising the steps:
A, to select 4 mouthfuls of bottles be reaction vessel, at 4 bottlenecks agitator, feeder is set respectively, is connected with the reflux exchanger and the thermometer of-10～-22 ℃ of cold media.
Described cold medium is an industrial alcohol.
B, by thick dechlorination raw material: zinc powder: dimethyl formamide [molecular formula (CH
3)
2NCHO is called for short DMF]=1: 1.1～2.5: 3～5 mol ratio, respectively zinc powder, DMF are added in the reaction vessel earlier, or be incorporated as the iodine of zinc powder weight 0.5～2.5%, the thick dechlorination raw material of in feeder, packing into then again.
The water content of described DMF is 500ppm.
C, reaction vessel is warming up to 40～50 ℃, drip thick dechlorination raw material gradually, after waiting to spend the inductive phase of reaction in 10～30 minutes, the temperature of reaction vessel is reduced to 30～40 ℃, simultaneously thick dechlorination raw material is dropwised gradually, be warming up to 45～55 ℃ more gradually, make the dechlorination raw material that remains in the solvent react to finish as far as possible and be converted into CF
3OCF=CF
2Crude monomer.
D, gas phase perfluor (methyl ethylene) the ether crude monomer that will go out reflux exchanger are collected in-78 ℃ the dry ice cold-trap.
Perfluor (methyl ethylene) the ether crude monomer (b.p-23 ℃) that the present invention reacts generation can not be condensed when reflux exchanger, and unreacted Trifluoromethyl-1,1,2-three fluoro-1,2-two chloro-ethyl ethers (b.p37 ℃) can be returned reaction vessel by abundant condensation and continue reaction.
The present invention compared with prior art, its outstanding advantage is:
1, solvent system of the present invention has guaranteed that dechlorination reaction can keep certain reaction speed from start to finish, do not have significantly and reduce, and original DMSO solvent system is when carrying out dechlorination reaction, even processed is carried out in zinc powder activation and DMSO, the speed in its reaction later stage still can obviously reduce even stopped reaction, as not carrying out zinc powder activation and DMSO dehydration, can more early slow down or stopped reaction, productive rate is also lower.
2, the present invention need not zinc powder activation and solvent dehydration pre-treatment, thereby has shortened the reaction times greatly, has simplified production technique, has reduced production cost, and this reaction yield height, reaches 90～95%, has improved 10～40% than prior art.
3, the present invention can produce more foam for preventing to react in the late phase reaction container, be easy to the phenomenon of liquid flooding, added a spot of iodine, but do not add iodine to the reaction process did not influence, reaction still can continue to last stage reaction always, and do not resemble the DMSO system, can slow down even stop at the reaction late phase reaction, thereby influenced the productive rate that reacts.
Embodiment
Embodiment 1
Trifluoromethyl-1,1,2-three fluoro-1,2-two chloro-ethyl ether dechlorination reaction process is characterized in that comprising the steps:
In 4 mouthfuls of glass reaction bottles of 1O00ml, agitator, feeder are set respectively, are connected with the reflux exchanger and the thermometer of-10～-22 ℃ of cold media.
In the reaction flask bottle, add zinc powder 213 grams, the DMF477 gram.Add thick dechlorination raw material (content 70.0%) 386 grams in feeder, be connected with-15～-22 ℃ the cold medium of industrial alcohol in the reflux exchanger, rewinding dry ice cold-trap keeps-78 ℃ approximately of temperature.Reaction flask is warming up to about 42 ℃, drip thick dechlorination raw material gradually, gradually reduce temperature of reaction to 32～37 ℃ thereafter, continue to drip thick dechlorination raw material until dropwising, for preventing to react the more foam of appearance in the late phase reaction bottle, need evenly slowly to stir, again reaction flask is warming up to about 50 ℃ gradually, the dechlorination raw material that remains in the solvent has been reacted as far as possible.Go out in the dry ice cold-trap that is collected in-78 ℃ after gas phase perfluor (methyl ethylene) the ether crude monomer liquefaction of reflux exchanger.The entire reaction time is 4 hours 55 minutes.The result gets thick perfluor (methyl ethylene) ether 233 grams, purity 77.1%, and productive rate is 94.9%.
Embodiment 2
Trifluoromethyl-1,1,2-three fluoro-1,2-two chloro-ethyl ether dechlorination reaction process is characterized in that comprising the steps:
A, to select 4 mouthfuls of glass of 1000ml be reaction vessel, at 4 bottlenecks agitator, feeder is set respectively, is connected with the reflux exchanger and the thermometer of-10～-22 ℃ of cold media;
Described cold medium is an industrial alcohol.
B, elder generation add zinc powder 218 grams, DMF478 gram, iodine 2 grams in the reaction vessels respectively, then the thick dechlorination raw material of adding (content 70.0%) 368 grams in feeder.
The water content of described DMF is 500ppm.
C, reaction vessel is warming up to 42 ℃, drip thick dechlorination raw material gradually, after waiting in 10～15 minutes to spend the inductive phase of reaction, the temperature of reaction vessel is reduced to 32～37 ℃, simultaneously thick dechlorination raw material is dropwised, be warming up to 55 ℃ more gradually, the dechlorination raw material that remains in the solvent has been reacted as far as possible.
D, will go out in the dry ice cold-trap that is collected in-78 ℃ after gas phase perfluor (methyl ethylene) the ether crude monomer liquefaction of reflux exchanger.The result gets thick perfluor (methyl ethylene) ether 224 grams, purity 80.46%, and productive rate is 95.23%.
Reference examples 1
In above-mentioned 1000ml four-hole reaction flask, add zinc powder 300 grams, this zinc powder under agitation vacuumizes and is heated to 130～140 ℃, constantly with nitrogen replacement, find time, make zinc powder realize activating.To put into the molecular sieve airtight immersion a few days of its 1/3 weight approximately among the DMSO, dehydration reduces its water-content as far as possible.The DMSO 648 that adds after dewatering restrains to reaction flask.In feeder, add thick dechlorination raw material totally 602 grams (content 81.5%), condenser and the same example of cold-trap temperature control.Reaction flask is warming up to about 40 ℃, and beginning drips thick dechlorination raw material gradually, when beginning backflow is arranged, reduce temperature of reaction to 32～35 ℃ gradually, slowly continue again to drip thick dechlorination raw material, until dropwising, after dropwising, be warming up to more than 40 ℃, reaction finishes as far as possible.Reaction consuming time 18 hours 35 minutes altogether.Final that the thick perfluor of product (methyl ethylene) ether 327 restrains (content 70.6%), productive rate is 67.2%.
Reference examples 2
Zinc powder activation and solvent DMSO dehydration are with reference examples 1.Add zinc powder (needing activation) 318 grams in 1000ml four-hole reaction flask, DMSO 687 grams of dehydration add thick dechlorination raw material 602 grams (content 86.4%) in feeder, and condenser and rewinding cold-trap temperature control are the same, reinforced and all the same example of reaction process.Reaction lasts 15 hours 35 minutes altogether.Get the thick perfluor of product (methyl ethylene) ether 400 grams (content 72.3%), productive rate is 79.3%.
Claims (3)
1, Trifluoromethyl-1,1,2-three fluoro-1,2-two chloro-ethyl ether dechlorination reaction process is characterized in that comprising the steps:
A, to select 4 mouthfuls of bottles be reaction vessel, at 4 bottlenecks agitator, feeder is set respectively, is connected with the reflux exchanger and the thermometer of-10～-22 ℃ of cold media;
B, by thick dechlorination raw material: zinc powder: DMF=1: 1.1～2.5: 3～5 mol ratio adds zinc powder, DMF in the reaction vessel respectively earlier, or be incorporated as the iodine of zinc powder weight 0.5～2.5%, the thick dechlorination raw material of packing into then again in feeder;
C, reaction vessel is warming up to 40～50 ℃, drips thick dechlorination raw material gradually, after waiting to spend the inductive phase of reaction in 10～30 minutes, the temperature of reaction vessel is reduced to 30～40 ℃, simultaneously thick dechlorination raw material is dropwised, be warming up to 45～55 ℃ more gradually;
D, the gas phase perfluor ether crude monomer that will go out reflux exchanger are collected in-78 ℃ the dry ice cold-trap.
2, dechlorination reaction technology according to claim 1 is characterized in that described cold medium is an industrial alcohol.
3, dechlorination reaction technology according to claim 1, the water content that it is characterized in that described DMF is 500ppm.
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| CNB2005100220943A CN1318366C (en) | 2005-11-18 | 2005-11-18 | Trifluoro methyl-1, 1, 2-trifluoro-1, 2-dichloro-ethyl ether dechlorination reaction process |
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| CNB2005100220943A CN1318366C (en) | 2005-11-18 | 2005-11-18 | Trifluoro methyl-1, 1, 2-trifluoro-1, 2-dichloro-ethyl ether dechlorination reaction process |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108929204A (en) * | 2017-05-25 | 2018-12-04 | 中昊晨光化工研究院有限公司 | A kind of synthetic method and synthesis device of 1,2- difluoromethyl vinyl ethers |
| CN107286060A (en) * | 2017-06-22 | 2017-10-24 | 山东华夏神舟新材料有限公司 | End group is the preparation method of the perfluoroalkyl vinyl ether of sulfonyl fluoride group |
| WO2019115654A1 (en) * | 2017-12-15 | 2019-06-20 | Solvay Specialty Polymers Italy S.P.A. | Process for the production of perfluorinated alkylvinylethers |
| CN109956855B (en) * | 2017-12-25 | 2022-04-15 | 中蓝晨光化工研究设计院有限公司 | Preparation method of high-purity perfluoromethyl vinyl ether |
| CN114174250A (en) * | 2020-11-06 | 2022-03-11 | 福建永晶科技股份有限公司 | Novel process for industrially synthesizing perfluoromethyl vinyl ether and 2-fluoro-1, 2-dichloro-trifluoromethoxyethylene |
| WO2022095625A1 (en) * | 2020-11-06 | 2022-05-12 | Fujian Yongjing Technology Co., Ltd | New industrial process for manufacturing of perfluoro (methyl vinyl ether) (pfmve) and of 2-fluoro-1, 2-dichloro-trifluoromethoxyethylene (fctfe) |
| EP4031517A4 (en) * | 2020-11-25 | 2022-11-09 | Fujian Yongjing Technology Co., Ltd | Industrial process for manufacturing of perfluoro(methyl vinyl ether) (pfmve) and of 1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane (tftfme) |
| CN115504867B (en) * | 2021-06-23 | 2024-04-12 | 中蓝晨光化工研究设计院有限公司 | Method for synthesizing fluorine-containing vinyl ether |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4996370A (en) * | 1988-06-30 | 1991-02-26 | Ausimont S.R.L. | Process for preparing fluorinated conjugated olefinic products and new products thus obtained |
| CN1431988A (en) * | 2000-05-31 | 2003-07-23 | 旭硝子株式会社 | Novel fluorine compound, process for producing same, and polymer thereof |
-
2005
- 2005-11-18 CN CNB2005100220943A patent/CN1318366C/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4996370A (en) * | 1988-06-30 | 1991-02-26 | Ausimont S.R.L. | Process for preparing fluorinated conjugated olefinic products and new products thus obtained |
| CN1431988A (en) * | 2000-05-31 | 2003-07-23 | 旭硝子株式会社 | Novel fluorine compound, process for producing same, and polymer thereof |
Non-Patent Citations (1)
| Title |
|---|
| OURNAL OF POLYMER SCIENCE:PART A VILLIAM S.,,Polymers of FluorocarbonEthersandSulfides.IrifluoromethylTrifluoro Vinyl Ether andSulfide. 1965 * |
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Assignee: CHENGUANG FLUORO & SILICONE ELASTOMERS CO.,LTD. Assignor: ZHONGLAN CHENGUANG CHEMICAL IN Contract fulfillment period: 2007.6.26 to 2025.11.17 Contract record no.: 2009510000039 Denomination of invention: Trifluoro methyl-1, 1, 2-trifluoro-1, 2-dichloro-ethyl ether dechlorination reaction process Granted publication date: 20070530 License type: Exclusive license Record date: 20090917 |
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