CN104557797A - Method for shortening induction period of epoxidation reaction of hexafluoropropylene - Google Patents
Method for shortening induction period of epoxidation reaction of hexafluoropropylene Download PDFInfo
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- CN104557797A CN104557797A CN201310519988.8A CN201310519988A CN104557797A CN 104557797 A CN104557797 A CN 104557797A CN 201310519988 A CN201310519988 A CN 201310519988A CN 104557797 A CN104557797 A CN 104557797A
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- propylene oxide
- shortening
- epoxidation reaction
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/48—Compounds containing oxirane rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms, e.g. ester or nitrile radicals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
- C07D301/06—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the liquid phase
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- Organic Chemistry (AREA)
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Abstract
The invention provides a method for shortening an induction period of epoxidation reaction of hexafluoropropylene. The method comprises the steps of reacting hexafluoropropylene with oxygen to prepare a corresponding product in the presence of an acyl halide compound and/or a hexafluoropropylene oxide polymer. According to the method provided by the invention, the induction period of epoxidation reaction of hexafluoropropylene can be effectively shortened; the reaction can be rapidly and stably carried out; and a target product with high yield is obtained.
Description
Technical field
The present invention relates to a kind of method shortening R 1216 epoxidation reaction inductive phase.
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, can react with various nucleophilic reagents such as water, alcohol, sulfuric acid, amine, Grignard reagent and organolithiums.Propylene oxide hexafluoride and can be used to produce the important organic fluorine product such as Perfluoroacetone, hexafluoroisopropanol, also may be used for the important monomer preparing perfluorinated ion-exchange membrane (or resin) and PFPE, can also for the preparation of medical anesthetic sevoflurane.Dimerization of hexafluoropropene oxide body, tripolymer, the tetramer can be used for the monomers such as synthesis PFPE.。
The preparation of Propylene oxide hexafluoride has vapour phase oxidation process and liquid phase oxidation, and what wherein have industrial application value is liquid phase oxidation.
Adopt oxygen liquid phase direct oxidation HFP to be a kind of method preparing HFPO with industrial prospect, this method is in suitable solvent, and by controlling temperature of reaction and pressure, HFP and oxygen are disperseed in a solvent, under catalyst-free condition, direct reaction generates HFPO.As CN1320598A and CN101157669B makes inert solvent with fluorochlorohydrocarbon, make initiator with halogen, trifluoromethyl Hydroxyl fluoride or tetrafluoroethylene, at 15-120 DEG C, liquid-phase oxidation HFP produces HFPO, and final transformation efficiency reaches 78%, productive rate reaches 77%.Because this method uses fluorochlorohydrocarbon to damage the ozone layer, thus do not advocated.Chinese patent CN1634902 develops and is solvent with the HFC-236fa R236 of not chloride atom, completes the method for the epoxidation reaction of HFP in the supercritical state, react more steady, and when reaction conversion ratio reaches 100%, the selectivity of HFPO is close to 70%.
But all there is the problem of R 1216 epoxidation reaction length inductive phase in these two kinds of methods, all add the beginning from raw material, autoreaction starts to carry out, and needs the waiting time through 1 ~ 5 hour.The existence of inductive phase obviously extends the reaction times, thus reduces the space-time yield of Autoclave; In addition due to the uncertainty of duration inductive phase, more strict requirement is carried to the on-line Control in reaction process, added the danger of epoxidation reaction operation.Therefore, need in actual production to seek a kind of method shortening R 1216 epoxidation inductive phase.
Summary of the invention
The present invention, by adding acyl halides compound and/or Propylene oxide hexafluoride polymer, makes shortening inductive phase of R 1216 epoxidation reaction, and reaction fast and stable is carried out, and obtains the target product of high yield.
Technical scheme provided by the invention is as follows:
Shorten the method for R 1216 epoxidation reaction inductive phase, under following structural formula (I) Suo Shi, acyl halides compound and/or the shown Propylene oxide hexafluoride polymer of structural formula (II) exist, R 1216 and oxygen reaction prepare corresponding product:
Wherein: R is selected from C1-C5 alkyl, C1-C5 haloalkyl, hydrogen or halogen atom, and X is selected from halogen atom;
CF
3CF
2CF
2O[CF(CF
3)CF
2O]
n-1CF(CF
3)COF （II）
Wherein: n is the integer of 1 ~ 5.
Above-mentioned acyl halides compound is preferably selected from COCl
2, COF
2, CH
3cOCl, CCl
3cOCl and CF
3one in COF, more than two or three combination, more preferably COF
2and/or CF
3cOF.
Above-mentioned Propylene oxide hexafluoride polymer is preferably CF
3cF
2cF
2oCF (CF
3) COF and/or CF
3cF
2cF
2o [CF (CF
3) CF
2o]
2cF (CF
3) COF.
Acyl halides compound of the present invention and/or the polymeric consumption of Propylene oxide hexafluoride are 10 ~ 10000ppm, more preferably 10 ~ 1000ppm based on the quality optimization of R 1216.
The present invention does not specially require reaction solvent, and the solvent that can be used for R 1216 epoxidation reaction all can be used for the present invention, as preferred mode, fluorine-containing alkane can be used, hydrogen fluorohydrocarbon can be preferably further, as particularly preferred mode, can HFC-236fa be used.The quality proportion optimization of R 1216 and solvent is 1:2 ~ 20, more preferably 1:5 ~ 10.
Product prepared by R 1216 epoxidation reaction of the present invention can be the one be selected from Propylene oxide hexafluoride, dimerization of hexafluoropropene oxide body, Propylene oxide hexafluoride tripolymer, the Propylene oxide hexafluoride tetramer and Propylene oxide hexafluoride pentamer, more than two or three combination.
Temperature of reaction of the present invention is preferably 90 ~ 150 DEG C, more preferably 110 ~ 130 DEG C; Reaction pressure is preferably 0.05-0.5MPa, more preferably 0.1 ~ 0.3MPa.
Exemplarily, the invention provides a kind of preparation method of Propylene oxide hexafluoride: react and carry out in autoclave, first add in a kettle. certain proportion reaction substrate HFP and solvent HFC-236fa, then add a small amount of above-mentioned acyl halides compound and/or Propylene oxide hexafluoride polymer.Reactor is sealed, is heated to assigned temperature, passes into the oxygen of certain pressure, and maintain oxygen partial pressure in still.Then, under certain temperature of reaction, HFP and oxygen are dropped in autoclave with certain proportioning and carries out epoxidation reaction.
The inductive phase of reacting is determined by the appearance of online GC detection product HFPO.
The calculating of above-mentioned time inductive phase is defined as: from reactor, pass into required time when oxygen begins to reach raw material HFP peak area 2% to GC on-line checkingi to product HFPO peak area.
It is long that method provided by the invention solves inductive phase in existing HFP epoxidation production technique, produces unstable shortcoming, makes reaction safer, controlled, and shorten the epoxidation reaction time simultaneously, improve the space-time yield of Autoclave.
Embodiment
The following examples illustrate several embodiment of the present invention for being used for, but do not limit the invention to these embodiments.One skilled in the art would recognize that all alternativess, improvement project and the equivalents that present invention encompasses and may comprise in Claims scope.
Embodiment 1
In the stainless steel HV XLPE power cables of 1L, add 50g substrate HFP and 275g HFC-236fa, then add acyl halides compound COCl
20.5g, is warming up to 90 DEG C, then passes into 0.202MPa oxygen.Reaction starts to occur, and is analyzed determine that decomposition induction time be 180min, HFPO selectivity is 70% by online GC.
Embodiment 2-12
Change kind and consumption, temperature of reaction, oxygen intake, HFP consumption and the HFC-236fa consumption of acyl halides compound, all the other are identical with embodiment 1, are analyzed and determine decomposition induction time, the results are shown in table 1 by online GC.
Table 1
Comparative example 1
In the stainless steel HV XLPE power cables of 1L, add 50g substrate HFP and 275g HFC-236fa, be warming up to 110 DEG C, then pass into 0.201MPa oxygen.Reaction starts to occur, and is analyzed determine that decomposition induction time be 242min, HFPO selectivity is 71% by online GC.
Comparative example 2-4
Change temperature of reaction, oxygen intake, HFP consumption and HFC-236fa consumption, all the other are identical with comparative example 1, are analyzed and determine decomposition induction time, the results are shown in table 2 by online GC.
Table 2
As can be seen from above-described embodiment, can be found out by contrast, acyl halides compound and/or Propylene oxide hexafluoride is polymeric adds the inductive phase that can shorten HFP epoxidation reaction significantly, and not affect the selectivity of product HFPO.
Claims (9)
1. one kind is shortened the method for R 1216 epoxidation reaction inductive phase, under it is characterized in that acyl halides compound and/or the shown Propylene oxide hexafluoride polymer of structural formula (II) exist following structural formula (I) Suo Shi, R 1216 and oxygen reaction prepare corresponding product:
Wherein: R is selected from C1-C5 alkyl, C1-C5 haloalkyl, hydrogen or halogen atom, and X is selected from halogen atom;
CF
3CF
2CF
2O[CF(CF
3)CF
2O]
n-1CF(CF
3)COF （II）
Wherein: n is the integer of 1 ~ 5.
2., according to the method for shortening R 1216 epoxidation reaction according to claim 1 inductive phase, it is characterized in that described acyl halides compound is selected from COCl
2, COF
2, CH
3cOCl, CCl
3cOCl and CF
3one in COF, more than two or three combination, described acyl halides compound and/or the polymeric consumption of Propylene oxide hexafluoride are 10 ~ 10000ppm based on the quality of R 1216.
3., according to the method for shortening R 1216 epoxidation reaction according to claim 2 inductive phase, it is characterized in that described acyl halides compound is selected from COF
2and/or CF
3cOF, described acyl halides compound and/or the polymeric consumption of Propylene oxide hexafluoride are 10 ~ 1000ppm based on the quality of R 1216.
4., according to the method for shortening R 1216 epoxidation reaction according to claim 1 inductive phase, it is characterized in that described Propylene oxide hexafluoride polymer is CF
3cF
2cF
2oCF (CF
3) COF and/or CF
3cF
2cF
2o [CF (CF
3) CF
2o]
2cF (CF
3) COF.
5., according to the method for shortening R 1216 epoxidation reaction according to claim 1 inductive phase, it is characterized in that reacting in the presence of solvent, described solvent is fluorine-containing alkane, and the quality proportioning of R 1216 and solvent is 1:2 ~ 20.
6. according to the method for shortening R 1216 epoxidation reaction according to claim 5 inductive phase, it is characterized in that described fluorine-containing alkane is hydrogen fluorohydrocarbon, under acyl halides compound and/or Propylene oxide hexafluoride polymer exist, R 1216 prepares corresponding product to oxygen liquid phase reaction, and the one, more than two or three that described product is selected from Propylene oxide hexafluoride, dimerization of hexafluoropropene oxide body, Propylene oxide hexafluoride tripolymer, the Propylene oxide hexafluoride tetramer and Propylene oxide hexafluoride pentamer combines.
7., according to the method for shortening R 1216 epoxidation reaction according to claim 6 inductive phase, it is characterized in that temperature of reaction is 90 ~ 150 DEG C, reaction pressure is 0.05-0.5MPa.
8., according to the method for shortening R 1216 epoxidation reaction according to claim 7 inductive phase, it is characterized in that temperature of reaction is 110 ~ 130 DEG C, reaction pressure is 0.1 ~ 0.3MPa.
9., according to the method for shortening R 1216 epoxidation reaction according to claim 6 inductive phase, it is characterized in that described hydrogen fluorohydrocarbon is HFC-236fa, the quality proportioning of described R 1216 and solvent is 1:5 ~ 10.
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| CN201310519988.8A CN104557797B (en) | 2013-10-28 | 2013-10-28 | A kind of method for shortening hexafluoropropene epoxidation reaction induction period |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06107650A (en) * | 1992-10-01 | 1994-04-19 | Daikin Ind Ltd | Production of hexafluoropropene oxide |
| JPH0952886A (en) * | 1995-08-09 | 1997-02-25 | Asahi Glass Co Ltd | Production of hexafluoropropylene oxide |
| CN1634902A (en) * | 2004-09-01 | 2005-07-06 | 浙江蓝天环保高科技股份有限公司 | Clean preparation process for hexafluropropylene oxide |
| RU2469030C1 (en) * | 2011-08-31 | 2012-12-10 | Общество с ограниченной ответственностью "ГалоПолимер Кирово-Чепецк" (ООО "ГалоПолимер Кирово-Чепецк") | Method of producing hexafluoropropylene oxide |
-
2013
- 2013-10-28 CN CN201310519988.8A patent/CN104557797B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06107650A (en) * | 1992-10-01 | 1994-04-19 | Daikin Ind Ltd | Production of hexafluoropropene oxide |
| JPH0952886A (en) * | 1995-08-09 | 1997-02-25 | Asahi Glass Co Ltd | Production of hexafluoropropylene oxide |
| CN1634902A (en) * | 2004-09-01 | 2005-07-06 | 浙江蓝天环保高科技股份有限公司 | Clean preparation process for hexafluropropylene oxide |
| RU2469030C1 (en) * | 2011-08-31 | 2012-12-10 | Общество с ограниченной ответственностью "ГалоПолимер Кирово-Чепецк" (ООО "ГалоПолимер Кирово-Чепецк") | Method of producing hexafluoropropylene oxide |
Non-Patent Citations (1)
| Title |
|---|
| 徐宇威等: "六氟环氧丙烷的合成", 《浙江化工》 * |
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