CN109651131A - The method that hexafluoropropylene dimmer prepares perfluor isobutyl acyl fluorides - Google Patents
The method that hexafluoropropylene dimmer prepares perfluor isobutyl acyl fluorides Download PDFInfo
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- CN109651131A CN109651131A CN201811459941.6A CN201811459941A CN109651131A CN 109651131 A CN109651131 A CN 109651131A CN 201811459941 A CN201811459941 A CN 201811459941A CN 109651131 A CN109651131 A CN 109651131A
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- hexafluoropropylene dimmer
- hexafluoropropylene
- acyl fluorides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
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Abstract
The invention belongs to fluorine chemical fields, and in particular to a kind of method that hexafluoropropylene dimmer prepares perfluor isobutyl acyl fluorides.Include the following steps: using oxygen and hexafluoropropene dimerization as raw material, reaction is prepared under the effect of the catalyst；Wherein oxygen and hexafluoropropylene dimmer/hexafluoropropylene trimer molar ratio are 1:10-10:1；The catalytic time is 0.1s to 200s；The pressure of reaction is 0-1MPa；Reaction temperature is 150-600 DEG C.The method that hexafluoropropylene dimmer provided by the invention prepares perfluor isobutyl acyl fluorides, reaction condition is mild, product yield is high, pollution-free, and is easy to large-scale production.
Description
Technical field
The invention belongs to fluorine chemical fields, and in particular to a kind of hexafluoropropylene dimmer prepares the side of perfluor isobutyl acyl fluorides
Method.
Background technique
The perfluor carbonyls object especially perfluor butyryl fluorine of high-quality is to prepare HFE-7100/7200/7300/
7500 important intermediate, the preparation method of perfluor butyryl fluorine is butyl chloride electrolysis method etc. at present.US6013795A electrosynthesis glyoxal
In method raw material inexpensively, but electrolytic efficiency is very low, be difficult to avoid that electrolysis impurity caused by product purity it is not high, be in addition electrolysed
Pole plate cost of manufacture is expensive, and cost of equipment is higher to be unfavorable for industrial implementation.Perfluor iodide and oleum are used in US3351644
Acid reaction is to prepare perfluoro acidyl compound, and severe reaction conditions, raw material is not easy to obtain, at high cost, is also not suitable for industry amplification life
It produces.
Summary of the invention
The purpose of the present invention is to provide a kind of methods that hexafluoropropylene dimmer prepares perfluor isobutyl acyl fluorides.
The present invention to achieve the above object, using following technical scheme:
A kind of method that hexafluoropropylene dimmer prepares perfluor isobutyl acyl fluorides, includes the following steps:
Hexafluoropropylene dimmer enters oxidation furnace and oxygen and carries out cracking reaction under catalysts conditions, and rectifying obtains perfluor
Isobutyl acyl fluorides；
Specific steps are as follows: using oxygen and hexafluoropropylene dimmer as raw material, reaction is prepared under the effect of the catalyst；
Wherein the molar ratio of oxygen and hexafluoropropylene dimmer is 1:10-10:1；The catalytic time is 0.1s to 200s；Reaction
Pressure be 0-1MPa；Reaction temperature is 150-600 DEG C.
The catalyst be loaded catalyst, active constituent Ag2O, Al2O3, CuO, AgF, NaF, KF, RbF or
Person CsF.
Hexafluoropropylene dimmer enters reactor with liquid form in step reaction, since fluid molecule is compared to gas point
Son has shorter intermolecular distance, therefore more gaseous state hexafluoropropylene dimmers are had in the slow gasification of liquid charging stock
Molecule comes into full contact with oxygen, so as to shorten the pyrolysis time of hexafluoropropylene dimmer, significantly improves raw material and integrally cracks effect
Rate.And the presence of the hexafluoropropylene dimmer more contacted with oxygen can prevent the perfluor isobutyl acyl fluorides being cracked to form and perfluor second
The further cracking of acyl fluorides, to guarantee that gained perfluor isobutyl acyl fluorides has higher degree.
It further include pre-activate step；Specifically include by hexafluoropropylene dimmer be passed through 180-220 DEG C filled with pre-activate
1-2h is activated in the reactor of carrier；The active constituent of the pre-activate carrier is four (pentafluorophenyl group) borates and alkyl fluoride
Aluminium salt according to mass ratio 1:1-1:5 mixture；Wherein n=1-6；The carrier of pre-activate carrier be SiO2, Al2O3 or
B2O3；Load capacity is 10%-20%.
The alkyl fluoride aluminium salt is Al ((CR1R2R3) n) 3 monomers or mixture；Wherein R1, R2 and R3 be H or
Person F and at least one be F, n=1-6.
(pentafluorophenyl group) borate and alkyl fluoride aluminium salt mixed catalyst have good activation to C=C four in the reaction
Effect is activated the activation energy that can further decrease C=C cracking to hexafluoropropylene dimmer using the mixed catalyst, mentioned
The accuracy of high C=C fracture.And the pyrolysis product of perfluoroolefine is usually present carbonyl fluoride or all phosphinylidynes in the prior art
Fluorine, thus pre-activate step implementation can guarantee hexafluoropropylene dimmer rule be cracked into perfluor isobutyl acyl fluorides and perfluor acetyl
Fluorine effectively avoids the generation of perfluor carbonyl fluoride by-product.
The hexafluoropropylene dimmer is obtained under the catalysis of support type ionic fluorides through gas phase reaction by hexafluoropropene；
Reaction temperature is 150-220 DEG C, time of contact 0.1-30s；The load capacity of support type ionic fluorides is 10%-20%；It carries
Body is activated carbon, aluminum oxide, silica or magnesia；Ionic fluorides are AgF, NaF, KF, RbF or CsF.System
When standby, the upper end product exit of the first catalytic reaction tube of the support type ionic fluorides and first with condensation water leg
The air inlet of one end of condenser is connected, and the first condenser other end is gas vent, and unreacted hexafluoropropene passes through gas
Outlet is recycled to the first catalytic reaction tube column of support type ionic fluorides.The fluid sample sample in the first condenser is taken to detect,
The purity of gained hexafluoropropylene dimmer is greater than 99%.
Compared with prior art, the beneficial effects of the present invention are:
The method that hexafluoropropylene dimmer provided by the invention prepares perfluor isobutyl acyl fluorides, reaction condition is mild and can
Control polymerization, product yield are high, pollution-free, and are easy to large-scale production.
Specific embodiment
In order to make those skilled in the art more fully understand technical solution of the present invention, implement below with reference to best
The present invention is described in further detail for example.
Embodiment 1: the preparation of hexafluoropropylene dimmer raw material: by hexafluoropropene gas by being catalyzed equipped with NaF/Al2O3
The catalytic reaction tube of agent, the load capacity of catalyst are 10%, time of contact 0.1s；The temperature of catalytic reaction tube is 150 DEG C, instead
Mixed gas after answering enters the condenser with cooling jacket by port entrance, and condensate temperature is 10 DEG C, and unreacted six
Fluoropropene is recycled to catalytic reaction tube through gas vent.The purity of liquid hexafluoropropylene dimmer in detection condenser receiver
It is 99.3%.The yield of hexafluoropropylene dimmer is shown in Table 1.
Embodiment 2: the preparation of hexafluoropropylene dimmer raw material: by hexafluoropropene gas by being equipped with AgF/C catalyst
Catalytic reaction tube, the load capacity of catalyst are 15%, and the temperature of catalyst filling column is 180 DEG C, time of contact 10s, reaction
Mixed gas afterwards enters the condenser with cooling jacket by air inlet, and condensate temperature is 10 DEG C；Unreacted hexafluoro third
Alkene is recycled to catalytic reaction tube column through outlet.The purity of liquid hexafluoropropylene dimmer is 99.2% in detection condenser.Set
1 is shown in Table with the yield of rear hexafluoropropylene dimmer.
Embodiment 3: hexafluoropropene gas the preparation of hexafluoropropylene dimmer raw material: is passed through into urging equipped with KF/C catalyst
Change reaction tube, the load capacity of catalyst is 20%, and the temperature of catalyst filling column is 220 DEG C, time of contact 30s；After reaction
Mixed gas by air inlet enter with cooling jacket condenser, condensate temperature be 10 DEG C, unreacted hexafluoropropene
Catalytic reaction tube is recycled to through outlet.The purity of liquid hexafluoropropylene dimmer is 99.3% in detection condenser.After applying
The yield of hexafluoropropylene dimmer is shown in Table 1.
Comparative example 1: the preparation of hexafluoropropylene trimer raw material: by hexafluoropropene gas by being catalyzed equipped with NaF/Al2O3
The catalytic reaction tube of agent, the load capacity of catalyst are 10%, and the temperature of catalyst reaction tube is 260 DEG C, and time of contact is
0.1s；Mixed gas after reaction enters the condenser with cooling jacket by air inlet, and condensate temperature is 10 DEG C, unreacted
Hexafluoropropene through outlet be recycled to catalyst reaction tube.The purity of liquid hexafluoropropylene trimer in detection condenser
It is 99.3%.The yield of hexafluoropropylene trimer is shown in Table 1.
Comparative example 2: the preparation of hexafluoropropylene trimer raw material: by hexafluoropropene gas by being equipped with AgF/C catalyst
Catalytic reaction tube, the load capacity of catalyst are 15%, and the temperature of catalyst reaction tube is 300 DEG C, time of contact 10s,
Mixed gas after reaction enters the condenser with cooling jacket by air inlet, and condensate temperature is 10 DEG C；Unreacted six
Fluoropropene is recycled to catalyst reaction tube through outlet.The purity of liquid hexafluoropropylene trimer is in detection condenser
99.3%.The yield for applying rear hexafluoropropylene trimer is shown in Table 1.
Comparative example 3: hexafluoropropene gas the preparation of hexafluoropropylene trimer raw material: is passed through into urging equipped with KF/C catalyst
Change reaction tube, the load capacity of catalyst is 20%, and the temperature of catalyst reaction tube is 320 DEG C, time of contact 30s；Instead
Mixed gas after answering enters the condenser with cooling jacket by air inlet, and condensate temperature is 10 DEG C, unreacted hexafluoro
Propylene is recycled to catalyst reaction tube through outlet.The purity of liquid hexafluoropropylene trimer is in detection condenser
99.3%.The yield for applying rear hexafluoropropylene trimer is shown in Table 1.
Table 1
Embodiment 4: it hexafluoropropylene dimmer cracking: 1) pre-activate: specifically includes and hexafluoropropylene dimmer is passed through 200 DEG C
The reactor filled with pre-activate carrier in activate 1.5h；The active constituent of the pre-activate carrier is four (pentafluorophenyl group) boron
Hydrochlorate and Al ((CF3) 3) 3 according to mass ratio 1:3 mixture；The carrier of pre-activate carrier is SiO2；Load capacity is 15%.2)
Load capacity is filled in pyrolysis furnace and is 15% Ag2O/Al2O3 catalyst, and pyrolysis furnace is heated to 400 DEG C.By oxygen and work
Hexafluoropropylene dimmer after change is passed through in pyrolysis furnace according to molar ratio 1:1.Reaction pressure is that 5bar. product is perfluor butyryl fluorine
50.09%, perfluor acetylfluoride 26.92%.
Embodiment 5: it hexafluoropropylene dimmer cracking: 1) pre-activate: specifically includes and hexafluoropropylene dimmer is passed through 200 DEG C
The reactor filled with pre-activate carrier in activate 1.5h；The active constituent of the pre-activate carrier is four (pentafluorophenyl group) boron
Hydrochlorate and Al ((CF3) 3) 3 according to mass ratio 1:3 mixture；The carrier of pre-activate carrier is SiO2；Load capacity is 15%.It splits
Load capacity is filled in solution furnace and is 15% KF/Al2O3 catalyst, and pyrolysis furnace is heated to 400 DEG C.After oxygen and activation
Hexafluoropropylene dimmer be passed through in pyrolysis furnace according to molar ratio 1:1, reaction pressure 5bar.Product is perfluor butyryl fluorine
62.46%, perfluor acetylfluoride 33.54%.
Embodiment 6: it hexafluoropropylene dimmer cracking: 1) pre-activate: specifically includes and hexafluoropropylene dimmer is passed through 180 DEG C
The reactor filled with pre-activate carrier in activate 2h；The active constituent of the pre-activate carrier is four (pentafluorophenyl group) boric acid
Salt and Al ((CFH2) 6) 3 according to mass ratio 1:1 mixture；The carrier of pre-activate carrier is Al2O3；Load capacity is 10%.It splits
Load capacity is filled in solution furnace and is 20% CuO/C catalyst, and pyrolysis furnace is heated to 600 DEG C.By six after oxygen and activation
Fluoropropene dimer is passed through in pyrolysis furnace according to molar ratio 10:1, and reaction pressure is normal pressure.Product is perfluor butyryl fluorine
57.90%, perfluor acetylfluoride 31.09%.
Embodiment 7: it hexafluoropropylene dimmer cracking: 1) pre-activate: specifically includes and hexafluoropropylene dimmer is passed through 220 DEG C
The reactor filled with pre-activate carrier in activate 1h；The active constituent of the pre-activate carrier is four (pentafluorophenyl group) boric acid
Salt and Al (CF2H) 3 according to mass ratio 1:5 mixture；The carrier of pre-activate carrier is B2O3；Load capacity is 20%.Pyrolysis furnace
In fill the CsF/C catalyst that load capacity is 10%, and pyrolysis furnace is heated to 150 DEG C.By the hexafluoro third after oxygen and activation
Alkene dimer is passed through in pyrolysis furnace according to molar ratio 1:10, reaction pressure 10bar.Product is perfluor butyryl fluorine 63.76%,
Perfluor acetylfluoride 34.24%.
Embodiment 8: hexafluoropropylene dimmer cracking: the Ag2O/Al2O3 that load capacity is 15% is filled in pyrolysis furnace and is catalyzed
Agent, and pyrolysis furnace is heated to 400 DEG C.Oxygen and hexafluoropropylene dimmer are passed through in pyrolysis furnace according to molar ratio 1:1.Reaction
Pressure is that 5bar. product is perfluor butyryl fluorine 35.13%, perfluor acetylfluoride 18.86%.Carbonyl fluoride 12.52%.
Embodiment 9: hexafluoropropylene dimmer cracking: filling the KF/Al2O3 catalyst that load capacity is 15% in pyrolysis furnace,
And pyrolysis furnace is heated to 400 DEG C.Oxygen and hexafluoropropylene dimmer are passed through in pyrolysis furnace according to molar ratio 1:1, reaction pressure
Power is 5bar.Product is perfluor butyryl fluorine 50.74%, perfluor acetylfluoride 27.25%.Carbonyl fluoride 6.32%.
Embodiment 10: hexafluoropropylene dimmer cracking: filling the CuO/C catalyst that load capacity is 20% in pyrolysis furnace, and
Pyrolysis furnace is heated to 600 DEG C.Oxygen and hexafluoropropylene dimmer are passed through in pyrolysis furnace according to molar ratio 10:1, reaction pressure
For normal pressure.Product is perfluor butyryl fluorine 44.24%, perfluor acetylfluoride 23.76%.Carbonyl fluoride 12.35%.
Embodiment 11: hexafluoropropylene dimmer cracking: filling the CsF/C catalyst that load capacity is 10% in pyrolysis furnace, and
Pyrolysis furnace is heated to 150 DEG C.Hexafluoropropylene dimmer after oxygen and activation is passed through pyrolysis furnace according to molar ratio 1:10
It is interior, reaction pressure 10bar.Product is perfluor butyryl fluorine 52.69%, perfluor acetylfluoride 28.3%, carbonyl fluoride 5.64%.
The above is only a preferred embodiment of the present invention, for those of ordinary skill in the art, according to the present invention
Thought, there will be changes in the specific implementation manner and application range, and the content of the present specification should not be construed as to the present invention
Limitation.
Claims (5)
1. a kind of method that hexafluoropropylene dimmer prepares perfluor isobutyl acyl fluorides, which is characterized in that include the following steps: hexafluoro third
Alkene dimer enters oxidation furnace and oxygen and carries out cracking reaction under catalysts conditions, and rectifying obtains perfluor isobutyl acyl fluorides；
2. the method that hexafluoropropylene dimmer according to claim 1 prepares perfluor isobutyl acyl fluorides, which is characterized in that specific
Step are as follows: using oxygen and hexafluoropropylene dimmer as raw material, reaction is prepared under the effect of the catalyst；Wherein oxygen and six
The molar ratio of fluoropropene dimer is 1:10-10:1；The catalytic time is 0.1s to 200s；The pressure of reaction is 0-
1MPa；Reaction temperature is 150-600 DEG C.
3. the method that hexafluoropropylene dimmer according to claim 2 prepares perfluor isobutyl acyl fluorides, which is characterized in that described
Catalyst is loaded catalyst, active constituent Ag2O, Al2O3, CuO, AgF, NaF, KF, RbF or CsF.
4. the method that hexafluoropropylene dimmer according to claim 3 prepares perfluor isobutyl acyl fluorides, which is characterized in that also wrap
Include pre-activate step；It specifically includes and hexafluoropropylene dimmer is passed through to 180-220 DEG C of the reactor filled with pre-activate carrier
Middle activation 1-2h；The active constituent of the pre-activate carrier is four (pentafluorophenyl group) borates and alkyl fluoride aluminium salt according to mass ratio
The mixture of 1:1-1:5；Wherein n=1-6；The carrier of pre-activate carrier is SiO2, Al2O3 or B2O3；Load capacity is
10%-20%.
5. the method that hexafluoropropylene dimmer according to claim 4 prepares perfluor isobutyl acyl fluorides, which is characterized in that described
Alkyl fluoride aluminium salt be Al ((CR1R2R3) n) 3 monomers or mixture；Wherein R1, R2 and R3 are H or F and at least within
One of be F, n=1-6.
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Application publication date: 20190419 |