CN103044362A - Method for preparing hexafluoropropylene oxide by using gas phase oxidation method - Google Patents
Method for preparing hexafluoropropylene oxide by using gas phase oxidation method Download PDFInfo
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- CN103044362A CN103044362A CN2012105899166A CN201210589916A CN103044362A CN 103044362 A CN103044362 A CN 103044362A CN 2012105899166 A CN2012105899166 A CN 2012105899166A CN 201210589916 A CN201210589916 A CN 201210589916A CN 103044362 A CN103044362 A CN 103044362A
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Abstract
The invention discloses a method for preparing hexafluoropropylene oxide by using gas phase oxidation method, which comprises the following steps: placing the perfluorinated alkyl amine into a sealing environment, vacuumizing, pumping in hexafluoropropylene, increasing the temperature to gasify the perfluorinated alkyl amine, then pumping in oxygen to perform gas phase epoxidation reaction and getting hexafluoropropylene oxide. Compared with the prior method, the method uses minute quantity of resolvent, the space-time yield coefficient is large and the cost is relatively inexpensive; the resolvent has a high boiling point and easy to be separated from the product; the conversion rate and the yield coefficient of the reaction are high, the reaction rate is high and the reaction temperature is relatively low; and the method is suitable for industrialization application.
Description
Technical field
The present invention relates to the fluorine field of fine chemical, be specifically related to the method that a kind of vapour phase oxidation process prepares Propylene oxide hexafluoride.
Background technology
Propylene oxide hexafluoride (Hexafluoropropylene epoxide, be called for short HFPO) be a kind of important fluorine chemical basic material, its epoxy construction has very high chemically reactive, the rearrangeable Perfluoroacetone that is converted under the Lewis acid catalysis can react with various nucleophilic reagents such as water, alcohol, sulfuric acid, amine, Grignard reagent and organolithiums.It is the intermediate of producing the important organic fluorine products such as Perfluoroacetone, hexafluoroisopropanol, also is the important monomer of preparation perfluorinated ion-exchange membrane (or resin) and PFPE, can also be used for the production of medical narcotic Ultane.And these organic fluorine products are often extremely expensive, therefore its starting material HFPO synthetic had very important commercial promise.
Adopting oxygen to directly oxidize R 1216 (Hexafluoropropylene is called for short HFP) is a kind of method for preparing HFPO with industrial prospect, is divided into vapour phase oxidation process and liquid phase oxidation.Liquid phase oxidation is in suitable solvent, by control temperature of reaction and pressure, HFP and oxygen is dispersed in the solvent, and direct reaction generates HFPO under the catalyst-free condition.Make inert solvent such as CN1320598A and CN101157669A with fluorochlorohydrocarbon, make initiator with halogen, trifluoromethyl Hydroxyl fluoride or tetrafluoroethylene, produce HFPO at 15 ℃ of-120 ℃ of lower liquid-phase oxidation HFP, final transformation efficiency reaches 78%, productive rate reaches 77%, this method adopts the non-fluorine halogen atom chlorine of introducing to damage the ozone layer, thereby is not advocated.CN1634902A then adopts the perfluoroparaffin of chloride atom not to finish the epoxidation reaction of HFP under supercritical state, so that reaction is more steady; And when reaction conversion ratio reached 100%, the selectivity of HFPO was near 70%.Japanese Nippon Mektron company (JP 1135780,1978) patent report utilized PFPE such as R in 1989
fO (XCF
2O)
n(CF
2CF
2O)
m(CF
2O)
3R
f(R
f=perfluoro alkane chain, n, m=1-3) be solvent, 110 ℃-130 ℃ of temperature, pressure 1-4MPa, the transformation efficiency of HFPO are near 100%, and yield is 83.9%; This is the highest response yield that discloses up to now the HFPO of report.Yet PFPE is expensive, has hindered the development of this technique.
The thinking that propylene oxidation prepares propylene oxide is used for reference in early stage research, and is more to vapour phase oxidation process research.The method mainly is to adopt traditional epoxidation catalyst copper or silver, under comparatively high temps (greater than 200 ℃), HFP and oxygen (or air) is reacted by tubular reactor.As Japan AGC company last century the seventies announced several pieces of patents (JP 52108914,1977; JP53021110,1978; JP 53021109,1978; JP 52053806,1977), adopt silicate and aluminum oxide or zeolite-loaded copper catalyst, 250 ℃-350 ℃ of temperature of reaction, the feed molar proportioning is HFP/O
2=(1-5): 1, duration of contact 30-180s, the transformation efficiency of the final HFPO that obtains reaches 31.7%, selectivity reaches 72.2%, but this method temperature high energy consumption is large, uses catalyzer also not reach very high selectivity.When not having the existing of copper, catalyzed oxidation will can not get target product HFPO.
Because liquid phase oxidation advocates that epoxidation reaction is that liquid phase is carried out, in reactor, often add heavy dose of solvent, the mass ratio that feeds intake such as solvent and HFP among the patent CN1966498A is 1-30,4-15 preferably, the mass ratio that feeds intake of solvent and HFP is 1-20 among the patent CN1634902A, more preferably being 2-15, further is 3-10.High feed ratio simultaneously also so that reaction pressure is very high, causes equipment investment to increase so that the reactor space-time yield descends greatly, also brings potential safety hazard for producing.In fact, because reaction substrate HFP and oxygen boiling point are all very low, even if adopted high boiling solvent, be difficult to also guarantee that oxygen and HFP are all dissolved and epoxidation reaction is occured in liquid phase.If adopt heavy dose of solvent, because solvent is limited to the dissolving power of oxygen, probably cause oxygen to be assembled at the reactor gas-phase space.And hyperoxia concentration can cause over oxidation, has increased the possibility of blasting.
Summary of the invention
The invention provides the method that a kind of vapour phase oxidation process prepares Propylene oxide hexafluoride, adopt a small amount of high boiling point (such as 50 ℃-150 ℃) solvent, gasification is rear as gas-solvent, make the epoxidation reaction of HFP and oxygen occur in gas phase, because the speed of the existence meeting regulating ring oxidizing reaction of gas-solvent is kept the high selectivity of epoxidation reaction simultaneously to stop over oxidation.
The present invention develops the perfluoroalkyl amine substance as solvent, and epoxidation reaction is carried out in gas phase.Perfluoroalkyl amine gasification under temperature of reaction, the perfluoroalkyl amine in the gas phase can be regulated HFP and oxygen in gas phase initial ring oxidizing reaction, make continuous, stable the carrying out of reaction, and the HFPO of acquisition high yield.
A kind of vapour phase oxidation process prepares the method for Propylene oxide hexafluoride, comprise step: perfluoroalkyl amine is placed sealed environment, vacuumize, pass into R 1216 and be warming up to the gasification of perfluoroalkyl amine, pass into again oxygen and carry out the gas-phase epoxidation reaction, make Propylene oxide hexafluoride.
The general structure of described perfluoroalkyl amine is
R
F1, R
F2, R
F3The three is identical or different, independently is selected from separately perfluoro-methyl, perfluor ethyl, perfluoro propyl or perfluoro butyl.Described perfluoroalkyl amine can also can be two or more perfluoroalkyl amine for a kind of perfluoroalkyl amine.
Described perfluoroalkyl amine can be selected one or more in perfluoro triethylamine, perfluamine, perfluorotributylamine, perfluor diethyl perfluoro propyl amine, the perfluor dibutyl perfluoro-methyl amine.
The mass ratio of described perfluoroalkyl amine and R 1216 is 1:2-20, is preferably 1:2-10.Be more conducive to HFP and be converted into HFPO fully.
The maximum oxygen partial pressure of oxygen is 0.2MPa in the sealed environment.Be more conducive to HFP and be converted into HFPO fully.
Described oxygen passes into several times, and oxygen depletion again replenishes after fully and passes into oxygen in sealed environment at every turn, passes at every turn that maximum oxygen partial pressure is 0.2MPa in the oxygen seal environment; Until HFP is transformed by 100%.Be more conducive to HFP and be converted into HFPO fully.
Passing into R 1216 is warming up to 80 ℃-160 ℃ and can guarantees perfluoroalkyl amine gasification.
The temperature of described gas-phase epoxidation reaction is 80 ℃-160 ℃, is preferably 130 ℃.Be more conducive to HFP and be converted into HFPO fully.
The described reaction times does not have strict restriction, and the general higher reaction times of temperature of reaction is shorter, can react the degree of carrying out by the prior art Real-Time Monitoring.
Raw material of the present invention adopts the commercially available prod.
The present invention's reaction can be carried out in the Autoclave reaction.In fact, because this epoxidation speed is very fast, by basic chemical engineering knowledge, be easy to realize that this reaction carries out in the successive reaction still.
The maximum difference of the inventive method is to have broken through the heavy dose of reaction solvent of existing employing, attempt epoxidation reaction is transferred to the thinking that liquid phase is carried out, provide and adopted a small amount of gas-solvent regulating ring rate of oxidation, the novel method that allows reaction mainly occur in gas phase.Compare with existing method, the inventive method possesses following advantage:
(1) solvent load is few, and solvent load only has the 1/20-1/2(w/w of HFP), be 1-30(CN1966498A far below the mass ratio that feeds intake of the solvent of announcing in the prior art and HFP) and the mass ratio that feeds intake of solvent and HFP be 1-20(CN1634902A); Space-time yield is high, and cost is relatively cheap;
(2) solvent boiling point is high, be easy to by adding the loss that condensation reflux unit prevents solvent in the exit, and with the separating of product;
(3) reaction conversion ratio and yield are high, can reach 99.8%-100% and 68.7%-71.3% respectively;
(4) speed of response is fast, and temperature of reaction is relatively low.Because oxygen concentration of gas phase is higher than liquid phase, and solvent partial pressure is lower, so that the HFP molecule is easy to react with the oxygen molecule collision.So reaction can be carried out fast at lesser temps.
Embodiment
Oxygen concentration in the reactor adopts online GC to carry out Real-Time Monitoring.
Embodiment 1-8
Perfluoroalkyl amine is joined in the autoclave of 1L drying, seal still and vacuumize 30min with vacuum pump, to remove foreign gas.Then in reactor, inject HFP, keep stirring velocity 350rpm.The stirring tank kettle is warming up to 90 ℃-160 ℃, keeps 0.5h ~ 1h to temperature-stable, then carefully fill into oxygen, oxygen partial pressure Δ P
O2=0.2MPa.Behind the reaction certain hour, detect the selectivity of HFP transformation efficiency and target product HFPO.
Reaction effect when at first studying the single oxygenating.Namely in the reactor that is mounted with in advance a certain amount of HFP, inject oxygen in shortage, after the oxygen completely consumed, namely finish reaction.The result is as shown in table 1:
Table 1 single oxygenating experimental result table
As can be seen from Table 1, when adopting perfluoroalkyl amine as the epoxidised solvent of HFP, epoxidation reaction can be stablized and carry out, and the transformation efficiency that single leads to oxygen (0.2MPa) reaction HFP is positioned at 9.32%-39.1%, and the selectivity of target product HFPO is positioned at 68.1%-72.1%.Show that perfluoroalkyl amine is a kind of desirable reaction solvent.The reaction times temperature influence is the most remarkable, and when temperature of reaction was 130 ℃, oxygenating 0.2MPa can be with oxygen depletion totally at 1.5-1.6h first.When temperature of reaction reaches 160 ℃, react very violent, can finish reaction in the 0.5h.Consider speed of reaction and security, preferable reaction temperature is 130 ℃.
For the HFP in the reactor is converted into HFPO fully, take oxygen depletion after pressure no longer changes, to fill into again 0.2MPa oxygen, until the pattern of HFP complete reaction.The result is as shown in table 2:
Many oxygenating experimental results of table 2 table
Embodiment 9-16
Perfluoroalkyl amine is joined in the autoclave of 1L drying, seal still and vacuumize 30min with vacuum pump, to remove foreign gas.In reactor, inject HFP, keep stirring velocity 350rpm.The stirring tank kettle is warming up to 130 ℃-160 ℃, keeps 0.5h ~ 1h to temperature-stable.Then careful oxygenating gas Δ P
O2=0.2MPa behind the reaction certain hour, detects the selectivity of HFP transformation efficiency and target product HFPO.The result is as shown in table 3:
Many oxygenating experimental results of table 3 table
Among the embodiment 9, for the first time pass into oxygen reaction 2h after, the HFP transformation efficiency is 16.8%, the selectivity of target product HFPO is 71.5%; Oxygenating Δ P again
O2=0.2MPa, behind the reaction 35min, the HFP transformation efficiency is 33.5%, the selectivity of target product HFPO is 71.2%; Oxygenating Δ P again
O2=0.2MPa, behind the reaction 33min, the HFP transformation efficiency is 50.5%, the selectivity of target product HFPO is 71.5%; Oxygenating Δ P again
O2=0.2MPa, behind the reaction 34min, the HFP transformation efficiency is 67.5%, the selectivity of target product HFPO is 71.0%; Oxygenating Δ P again
O2=0.2MPa, behind the reaction 40min, the HFP transformation efficiency is 85.5%, the selectivity of target product HFPO is 71.1%; Oxygenating Δ P again
O2=0.2MPa, behind the reaction 35min, HFP transformation efficiency 100%, the selectivity of target product HFPO is 70.2%.
React total oxygenating number of times 6 times, total reaction time 4.95h.The final transformation efficiency of HFP reaches 100%, and the selectivity of target product HFPO is 70.2%.
As can be seen from Table 3, when temperature of reaction was 130 ℃, continuously the oxygenating reaction can stablize and be carried out, and about 5 hours reaction times, finally transformation efficiency is near 100%, finally selectivity 68.7%-71.3%.When temperature of reaction reaches 150-160 ℃, react very violent during oxygenating, temperature and pressure sharply raises and causes reaction normally not carry out.Therefore, the factors such as combined reaction speed, reaction safety, reaction conversion ratio and selectivity, preferable reaction temperature is 130 ℃.
Among the present invention, owing to adopt perfluoroalkyl amine as the gas-phase reaction solvent, can realize that HFP and oxygen generate target product HFPO in gas phase initial ring oxidizing reaction, and reaction can continuous, stable carrying out, and acquisition higher yields and selectivity, the variation of the wide parameter of setting forth does not affect the preparation of target product HFPO among the preparation method of the present invention, and therefore, the arbitrary combination of wide parameter that the present invention sets forth all can be synthesized target product HFPO according to the method described in the present invention.Do not repeat them here.
Claims (10)
1. a vapour phase oxidation process prepares the method for Propylene oxide hexafluoride, it is characterized in that, comprises step: perfluoroalkyl amine is placed sealed environment, vacuumize, pass into R 1216 and be warming up to the gasification of perfluoroalkyl amine, pass into again oxygen and carry out the gas-phase epoxidation reaction, make Propylene oxide hexafluoride.
2. vapour phase oxidation process according to claim 1 prepares the method for Propylene oxide hexafluoride, it is characterized in that, the general structure of described perfluoroalkyl amine is
R
F1, R
F2, R
F3The three is identical or different, independently is selected from separately perfluoro-methyl, perfluor ethyl, perfluoro propyl or perfluoro butyl.
3. vapour phase oxidation process according to claim 1 and 2 prepares the method for Propylene oxide hexafluoride, it is characterized in that described perfluoroalkyl amine is one or more in perfluoro triethylamine, perfluamine, perfluorotributylamine, perfluor diethyl perfluoro propyl amine, the perfluor dibutyl perfluoro-methyl amine.
4. vapour phase oxidation process according to claim 1 prepares the method for Propylene oxide hexafluoride, it is characterized in that, the mass ratio of described perfluoroalkyl amine and R 1216 is 1:2-20.
5. vapour phase oxidation process according to claim 1 prepares the method for Propylene oxide hexafluoride, it is characterized in that, the mass ratio of described perfluoroalkyl amine and R 1216 is 1:2-10.
6. vapour phase oxidation process according to claim 1 prepares the method for Propylene oxide hexafluoride, it is characterized in that, the maximum oxygen partial pressure of oxygen is 0.2MPa in the sealed environment.
According to claim 1 or 6 described vapour phase oxidation processes prepare the method for Propylene oxide hexafluoride, it is characterized in that, described oxygen passes into several times, oxygen depletion again replenishes after fully and passes into oxygen in sealed environment at every turn, passes at every turn that maximum oxygen partial pressure is 0.2MPa in the oxygen seal environment.
8. vapour phase oxidation process according to claim 1 prepares the method for Propylene oxide hexafluoride, it is characterized in that, passes into R 1216 and is warming up to 80 ℃-160 ℃ and gasifies to perfluoroalkyl amine.
9. vapour phase oxidation process according to claim 1 prepares the method for Propylene oxide hexafluoride, it is characterized in that, the temperature of described gas-phase epoxidation reaction is 80 ℃-160 ℃.
10. vapour phase oxidation process according to claim 9 prepares the method for Propylene oxide hexafluoride, it is characterized in that, the temperature of described gas-phase epoxidation reaction is 130 ℃.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104557788A (en) * | 2013-10-28 | 2015-04-29 | 浙江蓝天环保高科技股份有限公司 | Preparation method of hexafluoropropylene oxide |
| CN104910103A (en) * | 2015-04-23 | 2015-09-16 | 上海应用技术学院 | Preparation method of darunavir intermediate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3536733A (en) * | 1967-08-10 | 1970-10-27 | Du Pont | Method for the preparation of halogenated epoxides |
| US20100016615A1 (en) * | 2006-10-24 | 2010-01-21 | Hideki Nakaya | Process for production of hexafluoropropylene oxide |
| EP2409970A1 (en) * | 2009-03-17 | 2012-01-25 | Daikin Industries, Ltd. | Method for producing hexafluoropropylene oxide |
| CN102675255A (en) * | 2012-04-18 | 2012-09-19 | 金华永和氟化工有限公司 | Preparation method for hexafluoropropylene oxide |
-
2012
- 2012-12-28 CN CN2012105899166A patent/CN103044362A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3536733A (en) * | 1967-08-10 | 1970-10-27 | Du Pont | Method for the preparation of halogenated epoxides |
| US20100016615A1 (en) * | 2006-10-24 | 2010-01-21 | Hideki Nakaya | Process for production of hexafluoropropylene oxide |
| EP2409970A1 (en) * | 2009-03-17 | 2012-01-25 | Daikin Industries, Ltd. | Method for producing hexafluoropropylene oxide |
| CN102675255A (en) * | 2012-04-18 | 2012-09-19 | 金华永和氟化工有限公司 | Preparation method for hexafluoropropylene oxide |
Non-Patent Citations (1)
| Title |
|---|
| 徐宇威 等.: "超临界流体中六氟环氧丙烷的合成研究", 《有机氟工业》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104557788A (en) * | 2013-10-28 | 2015-04-29 | 浙江蓝天环保高科技股份有限公司 | Preparation method of hexafluoropropylene oxide |
| CN104910103A (en) * | 2015-04-23 | 2015-09-16 | 上海应用技术学院 | Preparation method of darunavir intermediate |
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Application publication date: 20130417 |