CN109761795A - The method that hexafluoropropylene trimer prepares perfluor isobutyl acyl fluorides - Google Patents
The method that hexafluoropropylene trimer prepares perfluor isobutyl acyl fluorides Download PDFInfo
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- CN109761795A CN109761795A CN201811459916.8A CN201811459916A CN109761795A CN 109761795 A CN109761795 A CN 109761795A CN 201811459916 A CN201811459916 A CN 201811459916A CN 109761795 A CN109761795 A CN 109761795A
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- hexafluoropropylene trimer
- hexafluoropropylene
- acyl fluorides
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- perfluor isobutyl
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Abstract
The invention belongs to fluorine chemical fields, and in particular to a kind of method that hexafluoropropylene trimer prepares perfluor isobutyl acyl fluorides.Include the following steps: using oxygen and hexafluoropropylene dimmer/hexafluoropropylene trimer 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 trimer 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 trimer 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
Inexpensively, but electrolytic efficiency is very low, is difficult to avoid that product purity caused by electrolysis impurity is not high for raw material in method, in addition electric
It is expensive to solve pole plate cost of manufacture, cost of equipment is higher to be unfavorable for industrial implementation.Using perfluor iodide and hair in US3351644
Cigarette sulfuric acid reaction prepares perfluoro acidyl compound, and severe reaction conditions, raw material is not easy to obtain, at high cost, is also not suitable for industry and puts
Mass production.
Summary of the invention
It is an object of the invention to overcome the deficiencies of existing technologies, providing a kind of hexafluoropropylene trimer, to prepare perfluor different
The method of butyl acyl fluorides.
The present invention to achieve the above object, using following technical scheme:
A kind of method that hexafluoropropylene trimer prepares perfluor isobutyl group acyl fluorides, includes the following steps:
Perfluor isobutyl acyl fluorides is prepared using oxygen, hexafluoropropylene trimer as raw material；
Using oxygen and hexafluoropropylene trimer as raw material, reaction is prepared under the effect of the catalyst；Wherein oxygen and
The molar ratio of hexafluoropropylene trimer 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.
The catalyst be loaded catalyst, active constituent Ag2O, Al2O3, CuO, AgF, NaF, KF, RbF or
Person CsF.
Hexafluoropropylene trimer enters reactor with liquid form in step reaction, since fluid molecule is compared to gas
Molecule has shorter intermolecular distance, therefore more gaseous state hexafluoropropenes three are had in the slow gasification of liquid charging stock
Polymer molecular comes into full contact with oxygen, so as to shorten the pyrolysis time of hexafluoropropylene trimer, significantly improves raw material and integrally splits
Solve efficiency.And the presence of the hexafluoropropylene trimer more contacted with oxygen can prevent the perfluor isobutyl acyl fluorides being cracked to form with
The further cracking of perfluor five-carbon ketone, to guarantee that gained perfluor isobutyl acyl fluorides has higher degree.
Hexafluoropropylene trimer further includes pre-activate step；It specifically includes and hexafluoropropylene trimer is passed through 180-220 DEG C
The reactor filled with pre-activate carrier in activate 1-2h；The active constituent of the pre-activate carrier is four (pentafluorophenyl groups)
Borate and alkyl fluoride aluminium salt according to mass ratio 1:1-1:5 mixture；Wherein n=1-6；The carrier of pre-activate carrier is
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 trimer 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 carbon in the prior art
Acyl fluorides, thus pre-activate step implementation can guarantee hexafluoropropylene trimer rule be cracked into perfluor isobutyl acyl fluorides and perfluor
Five-carbon ketone effectively avoids the generation of perfluor carbonyl fluoride by-product.
The hexafluoropropylene trimer is obtained under the catalysis of support type ionic fluorides through gas phase reaction by hexafluoropropene
It arrives；Reaction temperature is 260-320 DEG C, time of contact 0.1-30s；The load capacity of support type ionic fluorides is 10%-
20%；Carrier is activated carbon, aluminum oxide, silica or magnesia；Ionic fluorides be AgF, NaF, KF, RbF or
Person CsF.When preparation, the upper end product exit of the catalytic reaction tube of the support type ionic fluorides with condensation water leg
The air inlet of one end of condenser be connected, the condenser other end is gas vent, and unreacted hexafluoropropene gone out by gas
Mouth is recycled to the catalytic reaction tube column of support type ionic fluorides.The fluid sample sample in condenser is taken to detect, gained hexafluoro third
The purity of alkene dimer is greater than 99%.
Compared with prior art, the beneficial effects of the present invention are:
The method that hexafluoropropylene trimer provided by the invention prepares perfluor isobutyl group acyl fluorides, reaction condition is mild, product
High income, it is pollution-free, and it is 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, below with reference to best reality
Applying example, the present invention is described in further detail.Percentage composition in the application is unless otherwise specified that quality percentage contains
Amount.
Embodiment 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, not instead
The hexafluoropropene answered is recycled to catalyst reaction tube through outlet.The liquid hexafluoropropylene trimer in detection condenser
Purity is 99.3%.The yield of hexafluoropropylene trimer is shown in Table 1.
Embodiment 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, and 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.
Embodiment 3: the preparation of hexafluoropropylene trimer raw material: by hexafluoropropene gas by being equipped with KF/C catalyst
Catalytic reaction tube, the load capacity of catalyst are 20%, and the temperature of catalyst reaction tube is 320 DEG C, time of contact 30s；
Mixed gas after reaction enters the condenser with cooling jacket by air inlet, and condensate temperature is 10 DEG C, and 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 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%, and the temperature of catalyst filling column is 150 DEG C, and time of contact is
0.1s；Mixed gas after reaction enters the condenser with cooling jacket by port entrance, and condensate temperature is 10 DEG C, not
The hexafluoropropene of reaction is recycled to catalytic reaction tube through gas vent.The liquid hexafluoropropene two in detection condenser receiver
The purity of aggressiveness is 99.3%.The yield of hexafluoropropylene dimmer is shown in Table 1.
Comparative example 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.
Comparative example 3: the preparation of hexafluoropropylene dimmer raw material: by hexafluoropropene gas by being equipped with KF/C catalyst
Catalytic reaction tube, the load capacity of catalyst are 20%, and the temperature of catalyst filling column is 220 DEG C, time of contact 30s；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 through outlet.The purity of liquid hexafluoropropylene dimmer is 99.3% in detection condenser.It applies
The yield of hexafluoropropylene dimmer is shown in Table 1 afterwards.
Table 1
Embodiment 4: it hexafluoropropylene trimer cracking: 1) pre-activate: specifically includes and hexafluoropropylene trimer 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 (phenyl-pentafluorides
Base) borate and Al ((CF3) 3) 3 according to mass ratio 1:3 mixture；The carrier of pre-activate carrier is SiO2；Load capacity is
15%.Load capacity is filled in pyrolysis furnace and is 10% Ag2O/Al2O3 catalyst, and pyrolysis furnace is heated to 400 DEG C.Oxygen and
Hexafluoropropylene trimer after activation is passed through in pyrolysis furnace according to molar ratio 1:1.Reaction pressure is that 5bar. product is perfluor five
Carbon ketone 41.87%, perfluor isobutyl acyl fluorides 34.13%.
Embodiment 5: it hexafluoropropylene trimer cracking: 1) pre-activate: specifically includes and hexafluoropropylene trimer 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 (phenyl-pentafluorides
Base) borate and Al ((CF3) 3) 3 according to mass ratio 1:3 mixture；The carrier of pre-activate carrier is SiO2；Load capacity is
15%.Load capacity is filled in pyrolysis furnace and is 10% KF/Al2O3 catalyst, and pyrolysis furnace is heated to 400 DEG C.Oxygen and work
Hexafluoropropylene trimer after change is passed through in pyrolysis furnace according to molar ratio 1:1, reaction pressure 5bar.Product is five carbon of perfluor
Ketone 52.33%, perfluor isobutyl acyl fluorides 42.66%.
Embodiment 6: it hexafluoropropylene trimer cracking: 1) pre-activate: specifically includes and hexafluoropropylene trimer 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 groups)
Borate and Al ((CFH2) 6) 3 according to mass ratio 1:1 mixture；The carrier of pre-activate carrier is Al2O3；Load capacity is
10%.Load capacity is filled in pyrolysis furnace and is 10% CuO/ activated-carbon catalyst, and pyrolysis furnace is heated to 600 DEG C.Oxygen and
Hexafluoropropylene trimer after activation is passed through in pyrolysis furnace according to molar ratio 10:1, and reaction pressure is normal pressure.Product is perfluor five
Carbon ketone 53.44%, perfluor isobutyl acyl fluorides 43.56%.
Embodiment 7: it hexafluoropropylene trimer cracking: 1) pre-activate: specifically includes and hexafluoropropylene trimer 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 groups)
Borate and Al (CF2H) 3 according to mass ratio 1:5 mixture；The carrier of pre-activate carrier is B2O3；Load capacity is 20%.
Load capacity is filled in pyrolysis furnace and is 10% CsF/ activated-carbon catalyst, and pyrolysis furnace is heated to 600 DEG C.Oxygen and activation
Hexafluoropropylene trimer afterwards is passed through in pyrolysis furnace according to molar ratio 10:1, and reaction pressure is normal pressure.Product is perfluor five-carbon ketone
53.44%, perfluor isobutyl acyl fluorides 43.56%.
Embodiment 8: hexafluoropropylene trimer cracking: the Ag2O/Al2O3 that load capacity is 10% is filled in pyrolysis furnace and is catalyzed
Agent, and pyrolysis furnace is heated to 400 DEG C.Oxygen and hexafluoropropylene trimer are passed through in pyrolysis furnace according to molar ratio 1:1.Reaction
Pressure is that 5bar. product is perfluor five-carbon ketone 27.54%, perfluor isobutyl acyl fluorides 22.45%, carbonyl fluoride 11.47%.
Embodiment 9: hexafluoropropylene trimer cracking: filling the KF/Al2O3 catalyst that load capacity is 10% in pyrolysis furnace,
And pyrolysis furnace is heated to 400 DEG C.Oxygen and hexafluoropropylene trimer are passed through in pyrolysis furnace according to molar ratio 1:1, reaction pressure
For 5bar.Product is perfluor five-carbon ketone 40.22%, perfluor isobutyl acyl fluorides 32.78%, carbonyl fluoride 3.47%.
Embodiment 10: the CuO/ activated carbon catalysis that load capacity is 10% hexafluoropropylene trimer cracking: is filled in pyrolysis furnace
Agent, and pyrolysis furnace is heated to 600 DEG C.Oxygen and hexafluoropropylene trimer are passed through in pyrolysis furnace according to molar ratio 10:1, reaction
Pressure is normal pressure.Product is perfluor five-carbon ketone 35.25%, perfluor isobutyl acyl fluorides 28.74%, carbonyl fluoride 12.64%.
Embodiment 11: the CsF/ activated carbon catalysis that load capacity is 10% hexafluoropropylene trimer cracking: is filled in pyrolysis furnace
Agent, and pyrolysis furnace is heated to 150 DEG C.Oxygen and hexafluoropropylene trimer are passed through in pyrolysis furnace according to molar ratio 1:10, reaction
Pressure is 10bar.Product is perfluor five-carbon ketone 42.97%, perfluor isobutyl acyl fluorides 35.02%, carbonyl fluoride 6.32%.
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 trimer prepares perfluor isobutyl group acyl fluorides, which is characterized in that include the following steps:
Hexafluoropropylene trimer 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 trimer according to claim 1 prepares perfluor isobutyl group acyl fluorides, which is characterized in that tool
Body step are as follows: using oxygen hexafluoropropylene trimer as raw material, reaction is prepared under the effect of the catalyst；Wherein oxygen and six
The molar ratio of fluoropropene hexafluoropropylene trimer is 1:10-10:1；The catalytic time is 0.1s to 200s；The pressure of reaction
For 0-1MPa；Reaction temperature is 150-600 DEG C.
3. the method that hexafluoropropylene trimer according to claim 2 prepares perfluor isobutyl group acyl fluorides, which is characterized in that institute
Stating catalyst is loaded catalyst, active constituent Ag2O, Al2O3, CuO, AgF, NaF, KF, RbF or CsF.
4. the method that hexafluoropropylene trimer according to claim 3 prepares perfluor isobutyl group acyl fluorides, which is characterized in that six
Fluoropropene tripolymer further includes pre-activate step；Specifically include by hexafluoropropylene trimer be passed through 180-220 DEG C filled with pre-
1-2h is activated in the reactor of activated carrier；The active constituent of the pre-activate carrier is four (pentafluorophenyl group) borates and alkyl
Fluorine 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%.
5. the method that hexafluoropropylene trimer according to claim 4 prepares perfluor isobutyl group acyl fluorides, which is characterized in that institute
The alkyl fluoride aluminium salt stated is Al ((CR1R2R3) n) 3 monomers or mixture；Wherein R1, R2 and R3 be H or F and at least its
One of be F, n=1-6.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110479196A (en) * | 2019-06-30 | 2019-11-22 | 天津市长芦化工新材料有限公司 | Acetonitrile recycles reaction unit |
| CN117160497A (en) * | 2023-11-03 | 2023-12-05 | 北京宇极科技发展有限公司 | Catalyst and method for preparing hexafluoropropylene dimer |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106946669A (en) * | 2017-03-21 | 2017-07-14 | 国家电网公司 | A kind of environmentally friendly insulating gas joint production process and industrial production device |
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- 2018-11-30 CN CN201811459916.8A patent/CN109761795A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106946669A (en) * | 2017-03-21 | 2017-07-14 | 国家电网公司 | A kind of environmentally friendly insulating gas joint production process and industrial production device |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110479196A (en) * | 2019-06-30 | 2019-11-22 | 天津市长芦化工新材料有限公司 | Acetonitrile recycles reaction unit |
| CN117160497A (en) * | 2023-11-03 | 2023-12-05 | 北京宇极科技发展有限公司 | Catalyst and method for preparing hexafluoropropylene dimer |
| CN117160497B (en) * | 2023-11-03 | 2024-03-08 | 北京宇极科技发展有限公司 | Catalyst and method for preparing hexafluoropropylene dimer |
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Application publication date: 20190517 |