CN103787854A - Preparation process of perfluoro-2-methyl-3-pentanone - Google Patents
Preparation process of perfluoro-2-methyl-3-pentanone Download PDFInfo
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
- C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
- C07C45/58—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in three-membered rings
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- C07D301/00—Preparation of oxiranes
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- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
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- C07D303/02—Compounds containing oxirane rings
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Abstract
The invention discloses a preparation process of perfluoro-2-methyl-3-pentanone, belonging to the technical field of preparation methods of perfluoroketone compounds in the field of organofluorine chemistry. The perfluoro-2-methyl-3-pentanone is obtained by performing an epoxidation reaction and a catalytic isomerization reaction on perfluoro-2-methyl-pentene serving as a raw material in sequence. The preparation process comprises the following steps: I, in a continuous liquid phase epoxidation reaction, mixing a corresponding proportion of aprotic polar solvent into a sodium hypochlorite solution to promote the reaction, increase the raw material conversion ratio and increase the reaction rate at least by 2-3 percent, wherein the step is characterized by easiness and convenience in operation, low equipment requirement and high reaction equipment efficiency; II, performing a continuous gas phase catalytic reaction, wherein the application of a solvent is effectively avoided, the cost and environmental pollution are lowered, the problems of the need of separating the solvent from a product in post-treatment, difficulty in recycling and treating the solvent and a catalyst, and the like are solved, and the product can be refined and purified more easily. The preparation process has the advantages of high process automation degree, easiness and convenience in operation, high product purity and high reaction equipment efficiency, and is suitable for industrial application.
Description
Technical field
The invention belongs to preparation method's technical field of perfluor ketone compounds in organic fluorine chemistry field, particularly a kind of preparation technology of perfluor-2-methyl-propione.
Background technology
Perfluor-2-methyl-propione (Perfluoro-2-methyl-3-pentanone), also claims FK-5-1-12, and it belongs to perfluor ketone compounds, and boiling point is 49 ℃, is colourless liquid under normal temperature and pressure.It has lower boiling, high volatile volatile, low toxicity, does not fire, is easy to the features such as accumulating, use properties excellence and good environmental protection, there is easy vaporization as fire-fighting medium, the features such as heat absorption capacity is strong, and extinguishing property is good, therefore mainly as the clean substitute of halon fire agent; Due to its good insulation preformance, do not belong to hazardous substance again, after release, do not leave over residue, cause damage can to the valuable properties such as sensitive electronic equipment, function unit and navigational aid, can be used to protect precision instrument and expensive equipment etc.The life-span of perfluor-2-methyl-propione in atmosphere only has 5 days, and its harm to environment, human body is almost equal to zero.
The synthetic method of perfluor-2-methyl-propione of bibliographical information mainly contains following three kinds: the method for the first synthetic perfluor-2-methyl-propione take R 1216 and Propylene oxide hexafluoride as raw material.Я. М. (the Zh. Vses. Khim. O-va. 1978 such as the Lie Enqike of committee, 23 (2), 236-7 (Russ). CA 89:23715p) employing CsF is catalyzer, take R 1216 and Propylene oxide hexafluoride as raw material, can synthesize perfluor-2-methyl-propione by single step reaction, but yield is only 34.6%.Main By product is F
3cCF
2cO (CF
2)
5cF
3, and F (42.6%)
3cCF
2cO (CF
2)
8cF
3(8%) etc., these by products may be caused by the side reaction such as dimerization or trimerization of R 1216.After this, Я. М. the Lie Enqike of committee etc. has carried out improving (SU698289 to above reaction, CA 102:220445p.), claim that adopting the sylvite (as KOCN, KSCN or KCN) of pseudohalogen is catalyzer, can bring up to 53.4-73.8% by the yield of reaction product perfluor-2-methyl-propione take acetonitrile as solvent.In addition, В. Г. (RU2010150091) the disclosed patents such as Barabbas promise husband claim under the CsF catalysis take gac as carrier, in gas-phase reaction mode, R 1216 and Propylene oxide hexafluoride are interacted, can make the yield of reaction product perfluor-2-methyl-propione bring up to more than 90%.The advantage of above synthesis method is that building-up reactions step is few, but needs R 1216 and two organic fluorine raw materials of Propylene oxide hexafluoride, and reaction yield need further raising.
It two is methods of synthetic perfluor-2-methyl-propione take R 1216 and perfluoro-propionyl fluoride as raw material.Fawcett Frank S. etc. (J.Am.Chem. Soc. 1962,84:4285-4288.) report the reaction that is generated perfluor ketone by perfluoroolefine and perfluoroacyl fluoride reaction the earliest.The invention disclosed patents such as the bright man of virtue and ability in Central Plains "
production of fluoroketone "in (JP1226846 (A)), adopt similar reactive mode.Rivers Paul E. etc. are in the patent (US6478979 (B1)) as fire-fighting medium application about perfluor-2-methyl-propione, also adopt take R 1216 and perfluoro-propionyl fluoride as raw material, in non-protonic solvent (as diglyme) and prepare the method for perfluor-2-methyl-propione under Compounds Catalyzed by Potassium Fluoride.This method subject matter is to need R 1216 and two organofluorine compound raw materials of perfluoro-propionyl fluoride, and especially perfluoro-propionyl fluoride there is no supply of commodities, need to form a complete production network.
It three is through the method for the synthetic perfluor-2-methyl-propione of the isomerization two-step reaction of epoxidation and epoxide (I and II) take hexafluoropropylene dimmer as raw material.Reaction formula is as follows:
More than reaction see the earliest Zapevalov A. Ya. etc. report (
oxides of hexafluoropropylene dimers. [J]. Izv. Akad. Nauk SSSR, Ser. Khim. 1979, (12), 2812-15 (Russ). CA 92:128624y).Wherein the epoxide of hexafluoropropylene dimmer (II) can be through selectively isomerization generation perfluor-2-methyl-propione of the catalysis height of cesium fluoride or triethylamine.Hexafluoropropylene dimmer can adopt the known method in this area to telomerize acquisition via R 1216.The advantage of this method is the organofluorine compound raw material that only needs this kind of commercial scale production of R 1216.But, from R 1216 need to be via telomerizing, several steps reactions such as the isomerization of epoxidation and epoxy compounds just can make perfluor-2-methyl-propione, its synthetic reactions steps is relatively many, require related each step reaction all to have higher yields just may have a total recovery that meets industrialization production requirements, the two-step reactions such as epoxidation especially below and epoxy compounds isomerization have higher yield level to have decisive significance to the practical value of this synthetic route.
Summary of the invention
For the above-mentioned problems in the prior art, the object of the present invention is to provide a kind of easy and simple to handle, level of automation is high, can suppress or reduce by product generation, improve synthesis yield and quality product, and can improve equipment service efficiency, reduce the preparation technology of perfluor-2-methyl-propione of quantity of three wastes.
The preparation technology of described a kind of perfluor-2-methyl-propione, it is characterized in that take perfluoro-2-methyl-2-amylene as raw material, obtain through epoxidation reaction and isoversion reaction successively, described epoxidation reaction is continuity reaction, and described isoversion reaction is vapor phase process reaction.
The preparation technology of described a kind of perfluor-2-methyl-propione, is characterized in that comprising the steps:
1) intermediate perfluor-2-methyl-2, the preparation of 3-epoxy pentane
Take perfluoro-2-methyl-2-amylene, clorox-aprotic polar solvent mixing solutions as raw material, it is-15～10 ℃ in temperature of reaction, reaction time is under 30～180s, to carry out Continuous Liquid Phase epoxidation reaction, after reaction finishes, filter, separate to obtain intermediate perfluor-2-methyl-2,3-epoxy pentane;
2) preparation of perfluor-2-methyl-propione
Perfluor-2-methyl-2 that obtain with step 1), 3-epoxy pentane is raw material, under supported catalyst effect, temperature of reaction is 100～250 ℃, pressure is under the condition of 0～0.25MPa, carries out continuous gas phase catalysis isomerization reaction, collects condensed gas, obtain perfluor-2-methyl-propione crude product, then obtain refining perfluor-2-methyl-propione product through rectifying.Supported catalyst involved in the present invention can directly use without special activation treatment, also can first after the pre-activation treatment of Propylene oxide hexafluoride, re-use.
The preparation technology of described a kind of perfluor-2-methyl-propione, the available chlorine content that it is characterized in that chlorine bleach liquor in step 1) is 10～20%, the molar ratio of perfluoro-2-methyl-2-amylene and clorox is 1: 1.05～1.5.
The preparation technology of described a kind of perfluor-2-methyl-propione, the available chlorine content that it is characterized in that chlorine bleach liquor in step 1) is 13～18%, the molar ratio of perfluoro-2-methyl-2-amylene and clorox is 1: 1.1～1.3.
The preparation technology of described a kind of perfluor-2-methyl-propione, is characterized in that in step 1), temperature of reaction is-10～0 ℃, and reaction time is 60～120 seconds.
The preparation technology of described a kind of perfluor-2-methyl-propione, it is characterized in that the non-proton property polar solvent described in step 1) is acetonitrile or diethylene glycol dimethyl ether, non-proton property polar solvent and chlorine bleach liquor's mass ratio is 0.2～5: 10, and preferred mass ratio is 0.5～1.5: 10.
The preparation technology of described a kind of perfluor-2-methyl-propione, is characterized in that step 2) in temperature of reaction be 150～220 ℃, reaction pressure is 0.10～0.15Mpa.
The preparation technology of described a kind of perfluor-2-methyl-propione, is characterized in that step 2) described in carried catalyst be that the complex compound of the cesium fluoride catalyzer take activated carbon as carrier or the Potassium monofluoride using activated carbon as carrier and 18-hat-6 is as catalyzer.
The preparation technology of described a kind of perfluor-2-methyl-propione, is characterized in that step 2) described in carried catalyst for take activated carbon or DMSO solvent as carrier, be preced with-6 complex compound as catalytic active component using cesium fluoride or Potassium monofluoride and 18-.
The preparation technology of described a kind of perfluor-2-methyl-propione, it is characterized in that step 2) preparation of middle supported catalyst employing pickling process, the mass ratio of catalytic active component and carrier is 5～30%, preferred mass ratio is 15～25%, and catalytic active component is the complex compound of cesium fluoride or Potassium monofluoride and 18-hat-6.
Preparation technology's equipment used of described a kind of perfluor-2-methyl-propione, it is characterized in that comprising the First Heat Exchanger and the second interchanger that are respectively used to add perfluoro-2-methyl-2-amylene and clorox-aprotic polar solvent mixing solutions, First Heat Exchanger is all connected with mixing tank with the second interchanger, mixing tank successively with Liquid-phase reactor, strainer and liquid liquid/gas separator connect, liquid liquid/gas separator bottom intermediate out enters volume pump, volume pump is connected with vaporizer bottom, vaporizer top successively with catalyticreactor, condenser and rectifying tower connect, after rectifying tower rectifying, obtain product.
By adopting above-mentioned technology, compared with prior art, beneficial effect of the present invention is as follows:
1) intermediate perfluor-2-of the present invention methyl-2, time prepared by 3-epoxy pentane, by adopting the rapid reaction of Continuous Liquid Phase epoxidation, and the intermediate obtaining after reaction hightails reaction system, directly put into next step reaction, intermediate perfluor-2-methyl-2 of having avoided reaction to obtain, 3-epoxy pentane has longer duration of contact with raw material alkalescence aqueous sodium hypochlorite solution within reaction time, greatly reduce perfluor-2-methyl-2,3-epoxy pentane is hydrolyzed the probability occurring, and improves selectivity and the yield of this epoxidation reaction;
2) in Continuous Liquid Phase epoxidation reaction of the present invention, the non-proton property of acetonitrile, the diethylene glycol dimethyl ether etc. of mixture corresponding proportion polar solvent in chlorine bleach liquor, the carrying out of promotion reaction, improves feed stock conversion;
3) Continuous Liquid Phase epoxidation of the present invention obtains product yield is high, purity stable, its reaction yield at least improves 2～3% than conventional epoxidation reaction mode at intermittence, the thick product content of the epoxidation reaction obtaining at least improves approximately 2% than conventional epoxidation reaction mode at intermittence, and Continuous Liquid Phase epoxidizing method is easy and simple to handle, low for equipment requirements and conversion unit efficiency is high;
4) second step of the present invention is by adopting continuous gas phase catalytic reaction, intermediate perfluor-2-methyl-2 that previous step is made, 3-epoxy pentane is high to be selected, change into high yield perfluor-2-methyl-propione, its transformation efficiency and yield reach the level of liquid phase method, even high than liquid phase method, and effectively avoid using solvent, cost and environmental pollution are reduced, and avoid needing solvent and product separation in aftertreatment, the problems such as the recycling difficulty of solvent and catalyzer, make the refining purification of product become easier, it is high that it has automation technolo degree, easy and simple to handle, product purity is high, conversion unit efficiency advantages of higher,
5) Continuous Liquid Phase epoxidation of the present invention and continuously gas phase catalytic reaction two-step approach, raw material perfluoro-2-methyl-2-amylene is converted into perfluor-2-methyl-propione, it have easy to operate, low for equipment requirements, cost is low, product be easy to separate, automation technolo degree is high, easy and simple to handle, product purity is high, conversion unit efficiency advantages of higher, its purity reaches more than 99.7%, reaches suitability for industrialized production application.
Embodiment
Below in conjunction with Figure of description and embodiment, the invention will be further described, and the following example is that indefiniteness of the present invention is described, and protection scope of the present invention is not limited in this:
As shown in Figure 1, the preparation technology of perfluor-2-methyl-propione of the present invention, specifically comprises the steps:
1) first by proportioning, preparation chlorine bleach liquor, in this solution, add the aprotic polar solvent (as acetonitrile or diethylene glycol dimethyl ether) of respective amount to mix, obtain clorox-aprotic polar solvent mixing solutions, the chlorine bleach liquor's that the present invention joins available chlorine content is 10～20%, and preferred concentration is 13～18%; Non-proton property polar solvent and chlorine bleach liquor's mass ratio is 0.2～5: 10, and preferred mass ratio is 0.5～1.5: 10;
2) perfluoro-2-methyl-2-amylene and clorox-aprotic polar solvent mixing solutions are added respectively in First Heat Exchanger and the second interchanger and be cooled to below-10 ℃, the cooling rear mixing tank that adds respectively mixes, proceed to again Liquid-phase reactor, it is-15～10 ℃ in temperature of reaction, reaction time is under 30～180s, to carry out Continuous Liquid Phase epoxidation reaction, after reaction finishes, enter strainer, the salt of separating out is removed, enter again liquid liquid/gas separator, waste water is removed in layering, obtain intermediate perfluor-2-methyl-2, 3-epoxy pentane crude product, the molar ratio of perfluoro-2-methyl-2-amylene and clorox is 1: 1.05～1.5, preferably molar ratio is 1: 1.1～1.3, preferable reaction temperature is-10～0 ℃, the preferred reaction residence time is 60～120 seconds,
3) after first carried catalyst being processed, add catalyticreactor, perfluor-2-methyl-2 that measure by volume pump again, 3-epoxy pentane adds vaporizer bottom to vaporize, after vaporization, add in catalyticreactor, it is 100～250 ℃ in temperature of reaction, pressure is under the condition of 0～0.25MPa, carry out continuous gas phase catalysis isomerization reaction, reaction finishes rear reactant and enters condenser and carry out cooling, collect cooling fluid, obtain thick product, add rectifying tower to carry out rectifying this thick product, obtain product, this rectifying can be once rectifying or secondary rectifying, improve the purity of product, in this step, preferable reaction temperature is 150～220 ℃, preferred reaction pressure is 0.10～0.15Mpa,
Carried catalyst of the present invention be cesium fluoride catalyzer take activated carbon as carrier or using activated carbon or DMSO solvent as the Potassium monofluoride of carrier and the complex compound of 18-hat-6 as catalyzer, this catalyzer adopts pickling process preparation, the mass ratio of catalytic active component and activity carbon carrier is 5～30%, preferred mass ratio is 15～25%, and catalytic active component is the complex compound of cesium fluoride or Potassium monofluoride and 18-hat-6.
Method of the present invention and uses thereof will further be illustrated by following examples, and the following example is that indefiniteness of the present invention is described.
Embodiment 1: Continuous Liquid Phase epoxidation process synthesizes perfluor-2-methyl-2,3-epoxy pentane
Carry out according to the following steps:
A. the chlorine bleach liquor that the freshly prepd available chlorine content of prefabricated 164.7kg is 16.98%, add 19.7L acetonitrile, mix and make clorox-acetonitrile solution, taking 98.6kg (0.329kmol) content is 97.4% perfluoro-2-methyl-2-amylene again, perfluoro-2-methyl-2-amylene of the present invention adopt known method by R 1216 through telomerizing and isomerization obtains;
B. by clorox-acetonitrile solution and perfluoro-2-methyl-2-amylene respectively with volume pump by proportioning metering after, be cooled to-10 ℃ of left and right by the second interchanger and First Heat Exchanger respectively and send into continuously afterwards mixing tank and mix;
C. the hybrid reaction material in mixing tank is sent in the Liquid-phase reactor of duct type continuously, the residence time is 1min, and control temperature is-10 ℃ and reacts;
D. the mixture salt that elimination is separated out through filter after reaction;
E. the reaction mixture of steps d step enters the separation of liquid liquid phase separator, discards waste water, obtains epoxide intermediates perfluor-2-methyl-2,3-epoxy pentane;
F. by gained perfluor-2-methyl-2,3-epoxy pentane measures rear sampling analysis.
Result: obtain epoxide crude product perfluor-2-methyl-2,3-epoxy pentane quality is 99.4kg (0.314kmol), and content is 97.18%, and yield is 95.49%.
Embodiment 2:
Continuous Liquid Phase epoxidation process synthesizes perfluor-2-methyl-2, and 3-epoxy pentane carries out according to the following steps:
The method operation identical with embodiment 1, difference is that clorox quality is 163.3kg, and available chlorine content is 17.11%, and acetonitrile consumption is 19.7L, perfluoro-2-methyl-2-amylene consumption is that 98.6kg (0.329kmol) content is 98.21%, and temperature of reaction is 0 ℃.
Result: obtaining epoxide crude product quality is 99.2kg (0.314kmol), and content is 97.83%, and yield is 95.14%.
Embodiment 3:
Continuous Liquid Phase epoxidation process synthesizes perfluor-2-methyl-2, and 3-epoxy pentane carries out according to the following steps:
The method operation identical with embodiment 1, difference is that clorox quality is 164.6kg, available chlorine content is 18.03%, and diethylene glycol dimethyl ether consumption is 22.6L, and perfluoro-2-methyl-2-amylene consumption is that 113.3kg (0.329kmol) content is 98.21%.
Result: obtaining epoxide crude product quality is 114.2kg (0.356kmol), and content is 97.62%, and yield is 95.12%.
Embodiment 4:
Continuous Liquid Phase epoxidation process synthesizes perfluor-2-methyl-2, and 3-epoxy pentane carries out according to the following steps:
The method operation identical with embodiment 1, difference is that clorox quality is 204.3kg, and available chlorine content is 13.27%, and acetonitrile consumption is 22.6L, perfluoro-2-methyl-2-amylene consumption is that 88.2kg (0.294kmol) content is 98.21%, and temperature of reaction is 0 ℃.
Result: obtaining epoxide crude product quality is 87.8kg (0.278kmol), and content is 97.24%, and yield is 93.57%.
Embodiment 5:
Vapor phase process synthesizes perfluor-2-methyl-propione to carry out according to the following steps:
A. 25% nitric acid and activated carbon particle are mixed (at least submergence), and in vapor bath, boil 6h, filter, wash after nitric acid, in 105 ℃ of oven dry;
B. take 1.8kg cesium fluoride 10kg distilled water wiring solution-forming by 15% ratio requirement, add by the pretreated activated carbon of proportioning metering, at room temperature and adopt ultrasonic concussion method to flood more than 4 hours;
C. by macerate in boiling water bath heating evaporation dehydration, after having dewatered, this 15% cesium fluoride-gac is put into vacuum drying oven and at 180 ℃, is carried out vacuum-drying to till constant weight;
D. by 15% cesium fluoride-activated carbon uniform filling in reaction tower, then this reaction tower system is vacuumized and is heated to 250 ℃ of left and right of activation temperature, with after pure nitrogen gas displacement several times again under decompression state the pure nitrogen gas (250 ℃) with low discharge the catalyzer in reaction tower is purged and is dried 3 hours;
E. heated Tube reactor to 180 ℃;
F. take 97.3kg (0.308kmol) perfluor-2-methyl-2,3-epoxy pentane (content 96.83%), joins in vaporizer, is preheating to 150 ℃;
G. open tubular reactor opening for feed, make perfluor-2-methyl-2 of preheating, 3-epoxy pentane gas imports in tubular reactor continuously.Control 180 ℃ of temperature, the about 0.1Mpa of pressure, 10 seconds residence time;
H. at tubular reactor discharge port, adopt condensation receive mode that reacted condensation of gas is received, and quantitative analysis.
Test-results: thick quality product is 96.9kg (0.307kmol), and content is 95.79%, and yield is 98.52%.
Embodiment 6:
Vapor phase process synthesizes perfluor-2-methyl-propione and clicks step and carry out:
The operation identical with embodiment tri-, difference is that " step b. in embodiment 3 " adopts Potassium monofluoride and 18-hat-6 complex compounds to substitute cesium fluoride as catalyzer, is dissolved in appropriate DMSO solvent as soaker altogether using Potassium monofluoride and 18-hat-6.
Result: thick quality product is 97.0kg (0.307kmol), and content is 95.51%, and yield is 98.33%.
Embodiment 7:
Vapor phase process synthesizes perfluor-2-methyl-propione and clicks step and carry out:
The operation identical with embodiment 5, difference is that temperature of reaction is 150 ℃, and reaction pressure is 0.05MPa, and the residence time is 20s.
Result: thick quality product is 97.1kg (0.307kmol), content is that 93.24%(also has 2.32% epoxide unconverted), yield is 96.09%.
Embodiment 8:
Vapor phase process synthesizes perfluor-2-methyl-propione and clicks step and carry out:
The operation identical with embodiment 5, difference is that temperature of reaction is 200 ℃, reaction pressure is 0.15MPa.
Result: thick quality product is 96.7kg (0.306kmol), and content is that 94.72%(by-products content increases), yield is 97.22%.
Embodiment 9:
The rectifying of crude product perfluor-2-methyl-propione:
Crude product perfluor-2-methyl-propione the 100.2kg (0.317kmol) obtaining by this technical process, content is that 95.68% to enter theoretical plate number be in 15 rectifying tower, carry out rectifying, obtain purity and be perfluor-2-methyl-propione product 94.3kg(0.298kmol of 99.72%), rectification yield is 98.09%.
Claims (10)
1. the preparation technology of perfluor-2-methyl-propione, it is characterized in that take perfluoro-2-methyl-2-amylene as raw material, obtain through epoxidation reaction and isoversion reaction successively, described epoxidation reaction is continuity reaction, and described isoversion reaction is vapor phase process reaction.
2. the preparation technology of a kind of perfluor-2-methyl-propione according to claim 1, is characterized in that comprising the steps:
1) intermediate perfluor-2-methyl-2, the preparation of 3-epoxy pentane
Take perfluoro-2-methyl-2-amylene, clorox-aprotic polar solvent mixing solutions as raw material, it is-15～10 ℃ in temperature of reaction, reaction time is under 30～180s, to carry out Continuous Liquid Phase epoxidation reaction, after reaction finishes, filter, separate to obtain intermediate perfluor-2-methyl-2,3-epoxy pentane;
2) preparation of perfluor-2-methyl-propione
Perfluor-2-methyl-2 that obtain with step 1), 3-epoxy pentane is raw material, under supported catalyst effect, temperature of reaction is 100～250 ℃, pressure is under the condition of 0～0.25MPa, carries out continuous gas phase catalysis isomerization reaction, collects condensed gas, obtain perfluor-2-methyl-propione crude product, then obtain refining perfluor-2-methyl-propione product through rectifying.
3. the preparation technology of a kind of perfluor-2-methyl-propione according to claim 2, the available chlorine content that it is characterized in that chlorine bleach liquor in step 1) is 10～20%, and the molar ratio of perfluoro-2-methyl-2-amylene and clorox is 1: 1.05～1.5.
4. the preparation technology of a kind of perfluor-2-methyl-propione according to claim 2, the available chlorine content that it is characterized in that chlorine bleach liquor in step 1) is 13～18%, and the molar ratio of perfluoro-2-methyl-2-amylene and clorox is 1: 1.1～1.3.
5. the preparation technology of a kind of perfluor-2-methyl-propione according to claim 2, is characterized in that in step 1), temperature of reaction is-10～0 ℃, and reaction time is 60～120 seconds.
6. the preparation technology of a kind of perfluor-2-methyl-propione according to claim 2, it is characterized in that the non-proton property polar solvent described in step 1) is acetonitrile or diethylene glycol dimethyl ether, non-proton property polar solvent and chlorine bleach liquor's mass ratio is 0.2～5: 10, and preferred mass ratio is 0.5～1.5: 10.
7. the preparation technology of a kind of perfluor-2-methyl-propione according to claim 2, is characterized in that step 2) in temperature of reaction be 150～220 ℃, reaction pressure is 0.10～0.15Mpa.
8. the preparation technology of a kind of perfluor-2-methyl-propione according to claim 2, it is characterized in that step 2) described in carried catalyst for take activated carbon or DMSO solvent as carrier, be preced with-6 complex compound as catalytic active component using cesium fluoride or Potassium monofluoride and 18-.
9. the preparation technology of a kind of perfluor-2-methyl-propione according to claim 8, it is characterized in that step 2) preparation of middle supported catalyst employing pickling process, the mass ratio of catalytic active component and carrier is 5～30%, preferred mass ratio is 15～25%, and catalytic active component is the complex compound of cesium fluoride or Potassium monofluoride and 18-hat-6.
10. preparation technology's equipment used of perfluor-2-methyl-propione, it is characterized in that comprising the First Heat Exchanger (1) and the second interchanger (2) that are respectively used to add perfluoro-2-methyl-2-amylene and clorox-aprotic polar solvent mixing solutions, First Heat Exchanger (1) is all connected with mixing tank (3) with the second interchanger (2), mixing tank (3) successively with Liquid-phase reactor (4), strainer (5) and liquid liquid/gas separator (6) connect, liquid liquid/gas separator (6) bottom intermediate out enters volume pump (7), volume pump (7) is connected with vaporizer (8) bottom, vaporizer (8) top successively with catalyticreactor (9), condenser (10) and rectifying tower (11) connect, after rectifying tower (11) rectifying, obtain product.
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Cited By (8)
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| CN105198719A (en) * | 2015-09-06 | 2015-12-30 | 浙江工业大学 | Preparation method of perfluoro-2-methyl-3-pentanone |
| CN105439835A (en) * | 2015-12-02 | 2016-03-30 | 上海三爱富新材料股份有限公司 | Preparation method of C6-fluoroketone |
| CN106542984A (en) * | 2016-10-13 | 2017-03-29 | 巨化集团技术中心 | A kind of preparation method of 2 methyl of perfluor, 3 pentanone |
| CN106645360A (en) * | 2016-11-25 | 2017-05-10 | 浙江诺亚氟化工有限公司 | Determination method of trace acid value in perfluoro-2-methyl-3-pentanone |
| CN107879912A (en) * | 2016-09-29 | 2018-04-06 | 中国科学院上海有机化学研究所 | A kind of continuous production technology of the pentanone of 2 methyl of perfluor 3 |
| CN112250552A (en) * | 2020-09-15 | 2021-01-22 | 浙江巨化技术中心有限公司 | Preparation method of perfluorohexanone |
| CN115785029A (en) * | 2022-12-08 | 2023-03-14 | 浙江诺亚氟化工有限公司 | Preparation method of perfluoro-2-methyl-2, 3-epoxypentane |
| CN116514642A (en) * | 2023-05-06 | 2023-08-01 | 多氟多新材料股份有限公司 | Preparation method and application of perfluoro-hexanone |
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| CN102844285A (en) * | 2010-02-18 | 2012-12-26 | 霍尼韦尔国际公司 | Integrated process and methods of producing (e)-1-chloro-3,3,3-trifluoropropene |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105198719A (en) * | 2015-09-06 | 2015-12-30 | 浙江工业大学 | Preparation method of perfluoro-2-methyl-3-pentanone |
| CN105439835A (en) * | 2015-12-02 | 2016-03-30 | 上海三爱富新材料股份有限公司 | Preparation method of C6-fluoroketone |
| CN107879912A (en) * | 2016-09-29 | 2018-04-06 | 中国科学院上海有机化学研究所 | A kind of continuous production technology of the pentanone of 2 methyl of perfluor 3 |
| CN107879912B (en) * | 2016-09-29 | 2022-08-16 | 上海爱默金山药业有限公司 | Continuous production process of perfluoro-2-methyl-3-pentanone |
| CN106542984A (en) * | 2016-10-13 | 2017-03-29 | 巨化集团技术中心 | A kind of preparation method of 2 methyl of perfluor, 3 pentanone |
| CN106645360A (en) * | 2016-11-25 | 2017-05-10 | 浙江诺亚氟化工有限公司 | Determination method of trace acid value in perfluoro-2-methyl-3-pentanone |
| CN112250552A (en) * | 2020-09-15 | 2021-01-22 | 浙江巨化技术中心有限公司 | Preparation method of perfluorohexanone |
| CN112250552B (en) * | 2020-09-15 | 2023-02-03 | 浙江巨化技术中心有限公司 | Preparation method of perfluorohexanone |
| CN115785029A (en) * | 2022-12-08 | 2023-03-14 | 浙江诺亚氟化工有限公司 | Preparation method of perfluoro-2-methyl-2, 3-epoxypentane |
| CN116514642A (en) * | 2023-05-06 | 2023-08-01 | 多氟多新材料股份有限公司 | Preparation method and application of perfluoro-hexanone |
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Effective date of registration: 20160606 Address after: 321300 Hangzhou Bay Shangyu economic and Technological Development Zone, Shangyu District, Zhejiang, Shaoxing Patentee after: Zhejiang Nuoya Fluorine Chemical Co., Ltd. Address before: 29 Luoyang Road, Singapore Patentee before: ORIENT CORPORATION PTE. LTD. |