CN1320598A - Process for preparing perfluoroepoxide - Google Patents
Process for preparing perfluoroepoxide Download PDFInfo
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- CN1320598A CN1320598A CN 00120011 CN00120011A CN1320598A CN 1320598 A CN1320598 A CN 1320598A CN 00120011 CN00120011 CN 00120011 CN 00120011 A CN00120011 A CN 00120011A CN 1320598 A CN1320598 A CN 1320598A
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- tetrafluoroethylene
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Abstract
A process for preparing perfluoroolefin oxide, which is used as the raw material to prepare a series of organic fluorine products, features that in the presence of initiator (Cl, F, Br, trifluoromethyl hypofluorous acid, or tetrafluoroethylene) the relative olefine is oxidized by oxygen in cold carrier or fluorochlorohydrocarbon liquid medium. Under inertial solvent layer, the gas-state olefin is introduced to oxidant gas flow. The yield and conversion are 77% and 78% for sexafluoroepoxypropane, or 87% and 93% of tetrafluoroepoxyethane.
Description
The present invention relates to prepare perfluoroolefine oxide compound field, particularly relate to preparation ptfe ring oxidative ethane (OT φ Э) and Propylene oxide hexafluoride (O Г φ II), their actual raw materials that is used as the synthesizing perfluoroalkyl vinyl ether, this ether are used to prepare ion-exchange membrane (when scale operation caustic alkali and chlorine can without mercury), surfactant, heat-resisting arctic rubber, oil, hydraulic fluid and other fluorine organic products.
Known method: with hydrogen peroxide (JP, 63-27487, C07 Д on May 2nd, 303/48,88) with following substances fluorine oxide alkene, with hypochlorous acid basic metal and alkaline earth salt (JP, 59-110687, C07 Д 301/03, on June 26th, 84), with peracid (RU, 317651, C07 Д on November 19th, 301/12,71), with peroxidation imido acid (Д E2557655, C07 Д on June 30th, 301/16,77), with anodic oxidation (Д E, 2658328, C25B3/02, on June 29th, 78).Yet, up to now,, still do not have the convenience of preparation perfluoroolefine oxide compound, the commercial run of safety though work in some field.
In all known means, the most preferably come fluorine oxide alkene with the most common and the most cheap oxygenant-oxygen.
The known method for preparing Propylene oxide hexafluoride with oxygen liquid-phase oxidation R 1216 (Г φ II) is at temperature 70-120 ℃, under the pressure 5.0MPa (50atm), be reflected in the steel reactor that is lined with tetrafluoroethylene, under existing, the polytetrafluoroethylene granule catalyzer of handling with the oxidation products of Г φ II carries out (RU, 608801, C07 Д on May 3rd, 303/08,78).Be the preparation catalyzer, in autoclave, add the solvent Freon 113, in the Г of subzero 70 ℃ of compressions φ II and be heated to 140 ℃.Then, the beginning bubbling added air 3 hours under 5.0MPa pressure.After this, in the reactor that Г φ II oxidation products is arranged, add polytetrafluoroethylene granule, extract solvent and low-boiling products then out.The particle of preparation is like this inserted in the reactor, add freonll-11 and be chilled to-70 ℃ Г φ II in advance, under pressure 50atm, bubbling adds air reactor is heated to 70-120 ℃.15 to 30 minutes reaction times.Reach 84% in 23% time reaction preference of transformation efficiency.
The shortcoming of described method is the intermittence of technology, the complicacy of preparation catalyzer, low-conversion, high pressure and explosion hazard.
The currently known methods of preparation fluorinated epoxide is at inert diluent-N
2, CO
2, Ar, CF
4, C
2F
6, ring C
4F
8, different C
6F
14, CCl
4, CF
2Cl
2, CF
2HCl, C
2F
3l
3, CF
3CF
2Br CFBr etc. exist down, add and depress, in 50-250 ℃ with haloolefin CF
2=CFX is H at this X, F, Cl, CF
3, CF
2H and other heat (US, 3536733,260-348, on October 27th, 70) with oxygen.According to described method, under agitation in autoclave, add thinner and alkene (tetrafluoroethylene or R 1216) and heated mixt, progressively oxygen supply.The productive rate of ptfe ring oxidative ethane is 60-80%, transformation efficiency 50-90%, and the productive rate of Propylene oxide hexafluoride is 71%, transformation efficiency 70%.
The shortcoming of described method is the discontinuity and the high pressure of technology, and this causes the explosion hazard of process.
Preparation ptfe ring oxidative ethane be in the presence of ozone near technical solution, in 0-40 ℃, at perfluor or fluorine chlorine organic liquid-1,1,2-three chloro-1,2, the 2-Halothane, fluoro trichloromethane, in the perfluoro-methyl cyclohexane medium, with molecular oxygen oxidation tetrafluoroethylene (T φ Э) (FR, 95620/1526663, C07D, on March 26th, 71).C
2F
4: O
3Molecular ratio be 10: 500.In reactor, add perfluor-or chlorine fluorine organic liquid for synthesizing, then, under continuous stirring, add tetrafluoroethylene and oxygen ozoniferous to the reaction medium bubbling by two conduits that place reactor bottom.The yield of OT φ Э is 46-62%, and the transformation efficiency of T φ Э is 45-58%.
The deficiency of aforesaid method is the not high last fluorine ethylene oxide yield and the low-conversion of tetrafluoroethylene.
Task of the present invention is to improve the productive rate of fluoro epoxide, increases the transformation efficiency of raw material olefin, also will set up a kind of blanketly, prepares the commercial run of perfluoroolefine oxide compound reliably.
Being proposed of task is finished as follows: in 15-120 ℃, in the presence of initiator, under the inert liq layer, supply with the gas phase perfluoroolefine in oxidant stream, with the corresponding perfluoroolefine of oxygen oxidation.
Be reflected in the reactor of circulation and carry out, reactor itself is a kind of column shape container, the pipeline that it has outer heating unit and input reactant and derives reaction product.Reactant enters reactor along two tubes, and this two tubes is arranged as one in another root (tube-in-tube), and interior pipe is shorter than outer tube, and the exit end of outer tube is installed in the reactor, under the inert liq layer.Reactant gases enters reactor through liquid level, derives through top pipeline.For the stopping reaction process can be in inert solvent restir participate in the gas of reaction.
In reactor, add inert liq, supply with the gaseous state perfluoroolefine, and supply with the oxygen that is mixed with initiator along outer tube along interior pipe.When fetrafluoroethylene oxide, oxygen can be supplied with together with inert diluent such as nitrogen.Mixing each component and olefin oxide in this case is under the inert solvent layer, carries out when gaseous olefin enters in the gaseous oxidizer mixture flow.
Use fluorochlorohydrocarbon liquid as inert solvent, 11 φ for example, 12 φ, 13 φ, its general formula are X (CF
2CFCl)
nX, x=F, Cl, n=1-12, their difference is molecular weight and boiling point (150-300 ℃); And cold carrier, for example, 51-12 (1,6-dichloro perfluor hexane), 318 (perfluorocyclobutanes).
Use halogen-chlorine, fluorine, bromine, trifluoromethyl Hydroxyl fluoride or tetrafluoroethylene to make initiator.For the preparation oxidation mixture adds halogen and trifluoromethyl Hydroxyl fluoride salt in the oxygen with the 0.1-15% volume, and tetrafluoroethylene adds in the R 1216 with the 1-15% volume.The content of initiator is increased to be higher than described scope be inappropriate, because the amount of by product (carbonyl fluoride, trifluoroacetyl group fluorine) all increases in all cases.When being lower than described scope, sharply reduces the content of initiator the transformation efficiency of perfluoroolefine.
Reaction is carried out continuously during at 15-70 ℃ of fetrafluoroethylene oxide with 60-120 ℃ of oxidation hexafluoroethylene.Oxidation rate reduces and the transforming degree minimizing when temperature is lower than down in limited time.Elevated temperature can be owing to darker oxidation increases by product.
To contain reaction product condensation when being chilled to subzero 120 ℃ of perfluoroepoxide, acid fluoride and unreacted alkene, separate with the gas-liquid chromatography analysis and with cryogenic rectification method.
Obtain Propylene oxide hexafluoride productive rate 77.2%, transformation efficiency 78.3% and tetrafluoro ethylene oxide yield 87%, transformation efficiency 93.8% by described method.
The supply that is provided and the method for blending ingredients make reaction process to carry out in a continuous manner under the condition of milder, and have got rid of explosion hazard, thereby make this technology have the prospect of commercial exploitation.
The distinguishing characteristics of the method that is provided is to use halogen, trifluoromethyl Hydroxyl fluoride and tetrafluoroethylene to make initiator, under the inert solvent layer gaseous olefin is sent into oxidant stream simultaneously.These features that the inventive method is different from immediate prior art do not disclose in other technical solution.
Embodiment given below is used for illustrating the invention that is provided.
Embodiment 1
To volume 310cm
3Have and add 200ml fluorochlorohydrocarbon liquid 12 φ in overcoat and the electrically heated cylindrical reactor.Send into gas raw material along the axial arranged fluoroplastics pipeline that stretches in the reactor: with 3.0 liters of/hour inputs of speed R 1216, is 6.0 liter/hour along outer tube input oxidation mixture (oxygen and trifluoromethyl Hydroxyl fluoride) speed along interior pipe.
Trifluoromethyl Hydroxyl fluoride (CF
3OF), the relative oxygen of content is 5.5% volume.The volume ratio of R 1216 and oxidation mixture is 1: 2.Carried out continuously 5 hours in 90 ℃ of reactions.The gas that comes out from reactor has following composition, the % volume: 51.2 Propylene oxide hexafluorides; 18.4 R 1216; 30.4 trifluoroacetyl group fluorine and carbonyl fluoride.Make reaction product gas by 5% sodium hydroxide solution to remove acidic impurities, dry and in subzero 120 ℃ of condensations in collector in the calcium chloride post then.
The gained crude product is depressed rectifying adding, and obtains 67.14g purity and be 99.5% Propylene oxide hexafluoride.Selectivity is 77.2%, and the transformation efficiency of R 1216 is 78.3%.
Similar embodiment 1 is carried out following synthetic (embodiment 2-12).The oxidizing condition of fluoroolefin and the results are shown in the table of obtaining.
| Test | Raw material olefin | Alkene consumption g | Solvent | Initiator | Initiator concentration % volume | Temperature, C | The composition of generated reactive gas, the % volume | Isolated epoxide, g | Olefin conversion, % | Selectivity, % | ||
| Acid fluoride | Epoxide | Alkene | ||||||||||
| 1. R 1216 100,5 liquid, 12 φ trifluoromethyl Hydroxyl fluoride salt 5,5 90 30,40 51,20 18,40 67,14 78,3 77,2 2. R 1216s 100,5 liquid, 12 φ trifluoromethyl Hydroxyl fluoride salt 15 85 33,2 36,60 30,20 48,8 63,8 68,8 3. R 1216s 100,5 liquid, 12 φ trifluoromethyl Hydroxyl fluoride salt 1,8 95 35,3 41,50 23,20 55,97 71,8 70,1 4. R 1216s, 115 liquid, 12 φ fluorine 0,1 80 22,8 53,70 23,50 63,33 76,5 70,2 5. R 1216s, 115 liquid, 12 φ fluorine 1 65 21 63,27 15,73 80,43 84,3 75 6. R 1216s, 115 cold carrier 51-12 fluorine 5 75 39,96 52,06 7,98 66,28 92,02 56,6 7. R 1216s, 105 liquid, 11 φ tetrafluoroethylene 1 120 28,3 41,70 30,00 48,47 70 59,6 8. R 1216s, 105 liquid, 13 φ chlorine 7,5 65 27,50 45,30 27,20 52,61 72,8 62,2 9. R 1216s, 105 cold carrier 51-12 vinyl fluorides 10 95 35,40 48,90 15,70 56,8 84,3 58 10 tetrafluoroethylene, 214,3 cold carriers, 318 trifluoromethyl Hydroxyl fluoride salt 1 20 21,9 72,60 5,50 202,8 93,8 87 11 vinyl fluorides 214,3 cold carriers, 318 fluorine 3 15 24,8 63,30 9,90 185,2 88,7 84 12 vinyl fluorides, 214,3 cold carriers, 318 bromines 10 60 21,43 50,31 28,16 139,9 68,3 82,4 | ||||||||||||
Claims (5)
1. in the presence of initiator, in inert solvent, heat up down, prepare the method for perfluoroepoxide with oxygen oxidation corresponding alkene, it is characterized in that using halogen, trifluoromethyl Hydroxyl fluoride or tetrafluoroethylene to make initiator and gaseous olefin is sent into oxidizer flow under the inert solvent layer.
2. according to the method for claim 1, it is characterized in that the halogen and the trifluoromethyl Hydroxyl fluoride of 0.1-15.0% volume are added in the oxygen.
3. according to the method for claim 1, it is characterized in that using R 1216 as alkene, to wherein adding tetrafluoroethylene, its amount is the 1.0-15.0% volume.
4. according to the method for claim 1, it is characterized in that, react under 15-120 ℃ and carry out.
5. according to the method for claim 1, it is characterized in that, make inert solvent with cold carrier and hydrofluoric ether liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00120011 CN1320598A (en) | 2000-04-25 | 2000-04-25 | Process for preparing perfluoroepoxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00120011 CN1320598A (en) | 2000-04-25 | 2000-04-25 | Process for preparing perfluoroepoxide |
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|---|---|
| CN1320598A true CN1320598A (en) | 2001-11-07 |
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ID=4588141
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1966498B (en) * | 2006-11-14 | 2010-05-12 | 上海三爱富新材料股份有限公司 | Hexafluoroepoxypropane preparation process |
-
2000
- 2000-04-25 CN CN 00120011 patent/CN1320598A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1966498B (en) * | 2006-11-14 | 2010-05-12 | 上海三爱富新材料股份有限公司 | Hexafluoroepoxypropane preparation process |
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