CN105315150A - Method for preparing perfluoropropionyl fluoride from hexafluoropropylene oxide oligomer - Google Patents
Method for preparing perfluoropropionyl fluoride from hexafluoropropylene oxide oligomer Download PDFInfo
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- CN105315150A CN105315150A CN201410379162.0A CN201410379162A CN105315150A CN 105315150 A CN105315150 A CN 105315150A CN 201410379162 A CN201410379162 A CN 201410379162A CN 105315150 A CN105315150 A CN 105315150A
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Abstract
The invention relates to a method for preparing perfluoropropionyl fluoride from a hexafluoropropylene oxide oligomer, belonging to the technical field of fine chemical industry of fluorine-contained compounds. The method is characterized by comprising the following steps: with the hexafluoropropylene oxide oligomer as a starting material, alkali metal fluoride as a catalyst and ether as a solvent, carrying out reaction under the condition of 90 to 200 DEG C and carrying out low-temperature reflux condensation at the same time until the bottom part of a reactor is colorless and transparent and a fluorous phase is completely decomposed, then stopping heating and carrying out cooling to room temperature, and subjecting gas generated in the reaction process to collection in a low-temperature cold trap so as to obtain a liquid product, i.e., the perfluoropropionyl fluoride. According to the invention, an important chemical intermediate, i.e., the perfluoropropionyl fluoride, is prepared through the reaction in the invention from the perspective of recovery utilization of resources, so the problem of treating a toxic byproduct, i.e., the hexafluoropropylene oxide oligomer, in the industrial production is solved; meanwhile, the method has the advantages of low raw material cost, mild reaction condition, high yield, and facilitation to large-scale production.
Description
Technical field
The invention belongs to fluorine-containing technical field of fine, particularly relate to a kind of method that Propylene oxide hexafluoride oligopolymer prepares perfluoro-propionyl fluoride.
Background technology
Propylene oxide hexafluoride oligopolymer comprises Propylene oxide hexafluoride trimer tetramer pentamer sexamer heptamer, and molecular weight, between 300-1000, is colorless and odorless transparent oily liquid under normal temperature state.It is the by product of synthesis dimerization of hexafluoropropene oxide body, and this series compound toxicity is very large.In the past, Propylene oxide hexafluoride trimer was converted into PFPE carboxylic acid, for the emulsifying agent of tetrafluoroethylene letex polymerization, but due to nine carbon perfluorocarboxylic acids in vivo cannot metabolism, prohibitted the use by developed country.Propylene oxide hexafluoride oligopolymer is destroyed by current industrial employing combustion method, and this process produces a large amount of poison gas.How turning waste into wealth, to be translated into useful compound be chemist's urgent need to solve the problem always.
Perfluoro-propionyl fluoride also known as five fluorine propionyl fluorides, molecular formula: CF
3cF
2cOF, boiling point :-28 DEG C is colourless gas under normal temperature, acid, easy and alcohol generation esterification, meets water and generates HF gas and perfluorinated acid.
Perfluoro-propionyl fluoride is as the intermediate of chemosynthesis perfluoroalkyl compound, and be the preparation high-purity grade of necessary polymerization single polymerization monomer of fluoropolymer etc. and the important compound that receives much attention, its derivative is widely used in every field.The preparation method of current perfluoro-propionyl fluoride mainly contains Propylene oxide hexafluoride isomerization process, propionyl chloride and hydrogen fluoride electrolytic process, perfluoro methyl vinyl ether isomerization process, tetrafluoroethylene and fluorophosgene telomerization method etc.Because perfluoro methyl vinyl ether, tetrafluoroethylene and fluorophosgene expensive starting materials are difficult to obtain, two technological lines as raw material are all unsuitable for large-scale production.Electrolytic synthesis Raw inexpensively, but electrolytic efficiency product purity that is very low, that be difficult to avoid electrolysis impurity to cause is not high, electrolytic pole board cost of manufacture is expensive in addition, and cost of equipment is higher is unfavorable for industrial implementation.At present, perfluoro-propionyl fluoride carries out isomerization reaction preparation primarily of Propylene oxide hexafluoride under basic catalyst effect, and according to the difference of catalyzer, required reaction conditions is each variant.US4729856 report is with KHF
2, Na
2cO
3, dimethyl amine, vulkacit H make catalyzer, make solvent with DMF or ethers etc., when autogenous pressure or pressurization, Propylene oxide hexafluoride can be isomerizated into perfluoro-propionyl fluoride; US5684193 report is with liquid-fluorination hydrogen amine complex ({ [R
1r
2r
3nH]
+[H]
n-1f
n}
-) making catalyzer, perfluoro propene oxid isomery turns to perfluoro-propionyl fluoride at a certain temperature.But above-mentioned severe reaction conditions, reactor design are complicated, are unfavorable for suitability for industrialized production.Catalyzer is combined into organic amine compound, five yuan or hexa-atomic nitrogenous heterocyclic compounds or hexa-atomic condensed ring class aryl compound and basic metal villiaumite by certain quality proportioning in CN103145544A, although building-up process process warm and, simple to operate, but feedstock conversion is incomplete, and need just can obtain highly purified perfluoro-propionyl fluoride through second distillation containing other impurity in product.In JP58038231 under KF or the CsF catalyst action being carrier with gac, product perfluoro-propionyl fluoride yield is 71%, and reaction conversion ratio is lower.Therefore be necessary to research and develop a kind of high security, high purity, high yield, the more economical method preparing perfluoro-propionyl fluoride.At this, we propose a kind of with industry malicious byproduct Propylene oxide hexafluoride oligopolymer for feed material degradation obtains the method for perfluoro-propionyl fluoride.
Summary of the invention
The present invention is directed to above-mentioned the deficiencies in the prior art; from the angle of resource recycling; a kind of method being prepared perfluoro-propionyl fluoride by Propylene oxide hexafluoride oligopolymer is provided; change toxic byproduct into important chemical intermediate; raw materials cost is low; reaction conditions is gentle, product yield is high, is easy to large-scale production.
Technical scheme of the present invention:
1, a production method for perfluoro-propionyl fluoride, be with Propylene oxide hexafluoride oligopolymer be raw material, alkaline metal fluoride cpd is catalyzer, ether for solvent, carry out decomposition reaction at a certain temperature and generate perfluoro-propionyl fluoride, reaction equation is as follows:
Wherein, the arbitrary integer of the polymerization degree n=1-5 of Propylene oxide hexafluoride oligopolymer.Its reaction mechanism is as follows:
2, a production method for perfluoro-propionyl fluoride, is characterized in that: the gas produced in reaction process passes in cryotrap to be collected, and obtains liquid product perfluoro-propionyl fluoride.
3, described ether is the Macrogol 200 of TEG diethyl ether, diethylene glycol diethyl ether, ethylene glycol diethyl ether, triethylene glycol diethyl ether, tetraethyleneglycol dimethyl ether, diethylene glycol dimethyl ether, glycol dimethyl ether, TRIGLYME, terminal methyl end-blocking.
4, described Propylene oxide hexafluoride oligopolymer prepares the method for perfluoro-propionyl fluoride, it is characterized in that described alkaline metal fluoride cpd is LiF, NaF, KF, RbF, CsF.
5, described alkaline metal fluoride cpd/Propylene oxide hexafluoride oligopolymer (g/ml)=1/100 ~ 1/15g/ml.
6, described temperature of reaction is 90 ~ 200 DEG C,
7, the described reaction times is 12 ~ 72h, until water white fluorine disappears mutually bottom reaction flask.
The invention has the beneficial effects as follows: this production process with malicious waste product Propylene oxide hexafluoride oligopolymer for initial reactant, under certain temperature, catalyst action, decompose and generate high value chemical intermediate perfluoro-propionyl fluoride, product yield more than 95%, achieve resource recycling, turn waste into wealth; Raw materials cost is low, and reaction conditions is gentle, and product purity is greater than 99%, can be directly used in industrial production; Reaction process is simple to operate, is easy to large-scale production.
Embodiment
Substantive distinguishing features of the present invention and effect can be embodied from following embodiment, but they are not impose any restrictions the present invention.
Embodiment 1: Propylene oxide hexafluoride trimer is decomposed into perfluoro-propionyl fluoride
In the dry reactor of 1 liter of tool reflux exchanger, add Sodium Fluoride (5g), diethylene glycol dimethyl ether (100mL), Propylene oxide hexafluoride trimer (150mL), reaction system is heated to 120 DEG C gradually, keeps 12h at such a temperature, cryogenic condensation backflow simultaneously, until reactor bottom water white transparency fluorine disappears mutually, stop heating, be down to room temperature, the gas produced in reaction process passes in cold-trap to be collected, proceed to again in steel cylinder, obtain liquid perfluoro-propionyl fluoride (212g), yield 80%.The head product collected carries out gas-chromatography test, wherein perfluoro-propionyl fluoride content more than 96%, and gas chromatographic analysis result is as follows:
| Composition | Content (%) |
| Perfluoro-propionyl fluoride | 96.105 |
| Dimerization of hexafluoropropene oxide body | 2.402 |
| Propylene oxide hexafluoride tripolymer | 1.228 |
| Other | 0.265 |
Embodiment 2: Propylene oxide hexafluoride trimer is decomposed into perfluoro-propionyl fluoride
In 1 liter of tool reflux exchanger dry reactor, add Potassium monofluoride (5g), tetraethyleneglycol dimethyl ether (100mL), Propylene oxide hexafluoride trimer (150mL), reaction system is heated to 160 DEG C gradually, keeps 12h at such a temperature, cryogenic condensation backflow simultaneously, until reactor bottom water white transparency fluorine disappears mutually, stop heating, be down to room temperature, the gas produced in reaction process passes in cold-trap to be collected, proceed to again in steel cylinder, obtain liquid perfluoro-propionyl fluoride (244g), yield 92%.The head product collected carries out gas-chromatography test, wherein perfluoro-propionyl fluoride content more than 98%, and gas chromatographic analysis result is as follows:
| Composition | Content (%) |
| Perfluoro-propionyl fluoride | 98.207 |
| Dimerization of hexafluoropropene oxide body | 0.998 |
| Propylene oxide hexafluoride tripolymer | 0.569 |
| Other | 0.226 |
Embodiment 3: Propylene oxide hexafluoride oligopolymer is decomposed into perfluoro-propionyl fluoride
In the dry reactor of 1 liter of tool reflux exchanger, add cesium fluoride (5g), tetraethyleneglycol dimethyl ether (100mL), Propylene oxide hexafluoride trimer (150mL) be heated to 160 DEG C gradually, heat 6h at such a temperature, magnetic agitation, cryogenic condensation backflow simultaneously, until reactor bottom water white transparency fluorine disappears mutually, stop heating, be down to room temperature, the gas produced in reaction process passes in cold-trap to be collected, proceed to again in steel cylinder, obtain liquid perfluoro-propionyl fluoride product (216g), yield 90%.Carry out gas-chromatography test to the head product collected, wherein perfluoro-propionyl fluoride content more than 98%, gas chromatographic analysis result is as follows:
| Composition | Content (%) |
| Perfluoro-propionyl fluoride | 98.151 |
| Dimerization of hexafluoropropene oxide body | 1.015 |
| Propylene oxide hexafluoride tripolymer | 0.505 |
| Other | 0.329 |
Embodiment 4: Propylene oxide hexafluoride oligopolymer is decomposed into perfluoro-propionyl fluoride
In the dry reactor of 1 liter of tool reflux exchanger, add cesium fluoride (3g), tetraethyleneglycol dimethyl ether (100mL), Propylene oxide hexafluoride oligopolymer (n=4 ~ 7) (150mL) be heated to 160 DEG C gradually, heat 12 hours at such a temperature, magnetic agitation, cryogenic condensation backflow simultaneously, until reactor bottom water white transparency fluorine disappears mutually, stop heating, be down to room temperature, the gas produced in reaction process passes in cold-trap to be collected, proceed to again in steel cylinder, obtain liquid perfluoro-propionyl fluoride product (228g), yield 95%.Carry out gas-chromatography test to the head product collected, wherein perfluoro-propionyl fluoride content more than 99%, gas chromatographic analysis result is as follows:
| Composition | Content (%) |
| Perfluoro-propionyl fluoride | 99.082 |
| Dimerization of hexafluoropropene oxide body | 0.643 |
| Propylene oxide hexafluoride tripolymer | 0.131 |
| Other | 0.144 |
Above example of the present invention has been described in detail, but described content being only the preferred embodiment of this product invention, can not being considered to for limiting practical range of the present invention.All equalizations done according to the present patent application scope change and improve, and all should still belong within patent covering scope of the present invention.
Claims (7)
1. a production method for perfluoro-propionyl fluoride, is characterized in that: with Propylene oxide hexafluoride oligopolymer be raw material, alkaline metal fluoride cpd is catalyzer, ether for solvent, carry out reaction at a certain temperature and generate perfluoro-propionyl fluoride, reaction equation is as follows:
Wherein, the arbitrary integer of the polymerization degree n=1-5 of Propylene oxide hexafluoride oligopolymer.
2. a production method for perfluoro-propionyl fluoride, is characterized in that: the gas produced in reaction process passes in cryotrap to be collected, and obtains liquid product perfluoro-propionyl fluoride.
3. Propylene oxide hexafluoride oligopolymer according to claim 1 prepares the method for perfluoro-propionyl fluoride, it is characterized in that described ether is the Macrogol 200 of TEG diethyl ether, diethylene glycol diethyl ether, ethylene glycol diethyl ether, triethylene glycol diethyl ether, tetraethyleneglycol dimethyl ether, diethylene glycol dimethyl ether, glycol dimethyl ether, TRIGLYME, terminal methyl end-blocking.
4. Propylene oxide hexafluoride oligopolymer according to claim 1 prepares the method for perfluoro-propionyl fluoride, it is characterized in that described catalyzer is one or more mixtures of alkaline metal fluoride cpd LiF, NaF, KF, RbF, CsF.
5. Propylene oxide hexafluoride oligopolymer according to claim 1 prepares the method for perfluoro-propionyl fluoride, it is characterized in that alkaline metal fluoride cpd/Propylene oxide hexafluoride oligopolymer (g/ml)=1/100 ~ 1/15g/ml.
6. Propylene oxide hexafluoride oligopolymer according to claim 1 prepares the method for perfluoro-propionyl fluoride, it is characterized in that described temperature of reaction is 90 ~ 200 DEG C.
7. Propylene oxide hexafluoride oligopolymer according to claim 1 prepares the method for perfluoro-propionyl fluoride, it is characterized in that the reaction times is 12 ~ 72h, until reactor bottom water white fluorine phase complete reaction.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106631770A (en) * | 2016-12-14 | 2017-05-10 | 天津市长芦化工新材料有限公司 | Method for synthesizing beta-halogen tetrafluoroacyl fluoride |
| KR20220005774A (en) * | 2020-07-07 | 2022-01-14 | 한국화학연구원 | Method for preparing hexafluoropropylene oxide dimer with high conversion rate |
| CN114620705A (en) * | 2022-02-24 | 2022-06-14 | 浙江诺亚氟化工有限公司 | Method for preparing high-purity carbonyl fluoride from hexafluoropropylene oxide |
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|---|---|---|---|---|
| JPS62270546A (en) * | 1986-05-19 | 1987-11-24 | Nippon Mektron Ltd | Production of perfluoropropionic acid fluoride |
| US4769184A (en) * | 1987-09-08 | 1988-09-06 | Nippon Mektron Limited | Process for producing carbonyl fluoride compound |
| JPH04139145A (en) * | 1990-09-28 | 1992-05-13 | Nippon Mektron Ltd | Production of perfluoro(2-lower alkoxypropionic acid) fluoride |
| US5684193A (en) * | 1995-11-13 | 1997-11-04 | Hoechst Aktiengesellschaft | Process for the preparation of perfluoropropionyl fluoride |
| CN103145544A (en) * | 2011-12-06 | 2013-06-12 | 中化蓝天集团有限公司 | Method for synthesis of pentafluoropropionyl fluoride |
| CN104016848A (en) * | 2014-06-30 | 2014-09-03 | 黄辉 | Preparation method of pentafluoropropionyl fluoride |
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2014
- 2014-08-04 CN CN201410379162.0A patent/CN105315150A/en active Pending
Patent Citations (6)
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|---|---|---|---|---|
| JPS62270546A (en) * | 1986-05-19 | 1987-11-24 | Nippon Mektron Ltd | Production of perfluoropropionic acid fluoride |
| US4769184A (en) * | 1987-09-08 | 1988-09-06 | Nippon Mektron Limited | Process for producing carbonyl fluoride compound |
| JPH04139145A (en) * | 1990-09-28 | 1992-05-13 | Nippon Mektron Ltd | Production of perfluoro(2-lower alkoxypropionic acid) fluoride |
| US5684193A (en) * | 1995-11-13 | 1997-11-04 | Hoechst Aktiengesellschaft | Process for the preparation of perfluoropropionyl fluoride |
| CN103145544A (en) * | 2011-12-06 | 2013-06-12 | 中化蓝天集团有限公司 | Method for synthesis of pentafluoropropionyl fluoride |
| CN104016848A (en) * | 2014-06-30 | 2014-09-03 | 黄辉 | Preparation method of pentafluoropropionyl fluoride |
Non-Patent Citations (1)
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|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106631770A (en) * | 2016-12-14 | 2017-05-10 | 天津市长芦化工新材料有限公司 | Method for synthesizing beta-halogen tetrafluoroacyl fluoride |
| CN106631770B (en) * | 2016-12-14 | 2019-11-22 | 天津市长芦化工新材料有限公司 | A kind of synthetic method of beta-halogen tetrafluoro propionyl fluoride |
| KR20220005774A (en) * | 2020-07-07 | 2022-01-14 | 한국화학연구원 | Method for preparing hexafluoropropylene oxide dimer with high conversion rate |
| KR102425264B1 (en) | 2020-07-07 | 2022-07-26 | 한국화학연구원 | Method for preparing hexafluoropropylene oxide dimer with high conversion rate |
| CN114620705A (en) * | 2022-02-24 | 2022-06-14 | 浙江诺亚氟化工有限公司 | Method for preparing high-purity carbonyl fluoride from hexafluoropropylene oxide |
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