CN109336751A - The method that gas phase prepares perfluor ketone - Google Patents
The method that gas phase prepares perfluor ketone Download PDFInfo
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- CN109336751A CN109336751A CN201811370841.6A CN201811370841A CN109336751A CN 109336751 A CN109336751 A CN 109336751A CN 201811370841 A CN201811370841 A CN 201811370841A CN 109336751 A CN109336751 A CN 109336751A
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- ketone
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- fluoride
- perfluoroolefine
- acyl fluorides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/69—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to carbon-to-carbon double or triple bonds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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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Abstract
The invention discloses a kind of methods for preparing gas phase and preparing perfluor ketone, it may be assumed that in the presence of addition catalyst, perfluoroolefine R1R2C=CR3R4With acyl fluorides R5- COF or perfluor substituted epoxy ethane Cyclio-O-CF2‑C(R6)(R7)-gas phase addition reaction occurs, obtains perfluor ketone CFR3R4‑CR1R2‑C(O)R5(R5For perfluoroalkyl) either CFR3R4‑CR1R2‑C(O)‑CR1R2‑CFR3R4(R5For F atom) either CFR3R4‑CR1R2‑C(O)‑CFR6R7.Not only perfluoroolefine and acyl fluorides are easy to get the method for the present invention, cheap, and the yield of perfluor ketone is high, which is easy to serialization large-scale industrial production.
Description
Technical field
The present invention relates to a kind of methods that gas phase prepares perfluor ketone, more particularly to one kind is with acyl fluorides or perfluor substituted epoxy
Ethane is starting material, and gas phase addition reaction occurs with perfluoroolefine in the presence of addition catalyst and obtains the preparation side of perfluor ketone
Method.
Background technique
Perfluor ketone is using trifluoromethyl perfluoroisopropyl ketone and pentafluoroethyl group perfluoroisopropyl ketone as main representative.By mesh
Before, all kinds of documents disclose the route of five synthesis perfluor ketone altogether.
First route is the liquid phase addition reaction of the isomer of perfluoroolefine and acyl fluorides or acyl fluorides.Perfluoroolefine can
To be hexafluoropropene etc., acyl fluorides can be trifluoro-ethylene acyl fluorides, five fluorine propionyl fluorides etc., and the isomer of acyl fluorides can be hexafluoro
Propylene oxide.Document [Molecules 2011,16,6512-6540.] reports in anhydrous diglyme solvent, urges
Agent KF is catalyzed hexafluoropropene and reacts 8h, the yield of trifluoromethyl perfluoroisopropyl ketone at 100-110 DEG C with trifluoro-acetic fluoride
It is 70%, equation is shown in reaction (1).Unlike the above method, world patent WO Pat.2007077174 reports DMF
As solvent, reaction is carried out at 80 DEG C, and the yield of trifluoromethyl perfluoroisopropyl ketone is 70-84%, and equation is shown in reaction (1).
Similarly, document [J.Amer.Chem.Soc.1962,84,4285-4288.] reports acetonitrile as solvent, reacts at 100 DEG C
4h, immediately 125 DEG C of reaction 5h, the yield of trifluoromethyl perfluoroisopropyl ketone are 75%, and equation is shown in reaction (1).United States Patent (USP)
US Pat.20030089877 is reported in diglyme solvent, and catalyst KF is catalyzed trifluoroacetic anhydride and hexafluoropropene
In 50 DEG C of reaction 16h reaction synthesis trifluoromethyl perfluoroisopropyl ketones, yield 57%, product purity 99.6%, equation
See reaction (2).Trifluoro-acetic fluoride is replaced not to be improved yield, and trifluoroacetic anhydride and hexafluoropropene using trifluoroacetic anhydride
A molecule trifluoroacetic acid can be generated after reaction, the synthetic route compared to trifluoro-acetic fluoride and hexafluoropropene has no advantage.Document
[Russian Journal of Applied Chemistry, 2013,86:376-386] is reported under liquid-phase condition, hexafluoro ring
Ethylene Oxide reacts to obtain pentafluoroethyl group perfluoroisopropyl ketone, yield 62% with hexafluoropropene, and equation is shown in reaction (3).Document
In the presence of [Russian Journal of Applied Chemistry, 2013,86:1243-1251] reports organic solvent,
Five fluorine propionyl fluorides react to obtain pentafluoroethyl group perfluoroisopropyl ketone, yield 20%-63.5% with hexafluoropropene, and equation is shown in instead
Answer (4).
Article 2 route is the radical reaction of perfluor 2,3- dimethyl -2- butylene.Document [J.Fluor.Chem.1985,
29,4.] perfluor 2 is reported, it is complete can to quickly generate trifluoromethyl via photochemistry radical reaction for 3- dimethyl -2- butylene
Fluorine nezukone, yield 48%, equation are shown in reaction (5).But photochemical reaction radical reaction is generally present in atmosphere
In, and reaction product is extremely complex, therefore does not have industrialized value.
Article 3 route is pyrolytic reaction under reflux conditions.Document [Bulletin of the Academy of
Sciences of the USSR.1988,37,2389-2389.] perfluor 4- methyl-2,3- diacetyl is reported in heating condition
Under, using CsF as catalyst, reacts 1 hour, obtain trifluoromethyl perfluoroisopropyl ketone, yield 76%, equation is shown in reaction
(6).Document [Journal of Organic Chemistry USSR (English Translation), 1985,21:1933-
1938] it reports in diglyme solvent, cesium fluoride and 2- (perfluoro-ethyl) -2- (perfluoropropane -2- base) -3 is added,
Bis- (trifluoromethyl) ethylene oxide of 3- flow back 2 hours, obtain pentafluoroethyl group perfluoroisopropyl ketone, hexafluoropropene and 2- fluoroform
Base perfluor -2- amylene, equation are shown in reaction (7).In the route, starting material is not easy to obtain, and industrial value is not high.
Article 4 route is liquid-phase fluorination route.Document [Bulletin of the Academy of Sciences of
The USSR, Division of Chemical Science (English Translation), 1982,31,1685-1687]
It reports in diglyme solvent, 2- chlorine 1,1, Isosorbide-5-Nitrae, 4,5,5, the 5 amyl- 3- ketone of octafluoro -2- (trifluoromethyl) and fluorination
Caesium occurs fluorination reaction and obtains pentafluoroethyl group perfluoroisopropyl ketone, yield 38%, and equation is shown in reaction (8).Document
[Bulletin of the Academy of Sciences of the USSR,Division of Chemical Science
(English Translation), 1990,39:1870-1876] it reports in DMF solvent, at 20 DEG C, cesium fluoride and sulfonic acid
Diester reacts 4 hours, obtains pentafluoroethyl group perfluoroisopropyl ketone and five fluorine propionic acid, the former yield is only 16%, and latter yield is
76%, equation is shown in reaction (9).
Article 5 route is isomerization route.Document [Journal of Organic Chemistry USSR (English
Translation), 1986,22:80-85] report in glycol dinitrate ether solvents, 50 DEG C, cesium fluoride is catalyzed 2,3- bis-
Fluoro- 2- (perfluoropropane -2- base) -3- (trifluoromethyl) ethylene oxide obtains the pentafluoroethyl group perfluoroisopropyl that yield is 92%
Ketone, equation are shown in reaction (10).Document [Bulletin of the Academy of Sciences of the USSR,
Division of Chemical Science (English Translation), 1991,40:2285-2291] it reports
Under liquid-phase condition, antimony pentafluoride is as catalyst, 2,3- bis- fluoro- 2- (perfluoropropane -2- base) -3- (trifluoromethyl) ethylene oxide
Isomerization reaction occurs, obtains pentafluoroethyl group perfluoroisopropyl ketone and 2, bis- (trifluoromethyls)-four of 2,3,4,4,5- hexafluoros -3,5-
Hydrogen furans, the mass ratio of the material of the two are 1:1, and yield summation is 90%, and equation is shown in reaction (11).Document [Journal of
Organic Chemistry USSR (English Translation), 1986,22:80-85] it also reported in diethylene glycol (DEG) two
In methyl ether solvent, 20 DEG C, sodium fluoride catalysis bis- (trifluoromethyl) the ethylene oxide isomerization of the fluoro- 2- of 2- (perfluoro-ethyl) -3,3- are obtained
The pentafluoroethyl group perfluoroisopropyl ketone for being 93% to yield, equation are shown in reaction (12)；It also reported 250 DEG C simultaneously, five fluorinations
Antimony and bis- (trifluoromethyl) the ethylene oxide progress vexed tanks of the fluoro- 2- of 2- (perfluoro-ethyl) -3,3- are 2-3 hours sub-, obtain pentafluoroethyl group
The mixture of perfluoroisopropyl ketone and trifluoromethyl perfluor isobutyl ketone, the total recovery of the two are 94.5%, and equation is shown in reaction
(13).Document [Bulletin of the Academy of Sciences of the USSR, Division of
Chemical Science (English Translation), 1982,31:1685-1687] it reports in diethylene glycol dimethyl ether
In solvent, in the presence of NaCl, bis- (trifluoromethyl) ethylene oxide of the fluoro- 2- of 2- (perfluoro-ethyl) -3,3- occur chlorine-fluorine exchange and obtain
To 2- chlorine 1,1, Isosorbide-5-Nitrae, 4,5,5, the 5 amyl- 3- ketone of octafluoro -2- (trifluoromethyl), while isomerization side reaction also occurs and obtains yield
For 35% pentafluoroethyl group perfluoroisopropyl ketone, equation is shown in reaction (14).Document [Russian Journal of Organic
Chemistry, 2011, Vol.47, No.5, pp.650-658.] it reports in acetonitrile solvent, the fluoro- 2- of 2- (perfluoro-ethyl)-
3,3- bis- (trifluoromethyl) ethylene oxide react with urea, obtain principal product 1- (1,1,1,3,3,3- hexafluoro propyl- 2- yl)-
3- (perfluoro-ethyl) urea, while side reaction isomerization also occurring simultaneously and obtains pentafluoroethyl group perfluoroisopropyl ketone, principal product and pair
The mass ratio of the material of product is 3:2, and equation is shown in reaction (15).
The above-mentioned prior art has the following problems: (1) first route is although raw material is easy to obtain, but uses and be difficult to
The organic solvent of recycling carries out liquid phase reactor, be easy to cause serious pollution；(2) Article 2 route use radical reaction also
There are the operating difficulties of uncontrollable reaction process, and yield is lower；(3) fragment type that Article 3 route is pyrolyzed is too
It is more, so that greatly reducing the selectivity of target product；(4) raw material of Article 3 route is difficult to obtain, and yield is extremely
Lowly；(5) raw material of Article 5 route is difficult to obtain, most low yield.
Summary of the invention
The technical problem to be solved by the present invention is to overcome deficiency present in background technique, provide a kind of raw material be easy to get,
The high perfluor ketone gas-phase production of yield.
The means used to solve the problem
In order to achieve the object of the present invention, the present invention is using acyl fluorides as raw material, using acyl fluorides or perfluor substituted epoxy ethane
Addition reaction with perfluoroolefine prepares perfluor ketone.
When acyl fluorides is carbonyl fluoride, the reaction of generation is as follows:
When the carbon atom number of acyl fluorides is two and its is above, the reaction of generation is as follows:
When perfluor substituted epoxy ethane is, the reaction of generation is as follows:
The present invention synthesizes perfluor ketone using single step reaction, when acyl fluorides is carbonyl fluoride, happens is that the perfluor alkene of two molecules
The addition reaction of the carbonyl fluoride of hydrocarbon and a molecule；When acyl fluorides is that carbon atom number is more than or equal to 2, happens is that the perfluor of a molecule
The addition reaction of the carbonyl fluoride of alkene and a molecule.
The method that gas phase prepares perfluor ketone, in the presence of addition catalyst, general formula R1R2C=CR3R4Perfluoroolefine with
Acyl fluorides R5Gas phase addition reaction occurs for-COF, and obtaining general formula is CFR3R4-CR1R2-C(O)R5Either CFR3R4-CR1R2-C(O)-
CR1R2-CFR3R4Perfluor ketone, wherein R1、R2、R3And R4General formula be CnF2n+1, n is nonnegative integer, R5General formula be
CmF2m+1, m is nonnegative integer.
As m=0, R5For fluorine atom, reaction equation are as follows:
When m is positive integer, R5For perfluoroalkyl, reaction equation are as follows:
Or in the presence of addition catalyst, general formula R1R2C=CR3R4Perfluoroolefine and perfluor substituted epoxy ethane
Cyclio-O-CF2-C(R6)(R7)-gas phase addition reaction occurs, obtaining general formula is CFR3R4-CR1R2-C(O)-CFR6R7Perfluor
Ketone, wherein R6And R7General formula is CqF2q+1, q is nonnegative integer.
Equation are as follows:
The addition catalyst includes active component and carrier, the active component be lithium fluoride, potassium fluoride, sodium fluoride,
At least one of rubidium fluoride RbF or cesium fluoride, carrier are aluminum fluoride, magnesium fluoride, ferric flouride, charomic fluoride, zinc fluoride, calcirm-fluoride, fluorination
One of strontium, barium fluoride, the mass percent of active component and carrier are 0-20%:80%-100%.
The addition catalyst the preparation method comprises the following steps: metal soluble salt is dissolved in the water, concentrated ammonia liquor is added dropwise and is precipitated,
Adjusting pH value is 7.5, is then aged 12 hours, washing, filtering, 12-48 hours dry in 80 DEG C of baking ovens, is then protected in nitrogen
Under shield, 300-500 DEG C roasting 5-20 hours, obtain metal oxide, this be metal fluoride support precursor.According to alkali metal
The percentage group of fluoride and metal fluoride support becomes 0-20% and 80%-100%, under temperature 50 C, using dipping
For method by alkali metal fluoride dip loading in metal oxide, filtering is 5-48 hours dry at 80 DEG C, and obtained solid is carried out powder
Broken, catalyst precarsor is made in compression molding, and catalyst precarsor 10mL is packed into the Monel material of 1/2 inch of internal diameter, long 30cm
Tubular reactor, be passed through nitrogen 300-500 DEG C roasting 5-20 hours, nitrogen air speed be 200h-1, then in temperature 200-
400 DEG C, while it being passed through the mixed gas of hydrogen fluoride and nitrogen composition that the mass ratio of the material is 1:2, the total air speed of gas is 220h-1,
Activation 5-20 hours, stops above-mentioned mixed gas, and addition catalyst is made.In the above method, metal soluble salt can be metal
Chloride or nitrate.Aluminum fluoride, magnesium fluoride, ferric flouride, charomic fluoride, zinc fluoride, fluorine can be prepared according to the method described above
Change calcium, strontium fluoride, the carrier loaded alkali metal fluoride of barium fluoride, obtains addition catalyst.
The gas phase addition reaction condition are as follows: reaction temperature is 50~300 DEG C, and perfluoroolefine and acyl fluorides or perfluor replace
The molar ratio of ethylene oxide is 1~5: 1,0.1~100s of time of contact.
The gas phase addition reaction condition are as follows: reaction temperature is 100~200 DEG C, and perfluoroolefine takes with acyl fluorides or perfluor
Molar ratio for ethylene oxide is 1~2: 1,0.1~30s of time of contact.
The gas phase addition reaction condition are as follows: reaction temperature is 100~200 DEG C, and perfluoroolefine takes with acyl fluorides or perfluor
Molar ratio for ethylene oxide is 1~2: 1,0.1~30s of time of contact.
The acyl fluorides is carbonyl fluoride, and the molar ratio of perfluoroolefine and carbonyl fluoride is 2: 1.
The acyl fluorides is perfluoroalkyl acyl fluorides, and the molar ratio of perfluoroolefine and carbonyl fluoride is 1: 1.
The molar ratio of the perfluoroolefine and perfluor substituted epoxy ethane is 1~2: 1.
The perfluoroolefine is tetrafluoroethene, and when acyl fluorides is carbonyl fluoride, perfluor ketone is bis- (perfluoro-ethyl) ketone；
Or the perfluoroolefine is tetrafluoroethene, when acyl fluorides is trifluoro-acetic fluoride, perfluor ketone is five fluorine second of trifluoromethyl
Base ketone；
Or the perfluoroolefine be tetrafluoroethene, acyl fluorides be five fluorine propionyl fluorides when, perfluor ketone be trifluoromethyl perfluor just
Propyl ketone；
Or the perfluoroolefine is tetrafluoroethene, acyl fluorides is seven fluorine isobutyl acyl fluorides, and perfluor ketone is pentafluoroethyl group perfluor
Nezukone；
Or the perfluoroolefine is hexafluoropropene, when acyl fluorides is carbonyl fluoride, perfluor ketone is bis- (perfluoroisopropyl) ketone；
Or the perfluoroolefine is hexafluoropropene, when acyl fluorides is trifluoro-acetic fluoride, perfluor ketone is trifluoromethyl perfluor
Nezukone；
Or the perfluoroolefine is hexafluoropropene, acyl fluorides is five fluorine propionyl fluorides, and perfluor ketone is that pentafluoroethyl group perfluor is different
Propyl ketone；
Or the perfluoroolefine is hexafluoropropene, when acyl fluorides is seven fluorine isobutyl acyl fluorides, perfluor ketone is bis- (perfluor isopropyls
Base) ketone；
Or the perfluoroolefine is octafluoro -1- butylene, when acyl fluorides is carbonyl fluoride, perfluor ketone is bis- (perfluor sec-butyls)
Ketone；
Or the perfluoroolefine is octafluoro -2- butylene, when acyl fluorides is carbonyl fluoride, perfluor ketone is bis- (perfluor sec-butyls)
Ketone.
Or the perfluoroolefine is hexafluoropropene, and when perfluor substituted epoxy ethane is perfluorinated ethylene oxide, perfluor ketone
For trifluoromethyl perfluoroisopropyl ketone；
Or the perfluoroolefine is hexafluoropropene, perfluor substituted epoxy ethane is 2,2,3- tri- fluoro- 3- (fluoroforms
Base) ethylene oxide when, perfluor ketone be pentafluoroethyl group perfluoroisopropyl ketone；
Or the perfluoroolefine is hexafluoropropene, perfluor substituted epoxy ethane is 2,2-, the bis- bis- (fluoroforms of fluoro- 3,3-
Base) ethylene oxide when, perfluor ketone be bis- (perfluoroisopropyl) ketone.
The present invention reaches suitable molar ratio by adjusting acyl fluorides and perfluoroolefine, for example, carbonyl fluoride and perfluoroolefine
Molar ratio close to 1:2, and the molar ratio of acyl fluorides of the carbon atom number more than or equal to 2 and perfluoroolefine is close to 1:1, reaction knot
Shu Hou, the perfluor ketone that purity is up to 98% or so can be collected by not needing rectifying.If necessary to the higher perfluor ketone of purity,
Then distillation operation can be carried out to perfluor ketone crude product is collected into.Such as: the boiling point of trifluoromethyl perfluoroisopropyl ketone is 24 DEG C of (pressure
For 760mmHg), pentafluoroethyl group perfluoroisopropyl ketone boiling point is 49 DEG C (pressure 760mmHg), the boiling of bis- (perfluoroisopropyl) ketone
Point is 72 DEG C (pressure 760mmHg).
The type of reactor that the present invention uses must be high voltage bearing tubular reactor, and the tubular type that can be 316 materials is anti-
Answer device or the tubular reactor of Monel material etc..In addition, adiabatic reactor or isothermal reactor also can be used.
Advantages of the present invention:
(1) addition catalyst is used, is catalyzed the gas phase addition reaction of perfluoroolefine and acyl fluorides, it is easy to accomplish the big rule of serialization
Mould produces perfluor ketone.
(2) raw material is easy to get, and cheap, easy to operate, safety in production easy to accomplish.
(3) yield of the invention for preparing perfluor ketone is very high, is greater than 95%.
Specific embodiment
Analysis instrument: Shimadzu GC-2010, chromatographic column are DB-VRX capillary column (i.d.0.32mm；
length30m；J&W Scientific Inc.).
GC analysis method: 250 DEG C of detector temperature, 250 DEG C of temperature of vaporization chamber, 40 DEG C of column initial temperature, holding 10 minutes, 15
DEG C/min is warming up to 230 DEG C, it is kept for 8 minutes.
The addition catalyst the preparation method comprises the following steps: metal soluble salt is dissolved in the water, concentrated ammonia liquor is added dropwise and is precipitated,
Adjusting pH value is 7.5, is then aged 12 hours, washing, filtering, 12-48 hours dry in 80 DEG C of baking ovens, is then protected in nitrogen
Under shield, 300-500 DEG C roasting 5-20 hours, obtain metal oxide, this be metal fluoride support precursor.According to alkali metal
The percentage group of fluoride and metal fluoride support becomes 0-20% and 80%-100%, under temperature 50 C, using dipping
For method by alkali metal fluoride dip loading in metal oxide, filtering is 5-48 hours dry at 80 DEG C, and obtained solid is carried out powder
Broken, catalyst precarsor is made in compression molding, and catalyst precarsor 10mL is packed into the Monel material of 1/2 inch of internal diameter, long 30cm
Tubular reactor, be passed through nitrogen 300-500 DEG C roasting 5-20 hours, nitrogen air speed be 200h-1, then in temperature 200-
400 DEG C, while it being passed through the mixed gas of hydrogen fluoride and nitrogen composition that the mass ratio of the material is 1:2, the total air speed of gas is 220h-1,
Activation 5-20 hours, stops above-mentioned mixed gas, and catalyst carrier is made.In the above method, metal soluble salt can be metal
Chloride or nitrate.Aluminum fluoride, magnesium fluoride, ferric flouride, charomic fluoride, zinc fluoride, fluorine can be prepared according to the method described above
Change the catalyst carriers carrying alkali metal fluorides such as calcium, strontium fluoride, barium fluoride, obtains addition catalyst.
Embodiment 1
1/2 inch of outer diameter, 30 milliliters of internal volume the tubular reactor because of Kang Hejin in filling 10 milliliters it is above-mentioned
The addition catalyst 20%CsF/80%CrF that preparation method obtains3.Reaction condition are as follows: 160 DEG C of reaction heating, trifluoro-acetic fluoride
Molar ratio with hexafluoropropene is 1:1, time of contact 0.25s, reaction pressure 0.1MPa.Reaction product is through polytetrafluoroethylene (PTFE)
The sampling bag of material is collected, and after reaction 10 hours, sampling carries out GC analysis, reaction result are as follows: trifluoro second from sampling bag
The conversion ratio of acyl fluorides is 96.9%, and the selectivity of trifluoromethyl perfluoroisopropyl ketone is 98.6%.
Embodiment 2
1/2 inch of outer diameter, 30 milliliters of internal volume the tubular reactor because of Kang Hejin in filling 110 milliliters it is above-mentioned
The addition catalyst 20%RbF/80%AlF that preparation method obtains3.Reaction condition are as follows: 160 DEG C of reaction heating, trifluoro-acetic fluoride
Molar ratio with hexafluoropropene is 1:1, time of contact 0.25s, reaction pressure 0.1MPa.Reaction product is through polytetrafluoroethylene (PTFE)
The sampling bag of material is collected, and after reaction 10 hours, sampling carries out GC analysis, reaction result are as follows: trifluoro second from sampling bag
The conversion ratio of acyl fluorides is 97.4%, and the selectivity of trifluoromethyl perfluoroisopropyl ketone is 98.8%.
Embodiment 3
1/2 inch of outer diameter, 30 milliliters of internal volume the tubular reactor because of Kang Hejin in filling 10 milliliters it is above-mentioned
The addition catalyst CrF of method preparation3.Reaction condition are as follows: 160 DEG C of reaction heating, mole of trifluoro-acetic fluoride and hexafluoropropene
Than for 1:1, time of contact 0.25s, reaction pressure 0.1MPa.Reaction product is carried out through the sampling bag of polytetrafluoroethylene (PTFE) material
It collects, after reaction 10 hours, sampling carries out GC analysis, reaction result from sampling bag are as follows: the conversion ratio of trifluoro-acetic fluoride is
97.7%, the selectivity of trifluoromethyl perfluoroisopropyl ketone is 99.0%.
Embodiment 4
1/2 inch of outer diameter, 30 milliliters of internal volume the tubular reactor because of Kang Hejin in filling 10 milliliters it is above-mentioned
The addition catalyst 10%KF/90%FeF of method preparation3.Reaction condition are as follows: 160 DEG C of reaction heating, five fluoracyl fluorides and hexafluoro
The molar ratio of propylene is 1:1, time of contact 0.25s, reaction pressure 0.1MPa.Reaction product is through polytetrafluoroethylene (PTFE) material
Sampling bag is collected, and after reaction 10 hours, sampling carries out GC analysis, reaction result are as follows: five fluoracyl fluorides from sampling bag
Conversion ratio is 100%, and the selectivity of pentafluoroethyl group perfluoroisopropyl ketone is 99.2%.
Embodiment 5
1/2 inch of outer diameter, 30 milliliters of internal volume the tubular reactor because of Kang Hejin in filling 10 milliliters it is above-mentioned
The addition catalyst 10%NaF/90%AlF of method preparation3.Reaction condition are as follows: reaction heating 160 DEG C, seven fluorine isobutyl acyl fluorides with
The molar ratio of tetrafluoroethene is 1:1, time of contact 0.25s, reaction pressure 0.1MPa.Reaction product is through polytetrafluoroethylene (PTFE) material
The sampling bag of matter is collected, and after reaction 10 hours, sampling carries out GC analysis, reaction result are as follows: seven fluorine isobutyls from sampling bag
The conversion ratio of acyl fluorides is 100%, and the selectivity of pentafluoroethyl group perfluoroisopropyl ketone is 97.6%.
Embodiment 6
1/2 inch of outer diameter, 30 milliliters of internal volume the tubular reactor because of Kang Hejin in filling 10 milliliters it is above-mentioned
The addition catalyst 10%LiF/90%AlF of method preparation3.Reaction condition are as follows: 160 DEG C of reaction heating, carbonyl fluoride and hexafluoro third
The molar ratio of alkene is 1:2, time of contact 0.25s, reaction pressure 0.1MPa.Reaction product takes through polytetrafluoroethylene (PTFE) material
Sample bag is collected, and after reaction 10 hours, sampling carries out GC analysis, reaction result are as follows: the conversion ratio of carbonyl fluoride from sampling bag
It is 100%, the selectivity of bis- (perfluoroisopropyl) ketone is 98.5%.
Embodiment 7
1/2 inch of outer diameter, 30 milliliters of internal volume the tubular reactor because of Kang Hejin in filling 10 milliliters it is above-mentioned
The addition catalyst 5%CsF/95%CrF that preparation method obtains3.Reaction condition are as follows: 160 DEG C of reaction heating, seven fluorine isobutyl acyl fluorides
Molar ratio with hexafluoropropene is 1:1, time of contact 0.25s, reaction pressure 0.1MPa.Reaction product is through polytetrafluoroethylene (PTFE)
The sampling bag of material is collected, and after reaction 10 hours, sampling carries out GC analysis, reaction result are as follows: seven fluorine are different from sampling bag
The conversion ratio of butyryl fluorine is 99.9%, and the selectivity of bis- (perfluoroisopropyl) ketone is 98.6%.
Embodiment 8
1/2 inch of outer diameter, 30 milliliters of internal volume the tubular reactor because of Kang Hejin in filling 10 milliliters it is above-mentioned
The addition catalyst 5%RbF/95%ZnF that preparation method obtains2.Reaction condition are as follows: 160 DEG C of reaction heating, carbonyl fluoride and tetrafluoro
The molar ratio of ethylene is 1:2, time of contact 0.25s, reaction pressure 0.1MPa.Reaction product is through polytetrafluoroethylene (PTFE) material
Sampling bag is collected, and after reaction 10 hours, sampling carries out GC analysis, reaction result are as follows: the conversion of carbonyl fluoride from sampling bag
Rate is 99.6%, and the selectivity of bis- (perfluoro-ethyl) ketone is 97.9%.
Embodiment 9
1/2 inch of outer diameter, 30 milliliters of internal volume the tubular reactor because of Kang Hejin in filling 10 milliliters it is above-mentioned
The addition catalyst 5%KF/95%FeF that preparation method obtains3.Reaction condition are as follows: reaction heating 160 DEG C, trifluoro-acetic fluoride with
The molar ratio of tetrafluoroethene is 1:1, time of contact 0.25s, reaction pressure 0.1MPa.Reaction product is through polytetrafluoroethylene (PTFE) material
The sampling bag of matter is collected, and after reaction 10 hours, sampling carries out GC analysis, reaction result are as follows: trifluoroacetyl from sampling bag
The conversion ratio of fluorine is 99.2%, and the selectivity of trifluoromethyl pentafluoroethyl group ketone is 99.6%.
Embodiment 10
1/2 inch of outer diameter, 30 milliliters of internal volume the tubular reactor because of Kang Hejin in filling 10 milliliters it is above-mentioned
The addition catalyst 10%CsF/90%CaF that preparation method obtains2.Reaction condition are as follows: 160 DEG C of reaction heating, five fluorine propionyl fluorides
Molar ratio with tetrafluoroethene is 1:1, time of contact 0.25s, reaction pressure 0.1MPa.Reaction product is through polytetrafluoroethylene (PTFE)
The sampling bag of material is collected, and after reaction 10 hours, sampling carries out GC analysis, reaction result are as follows: five fluorine third from sampling bag
The conversion ratio of acyl fluorides is 99.7%, and the selectivity of trifluoromethyl perfluor n-propyl ketone is 99.2%.
Embodiment 11
1/2 inch of outer diameter, 30 milliliters of internal volume the tubular reactor because of Kang Hejin in filling 10 milliliters it is above-mentioned
The addition catalyst 10%RbF/90%SrF that preparation method obtains2.Reaction condition are as follows: 160 DEG C of reaction heating, carbonyl fluoride and eight
The molar ratio of fluoro- 1- butylene is 1:2, time of contact 0.25s, reaction pressure 0.1MPa.Reaction product is through polytetrafluoroethylene (PTFE)
The sampling bag of material is collected, and after reaction 10 hours, sampling carries out GC analysis, reaction result are as follows: carbonyl fluoride from sampling bag
Conversion ratio be 99.1%, the selectivity of bis- (perfluor sec-butyl) ketone is 98.8%.
Embodiment 12
1/2 inch of outer diameter, 30 milliliters of internal volume the tubular reactor because of Kang Hejin in filling 10 milliliters it is above-mentioned
The addition catalyst 10%NaF/80%BaF that preparation method obtains2.Reaction condition are as follows: 160 DEG C of reaction heating, carbonyl fluoride and eight
The molar ratio of fluoro- 2- butylene is 1:2, time of contact 0.25s, reaction pressure 0.1MPa.Reaction product is through polytetrafluoroethylene (PTFE)
The sampling bag of material is collected, and after reaction 10 hours, sampling carries out GC analysis, reaction result are as follows: carbonyl fluoride from sampling bag
Conversion ratio be 99.4%, the selectivity of bis- (perfluor sec-butyl) ketone is 99.3%.
Embodiment 13
1/2 inch of outer diameter, 30 milliliters of internal volume the tubular reactor because of Kang Hejin in filling 10 milliliters it is above-mentioned
The addition catalyst 15%KF/85%CaF that preparation method obtains2.Reaction condition are as follows: 160 DEG C of reaction heating, perfluorinated ethylene oxide
Molar ratio with hexafluoropropene is 1:2, time of contact 0.25s, reaction pressure 0.1MPa.Reaction product is through polytetrafluoroethylene (PTFE)
The sampling bag of material is collected, and after reaction 10 hours, sampling carries out GC analysis, reaction result are as follows: perfluor ring from sampling bag
The conversion ratio of oxidative ethane is 99.5%, and the selectivity of trifluoromethyl perfluoroisopropyl ketone is 99.1%.
Embodiment 14
1/2 inch of outer diameter, 30 milliliters of internal volume the tubular reactor because of Kang Hejin in filling 10 milliliters it is above-mentioned
The addition catalyst 15%LiF/85%SrF that preparation method obtains2.Reaction condition are as follows: 160 DEG C of reaction heating, 2,2,3- tri- is fluoro-
The molar ratio of 3- (trifluoromethyl) ethylene oxide and hexafluoropropene is 1:2, time of contact 0.25s, reaction pressure 0.1MPa.
Reaction product is collected through the sampling bag of polytetrafluoroethylene (PTFE) material, and after reaction 10 hours, sampling carries out GC points from sampling bag
Analysis, reaction result are as follows: the conversion ratio of 2,2,3- tri- fluoro- 3- (trifluoromethyl) ethylene oxide is 99.0%, and pentafluoroethyl group perfluor is different
The selectivity of propyl ketone is 99.4%.
Embodiment 15
1/2 inch of outer diameter, 30 milliliters of internal volume the tubular reactor because of Kang Hejin in filling 10 milliliters it is above-mentioned
The addition catalyst 15%RbF/85%BaF that preparation method obtains2.Reaction condition are as follows: 160 DEG C of reaction heating, 2,2- bis- fluoro- 3,
The molar ratio of bis- (trifluoromethyl) ethylene oxide of 3- and hexafluoropropene is 1:2, time of contact 0.25s, and reaction pressure is
0.1MPa.Reaction product is collected through the sampling bag of polytetrafluoroethylene (PTFE) material, reaction 10 hours after, sampled from sampling bag into
Row GC analysis, reaction result are as follows: the conversion ratio of 2,2- bis- fluoro- bis- (trifluoromethyl) ethylene oxide of 3,3- is 99.6%, bis- (perfluors
Isopropyl) ketone selectivity be 99.3%.
Claims (10)
1. the method that gas phase prepares perfluor ketone, in the presence of addition catalyst, general formula R1R2C=CR3R4Perfluoroolefine and acyl
Fluorine R5Gas phase addition reaction occurs for-COF, and obtaining general formula is CFR3R4-CR1R2-C(O)R5Either CFR3R4-CR1R2-C(O)-
CR1R2-CFR3R4Perfluor ketone, wherein R1、R2、R3And R4General formula be CnF2n+1, n is nonnegative integer, R5General formula be
CmF2m+1, m is nonnegative integer；
Or in the presence of addition catalyst, general formula R1R2C=CR3R4Perfluoroolefine and perfluor substituted epoxy ethane
Cyclio-O-CF2-C(R6)(R7)-gas phase addition reaction occurs, obtaining general formula is CFR3R4-CR1R2-C(O)-CFR6R7Perfluor
Ketone, wherein R6And R7General formula is CqF2q+1, q is nonnegative integer；
The addition catalyst includes active component and carrier, and the active component is lithium fluoride, potassium fluoride, sodium fluoride, fluorination
At least one of rubidium or cesium fluoride, carrier be aluminum fluoride, magnesium fluoride, ferric flouride, charomic fluoride, zinc fluoride, calcirm-fluoride, strontium fluoride,
One of barium fluoride, the mass percent of active component and carrier are 0-20%:80%-100%.
2. according to the method described in claim 1, the addition catalyst the preparation method comprises the following steps: metal soluble salt is dissolved in water
In, concentrated ammonia liquor is added dropwise and is precipitated, adjusting pH value is 7.5, is then aged 12 hours, and washing, filtering are dry in 80 DEG C of baking ovens
12-48 hours, then under nitrogen protection, 300-500 DEG C roasting 5-20 hours, obtain metal oxide, this is metal pentafluoride
The precursor of object carrier；Become 0-20% and 80%- according to the percentage group of alkali metal fluoride and metal fluoride support
100%, under temperature 50 C, alkali metal fluoride dip loading is filtered, on metal oxide at 80 DEG C using infusion process
It is 5-48 hours dry, obtained solid is crushed, compression molding, catalyst precarsor is made；Catalyst precarsor is packed into tubular type
Reactor, be passed through nitrogen 300-500 DEG C roasting 5-20 hours, nitrogen air speed be 200h-1, then at 200-400 DEG C of temperature, together
When be passed through the mass ratio of the material be 1:2 hydrogen fluoride and nitrogen composition mixed gas, the total air speed of gas be 220h-1, activate 5-20
Hour, stopping is passed through mixed gas, and addition catalyst is made；The metal soluble salt is metallic aluminium, magnesium, iron, chromium, zinc, calcium, strontium
Or the chloride or nitrate of barium.
3. according to the method described in claim 1, the gas phase addition reaction condition are as follows: reaction temperature is 50~300 DEG C, perfluor
The molar ratio of alkene and acyl fluorides or perfluor substituted epoxy ethane is 1~5: 1,0.1~100s of time of contact.
4. according to the method described in claim 3, the gas phase addition reaction condition are as follows: reaction temperature is 100~200 DEG C, entirely
The molar ratio of fluoroolefins and acyl fluorides or perfluor substituted epoxy ethane is 1~2: 1,0.1~30s of time of contact.
5. the molar ratio of perfluoroolefine and carbonyl fluoride is 2: 1 according to the method described in claim 4, the acyl fluorides is carbonyl fluoride.
6. according to the method described in claim 4, the acyl fluorides is perfluoroalkyl acyl fluorides, the molar ratio of perfluoroolefine and carbonyl fluoride
It is 1: 1.
7. according to the method described in claim 4, the molar ratio of the perfluoroolefine and perfluor substituted epoxy ethane is 1~2: 1.
8. when acyl fluorides is carbonyl fluoride, perfluor ketone is according to the method described in claim 4, the perfluoroolefine is tetrafluoroethene
Bis- (perfluoro-ethyl) ketone；
Or the perfluoroolefine is tetrafluoroethene, when acyl fluorides is trifluoro-acetic fluoride, perfluor ketone is trifluoromethyl pentafluoroethyl group ketone；
Or the perfluoroolefine is tetrafluoroethene, when acyl fluorides is five fluorine propionyl fluoride, perfluor ketone is trifluoromethyl perfluor n-propyl
Ketone；
Or the perfluoroolefine is tetrafluoroethene, acyl fluorides is seven fluorine isobutyl acyl fluorides, and perfluor ketone is pentafluoroethyl group perfluor isopropyl
Base ketone；
Or the perfluoroolefine is hexafluoropropene, when acyl fluorides is carbonyl fluoride, perfluor ketone is bis- (perfluoroisopropyl) ketone；
Or the perfluoroolefine is hexafluoropropene, when acyl fluorides is trifluoro-acetic fluoride, perfluor ketone is trifluoromethyl perfluor isopropyl
Base ketone；
Or the perfluoroolefine is hexafluoropropene, acyl fluorides is five fluorine propionyl fluorides, and perfluor ketone is pentafluoroethyl group perfluoroisopropyl
Ketone；
Or the perfluoroolefine is hexafluoropropene, when acyl fluorides is seven fluorine isobutyl acyl fluorides, perfluor ketone is bis- (perfluoroisopropyls)
Ketone；
Or the perfluoroolefine is octafluoro -1- butylene, when acyl fluorides is carbonyl fluoride, perfluor ketone is bis- (perfluor sec-butyl) ketone；
Or the perfluoroolefine is octafluoro -2- butylene, when acyl fluorides is carbonyl fluoride, perfluor ketone is bis- (perfluor sec-butyl) ketone.
Or the perfluoroolefine is hexafluoropropene, when perfluor substituted epoxy ethane is perfluorinated ethylene oxide, perfluor ketone is three
Methyl fluoride perfluoroisopropyl ketone；
Or the perfluoroolefine is hexafluoropropene, perfluor substituted epoxy ethane is 2,2,3- tri- fluoro- 3- (trifluoromethyl) rings
When oxidative ethane, perfluor ketone is pentafluoroethyl group perfluoroisopropyl ketone；
Or the perfluoroolefine is hexafluoropropene, perfluor substituted epoxy ethane is that fluoro- 3, the 3- of 2,2- bis- is bis- (trifluoromethyl)
When ethylene oxide, perfluor ketone is bis- (perfluoroisopropyl) ketone.
9. according to the method described in claim 1, the reactor of the gas phase addition reaction is high voltage bearing tubular reactor.
10. according to the method described in claim 9, the reactor of the gas phase addition reaction is the tubular reactor of 316 materials
Or the tubular reactor of Monel material.
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| CN110433515A (en) * | 2019-06-30 | 2019-11-12 | 天津市长芦化工新材料有限公司 | Plate distillation column purifies reaction system |
| CN116143594A (en) * | 2022-12-09 | 2023-05-23 | 天津长芦新材料研究院有限公司 | Synthesis method of bis (heptafluoroisopropyl) ketone |
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| CN110433515A (en) * | 2019-06-30 | 2019-11-12 | 天津市长芦化工新材料有限公司 | Plate distillation column purifies reaction system |
| CN116143594A (en) * | 2022-12-09 | 2023-05-23 | 天津长芦新材料研究院有限公司 | Synthesis method of bis (heptafluoroisopropyl) ketone |
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