CN107473929A - A kind of method that coproduction prepares the amylene of 2 methyl of perfluor 2 and the amylene of 4 methyl of perfluor 2 - Google Patents
A kind of method that coproduction prepares the amylene of 2 methyl of perfluor 2 and the amylene of 4 methyl of perfluor 2 Download PDFInfo
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- CN107473929A CN107473929A CN201710616035.1A CN201710616035A CN107473929A CN 107473929 A CN107473929 A CN 107473929A CN 201710616035 A CN201710616035 A CN 201710616035A CN 107473929 A CN107473929 A CN 107473929A
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- 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
- C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
- C07C17/278—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of only halogenated hydrocarbons
- C07C17/281—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of only halogenated hydrocarbons of only one compound
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- Y02P20/584—Recycling of catalysts
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Abstract
The invention discloses a kind of method that coproduction prepares the amylene of 2 methyl of perfluor 2 and the amylene of 4 methyl of perfluor 2, including a kind of recycled technique.Have the characteristics that high conversion and selectivity, the gentle controllable, catalysts and solvents of reaction condition can in reactor recycled and reaction product separate it is simple.
Description
Technical field
The present invention relates to a kind of oligomerisation reaction, and perfluor -2- methyl -2- is prepared by oligomerization of hexafluoropropylene more particularly, to one kind
The method of amylene and perfluor -4- methyl -2- amylenes.
Background technology
Oligomerisation reaction refers to certain olefinic monomer (C2-C14) under catalyst action, the one or more knots of polymerization generation
Structure unit repeats the course of reaction of connected compound.The catalytic reaction is in chemical fields such as petroleum refinings since nineteen thirty-five
It is used widely.Oligomerisation reaction and the molecular weight of product for differing from polymerisation of general polymerization reaction are very big
Polymer, and oligomerisation reaction mainly produce olefinic monomer two, three, four, pentamer.
The dimer and tripolymer that oligomerization of hexafluoropropylene obtains all are particularly useful industrial chemicals, can be derived many fluorine-containing
Surfactant.There is the perfluor carbochain of its hydrophobic height to be branched, and compared with general straight chain perfluorinated surfactant, increase
Some special physical properties.
Hexafluoropropylene dimmer has two kinds of structures, perfluoro-2-methyl-2-amylene and perfluor -4- methyl -2- amylenes, for
Their preparation method, there is following report in the prior art：
United States Patent (USP) US4377717 discloses the side that hexafluoropropene gas-phase catalytic polymerisation prepares perfluoro-2-methyl-2-amylene
Method, using activated carbon as catalyst, 410~420 DEG C of reaction temperature, 13 seconds residence times, yield 29.6%, selectivity 64.5%.
The method reaction temperature is high, and reaction conversion ratio and selectivity are relatively low.
United States Patent (USP) US5387728 discloses the side that hexafluoropropene liquid-phase catalysis polymerization prepares perfluor -4- methyl -2- amylenes
Method, in the presence of the non-polar solvens such as diethylene glycol diethyl ether, tetrahydrofuran and acetonitrile, with amine compound such as N, N, N ', N '-tetra-
Methyl ethylenediamine and fluoride such as potassium fluoride, cesium fluoride etc. are catalyst, are reacted at 30~40 DEG C through high degree of agitation and are made complete
Fluoro- 4- methyl -2- amylenes.The method catalyst solvent system is complicated, and product separation is difficult, and stirring dynamic sealing is easily let out under high pressure
Leakage.
Chinese patent CN1876611A discloses one kind and uses non-polar solven acetonitrile as solvents, is catalyzed with potassium rhodanide
Agent, the method that hexafluoropropylene dimmer is made is reacted at 10~50 DEG C.This patent, which also discloses, prepares hexafluoropropylene dimmer
Reaction unit, crank connecting link drive move back and forth, material is stirred well, while also avoid dynamic sealing.This device
Although material can be made to be stirred well, it is unfavorable for industrial amplification.
The content of the invention
It is an object of the invention to provide a kind of coproduction to prepare perfluoro-2-methyl-2-amylene and perfluor -4- methyl -2- penta
The method of alkene, have high conversion and the gentle controllable, catalysts and solvents of selectivity, reaction condition can in reactor circulating sleeve
The advantages that simple is separated with reaction product.
It is to reach goal of the invention the technical solution adopted by the present invention：
A kind of method that coproduction prepares perfluoro-2-methyl-2-amylene and perfluor -4- methyl -2- amylenes, including following circulation
Apply mechanically technique：
(1) in reactor, in the presence of solvent, under catalyst action, hexafluoropropene occurs oligomerisation reaction and is made complete
Fluoro- 2- methyl -2- amylenes and perfluor -4- methyl -2- amylenes；
(2) stand, reactant is divided into three layers from top to bottom, solvent layer, reaction product layer and catalyst layer；
(3) intermediate reaction product layer is extruded from reactor using nitrogen or inert gas；
(4) hexafluoropropene, repeat step (1) to (3) are added toward reactor；
The solvent is selected from DMF, DMA, sulfolane, acetonitrile, tetrahydrofuran, two
One kind in methyl sulfoxide, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, ethylene glycol diethyl ether and Propylene Glycol Dimethyl Ether, two
Kind or three kinds of combination of the above；
One kind, two or three combination of the above of the catalyst in CsF, NaF, LiF, KF and RbF；
Solubility≤1% of the catalyst in a solvent, solubility≤2% of reaction product in a solvent；
The solvent density ＜ reaction products density ＜ density of catalyst.
The present invention is effectively utilized solvent, reaction product and catalyst three by selecting suitable catalysts and solvents
Between density contrast and poor solubility, reaction terminate stand after, reactant is divided into three layers from top to bottom in reactor, solvent
Layer, reaction product layer and catalyst layer, then by adding nitrogen or inert gas by reaction product via suction pipe to reactor
Extrude reactor.Present invention reaction be intermittent reaction, and after the completion of primary first-order equation, reaction dissolvent and catalyst attrition are small, only need
Secondary response can be achieved after adding hexafluoropropene toward reactor, and do not need separating catalyst and solvent, cleaning reactor etc.
Step, after recycled tens times, feed stock conversion and selectivity of product there is no change.
As preferable mode, above-mentioned solvent in diethylene glycol diethyl ether, diethylene glycol dimethyl ether and acetonitrile one
Plant, two or three.Moisture in solvent has an impact to reaction, and higher moisture can reduce reaction speed, extend reaction
Time, preferable solvent water content≤1000PPM, more preferably moisture≤300PPM.The dosage of one-pot solvent
Preferably 200~800kg/1000kg hexafluoropropenes, more preferably 400~600kg/1000kg hexafluoropropenes.
The catalyst that the present invention uses needs the solubility in solvent and reaction product with very little, and suitable catalyst is
One kind, two or three of combination of the above in CsF, NaF, LiF, KF and RbF, more preferably selected from CsF, NaF and
One kind in KF, two or three.The dosage of one-pot catalyst is preferably 2~15kg/1000kg hexafluoropropenes, further preferably
For 7~10kg/1000kg hexafluoropropenes.
The temperature of reaction of the present invention is preferably 30~150 DEG C, more preferably 50~100 DEG C.Too low temperature
Reaction speed can be reduced, too high temperature can generate other accessory substances, and can increase the unsafe factor of reaction.
The pressure of reaction of the present invention is preferably 0.1~1.5MPa, more preferably 0.5~0.8MPa.Too low
Pressure can reduce reaction rate, and too high pressure can not only generate other accessory substances, and reaction speed easily causes very much soon
Unsafe factor.
In reaction of the present invention, discharge nozzle is generally set in a kettle, discharge nozzle lower end is located at reaction product layer, gone out
Expects pipe upper end is arranged on outside reactor, the method by adding nitrogen or inert gas to reactor, by reaction product via going out
Expects pipe extrudes reactor.Suitable inert gas includes helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe) and radon (Rn).
After reaction product extrudes reactor via discharge nozzle, it need to only pass through simple distillation operation and can obtain purity more than 99.9%
Perfluoro-2-methyl-2-amylene and perfluor -4- methyl -2- amylenes.
The method of the invention compared with prior art, has the characteristics that：
(1) recycled technique can realize catalysts and solvents system recycled in reactor, after simplifying reaction
Treatment process, the utilization rate and production efficiency of catalysts and solvents are improved, reduces production cost；
(2) realize prepared by the coproduction of perfluoro-2-methyl-2-amylene and perfluor -4- methyl -2- amylenes, conversion ratio and selection
Property it is high, reaction condition is gently controllable；
(3) reaction product separation method is novel, easy, efficiency high.
Embodiment
The present invention is further described with reference to specific embodiment, but does not limit the invention to these tools
Body embodiment.One skilled in the art would recognize that present invention encompasses may include in Claims scope
All alternatives, improvement project and equivalents.
Embodiment 1
The present embodiment uses CsF as catalyst, and acetonitrile is that solvent progress hexafluoropropene liquid phase oligomerisation prepares perfluor -2- first
Base -2- amylenes and perfluor -4- methyl -2- amylenes.
The CsF of 600kg acetonitrile and 10kg is added into 2m by charge door3In autoclave, then closed reactor,
Vacuumize repeatedly, carry out nitrogen displacement, oxygen content in kettle is less than 20ppm.Then stirring is opened, 50 DEG C is warming up to, persistently delays
1000kg raw material hexafluoropropenes are slowly passed through, control reaction pressure is in 0.5MPa or so.Reaction speed depends on being passed through hexafluoro third
The speed of alkene, the speed for being passed through hexafluoropropene should not be too fast, and otherwise reaction temperature is difficult to control.After raw material has led to, reaction is kept
Temperature is at 50 DEG C in kettle, untill reactor pressure drops to 0.16MPa.Then cooling stands 3 hours, after standing, perfluor -2- first
Base -2- amylenes and perfluor -4- methyl -2- amylenes crude product are pressed into High Purity Nitrogen, reaction production into reactor in intermediate reaction product layer
Nitride layer is pressed out to product groove via discharge nozzle, retains solvent layer and catalyst layer, in case lower secondary response uses.Through gas-chromatography
Analysis, product data such as table 1.
Embodiment 2
The present embodiment uses NaF as catalyst, and diethylene glycol diethyl ether is that solvent carries out hexafluoropropene liquid phase oligomerisation preparation
Perfluoro-2-methyl-2-amylene and perfluor -4- methyl -2- amylenes.
The NaF of 600kg diethylene glycol diethyl ether and 8kg is added into 2m by charge door3In autoclave, Ran Houmi
Reactor is closed, is vacuumized repeatedly, is carried out nitrogen displacement, oxygen content in kettle is less than 20ppm.Then stirring is opened, is warming up to 50
DEG C, continue slowly to be passed through 1000kg raw material hexafluoropropenes, control reaction pressure is in 0.5MPa or so.Reaction speed depends on logical
Enter the speed of hexafluoropropene, the speed for being passed through hexafluoropropene should not be too fast, and otherwise reaction temperature is difficult to control.After raw material has led to,
Temperature is at 50 DEG C in holding reactor, untill reactor pressure drops to 0.16MPa.Then cooling stands 3 hours, after standing,
Perfluoro-2-methyl-2-amylene and perfluor -4- methyl -2- amylenes crude product are pressed into high-purity into reactor in intermediate reaction product layer
Nitrogen, reaction product layer are pressed out to product groove via discharge nozzle, retain solvent layer and catalyst layer, in case lower secondary response uses.
Through gas chromatographic analysis, product data such as table 1.
Embodiment 3
The present embodiment uses CsF as catalyst, and diethylene glycol dimethyl ether is that solvent carries out hexafluoropropene liquid phase oligomerisation preparation
Perfluoro-2-methyl-2-amylene and perfluor -4- methyl -2- amylenes.
The CsF of 600kg diethylene glycol dimethyl ether and 8kg is added into 2m by charge door3In autoclave, Ran Houmi
Reactor is closed, is vacuumized repeatedly, is carried out nitrogen displacement, oxygen content in kettle is less than 20ppm.Then stirring is opened, is warming up to 50
DEG C, continue slowly to be passed through 1000kg raw material hexafluoropropenes, control reaction pressure is in 0.5MPa or so.Reaction speed depends on logical
Enter the speed of hexafluoropropene, the speed for being passed through hexafluoropropene should not be too fast, and otherwise reaction temperature is difficult to control.After raw material has led to,
Temperature is at 50 DEG C in holding reactor, untill reactor pressure drops to 0.16MPa.Then cooling stands 3 hours, after standing,
Perfluoro-2-methyl-2-amylene and perfluor -4- methyl -2- amylenes crude product are pressed into high-purity into reactor in intermediate reaction product layer
Nitrogen, reaction product layer are pressed out to product groove via discharge nozzle, retain solvent layer and catalyst layer, in case lower secondary response uses.
Through gas chromatographic analysis, product data such as table 1.
Embodiment 4
The present embodiment uses KF as catalyst, acetonitrile be solvent carry out hexafluoropropene liquid phase oligomerisation prepare perfluor -2- methyl -
2- amylenes and perfluor -4- methyl -2- amylenes.
The KF of 400kg acetonitrile and 7kg is added into 2m by charge door3In autoclave, then closed reactor, takes out
Vacuum is multiple, carries out nitrogen displacement, oxygen content in kettle is less than 20ppm.Then stirring is opened, is warming up to 50 DEG C, is continued slowly
Ground is passed through 1000kg raw material hexafluoropropenes, and control reaction pressure is in 0.5MPa or so.Reaction speed depends on being passed through hexafluoropropene
Speed, be passed through that the speed of hexafluoropropene is unsuitable too fast, and otherwise reaction temperature is difficult to control.After raw material has led to, reactor is kept
Interior temperature is at 50 DEG C, untill reactor pressure drops to 0.16MPa.Then cooling stands 3 hours, after standing, perfluor -2- first
Base -2- amylenes and perfluor -4- methyl -2- amylenes crude product are pressed into High Purity Nitrogen, reaction production into reactor in intermediate reaction product layer
Nitride layer is pressed out to product groove via discharge nozzle, retains solvent layer and catalyst layer, in case lower secondary response uses.Through gas-chromatography
Analysis, product data such as table 1.
Embodiment 5
The present embodiment uses CsF as catalyst, and diethylene glycol diethyl ether is that solvent carries out hexafluoropropene liquid phase oligomerisation preparation
Perfluoro-2-methyl-2-amylene and perfluor -4- methyl -2- amylenes.
The CsF of 500kg diethylene glycol diethyl ether and 10kg is added into 2m by charge door3In autoclave, then
Closed reactor, vacuumize repeatedly, carry out nitrogen displacement, oxygen content in kettle is less than 20ppm.Then stirring is opened, is warming up to
50 DEG C, continue slowly to be passed through 1000kg raw material hexafluoropropenes, control reaction pressure is in 0.5MPa or so.Reaction speed depends on
The speed of hexafluoropropene is passed through, the speed for being passed through hexafluoropropene should not be too fast, and otherwise reaction temperature is difficult to control.Raw material has led to
Afterwards, temperature is at 50 DEG C in holding reactor, untill reactor pressure drops to 0.16MPa.Then cooling stands 3 hours, stands
Afterwards, perfluoro-2-methyl-2-amylene and perfluor -4- methyl -2- amylenes crude product are pressed into reactor in intermediate reaction product layer
High Purity Nitrogen, reaction product layer are pressed out to product groove via discharge nozzle, retain solvent layer and catalyst layer, in case lower secondary response makes
With.Through gas chromatographic analysis, product data such as table 1.
Embodiment 6
The present embodiment uses CsF as catalyst, and diethylene glycol dimethyl ether is that solvent carries out hexafluoropropene liquid phase oligomerisation preparation
Perfluoro-2-methyl-2-amylene and perfluor -4- methyl -2- amylenes.
The CsF of 400kg diethylene glycol dimethyl ether and 10kg is added into 2m by charge door3In autoclave, then
Closed reactor, vacuumize repeatedly, carry out nitrogen displacement, oxygen content in kettle is less than 20ppm.Then stirring is opened, is warming up to
60 DEG C, continue slowly to be passed through 1000kg raw material hexafluoropropenes, control reaction pressure is in 0.5MPa or so.Reaction speed depends on
The speed of hexafluoropropene is passed through, the speed for being passed through hexafluoropropene should not be too fast, and otherwise reaction temperature is difficult to control.Raw material has led to
Afterwards, temperature is at 60 DEG C in holding reactor, untill reactor pressure drops to 0.16MPa.Then cooling stands 3 hours, stands
Afterwards, perfluoro-2-methyl-2-amylene and perfluor -4- methyl -2- amylenes crude product are pressed into reactor in intermediate reaction product layer
High Purity Nitrogen, reaction product layer are pressed out to product groove via discharge nozzle, retain solvent layer and catalyst layer, in case lower secondary response makes
With.Through gas chromatographic analysis, product data such as table 1.
Embodiment 7
The present embodiment uses KF as catalyst, acetonitrile be solvent carry out hexafluoropropene liquid phase oligomerisation prepare perfluor -2- methyl -
2- amylenes and perfluor -4- methyl -2- amylenes.
The KF of 600kg acetonitrile and 8kg is added into 2m by charge door3In autoclave, then closed reactor, takes out
Vacuum is multiple, carries out nitrogen displacement, oxygen content in kettle is less than 20ppm.Then stirring is opened, is warming up to 60 DEG C, is continued slowly
Ground is passed through raw material 1000kg hexafluoropropenes, and control reaction pressure is in 0.7MPa or so.Reaction speed depends on being passed through hexafluoropropene
Speed, be passed through that the speed of hexafluoropropene is unsuitable too fast, and otherwise reaction temperature is difficult to control.After raw material has led to, reactor is kept
Interior temperature is at 60 DEG C, untill reactor pressure drops to 0.16MPa.Then cooling stands 3 hours, after standing, perfluor -2- first
Base -2- amylenes and perfluor -4- methyl -2- amylenes crude product are pressed into High Purity Nitrogen, reaction production into reactor in intermediate reaction product layer
Nitride layer is pressed out to product groove via discharge nozzle, retains solvent layer and catalyst layer, in case lower secondary response uses.Through gas-chromatography
Analysis, product data such as table 1.
Embodiment 8
The present embodiment uses KF as catalyst, acetonitrile be solvent carry out hexafluoropropene liquid phase oligomerisation prepare perfluor -2- methyl -
2- amylenes and perfluor -4- methyl -2- amylenes.
The KF of 800kg acetonitrile and 10kg is added into 2m by charge door3In autoclave, then closed reactor,
Vacuumize repeatedly, carry out nitrogen displacement, oxygen content in kettle is less than 20ppm.Then stirring is opened, 100 DEG C is warming up to, persistently delays
1000kg raw material hexafluoropropenes are slowly passed through, control reaction pressure is in 0.8MPa or so.Reaction speed depends on being passed through hexafluoro third
The speed of alkene, the speed for being passed through hexafluoropropene should not be too fast, and otherwise reaction temperature is difficult to control.After raw material has led to, reaction is kept
Temperature is at 100 DEG C in kettle, untill reactor pressure drops to 0.16MPa.Then cooling stands 3 hours, after standing, perfluor -2-
Methyl -2- amylenes and perfluor -4- methyl -2- amylenes crude product are pressed into High Purity Nitrogen into reactor, reacted in intermediate reaction product layer
Product layer is pressed out to product groove via discharge nozzle, retains solvent layer and catalyst layer, in case lower secondary response uses.Through gas phase color
Spectrum analysis, product data such as table 1.
Embodiment 9
The present embodiment uses CsF as catalyst, and diethylene glycol diethyl ether is that solvent carries out hexafluoropropene liquid phase oligomerisation preparation
Perfluoro-2-methyl-2-amylene and perfluor -4- methyl -2- amylenes.
The CsF of 500kg diethylene glycol diethyl ether and 10kg is added into 2m by charge door3In autoclave, then
Closed reactor, vacuumize repeatedly, carry out nitrogen displacement, oxygen content in kettle is less than 20ppm.Then stirring is opened, is warming up to
80 DEG C, continue slowly to be passed through 1000kg raw material hexafluoropropenes, control reaction pressure is in 0.6MPa or so.Reaction speed depends on
The speed of hexafluoropropene is passed through, the speed for being passed through hexafluoropropene should not be too fast, and otherwise reaction temperature is difficult to control.Raw material has led to
Afterwards, temperature is at 80 DEG C in holding reactor, untill reactor pressure drops to 0.16MPa.Then cooling stands 3 hours, stands
Afterwards, perfluoro-2-methyl-2-amylene and perfluor -4- methyl -2- amylenes crude product are pressed into reactor in intermediate reaction product layer
High Purity Nitrogen, reaction product layer are pressed out to product groove via discharge nozzle, retain solvent layer and catalyst layer, in case lower secondary response makes
With.Through gas chromatographic analysis, product data such as table 1.
Embodiment 10
The present embodiment uses CsF as catalyst, and diethylene glycol diethyl ether is that solvent carries out hexafluoropropene liquid phase oligomerisation preparation
Perfluoro-2-methyl-2-amylene and perfluor -4- methyl -2- amylenes.
The CsF of 600kg diethylene glycol diethyl ether and 10kg is added into 2m by charge door3In autoclave, then
Closed reactor, vacuumize repeatedly, carry out nitrogen displacement, oxygen content in kettle is less than 20ppm.Then stirring is opened, is warming up to
100 DEG C, continue slowly to be passed through 1000kg raw material hexafluoropropenes, control reaction pressure is in 0.8MPa or so.Reaction speed depends on
In the speed for being passed through hexafluoropropene, the speed for being passed through hexafluoropropene should not be too fast, and otherwise reaction temperature is difficult to control.Raw material has led to
Afterwards, temperature is at 100 DEG C in holding reactor, untill reactor pressure drops to 0.16MPa.Then cooling stands 3 hours, stands
Afterwards, perfluoro-2-methyl-2-amylene and perfluor -4- methyl -2- amylenes crude product are pressed into reactor in intermediate reaction product layer
High Purity Nitrogen, reaction product layer are pressed out to product groove via discharge nozzle, retain solvent layer and catalyst layer, in case lower secondary response makes
With.Through gas chromatographic analysis, product data such as table 1.
The different catalysts of table 1. and solvent carry out reaction result
Embodiment 11
The present embodiment uses 1 reacted solvent of embodiment and catalyst, investigates the solvent and catalyst pair of recycling
The influence of reaction, other operation conditions are same as Example 1, reaction result such as table 2.
The catalyst of table 2. recycles result with solvent
From the interpretation of result of embodiment 11, after solvent and catalyst carry out in kettle recycled 18 times, the reaction turns
Rate is basically unchanged with selectivity, illustrates that solvent and catalyst recycled technique of the present invention is feasible.
Claims (10)
1. a kind of method that coproduction prepares perfluoro-2-methyl-2-amylene and perfluor -4- methyl -2- amylenes, it is characterised in that including
Following recycled technique：
(1) in reactor, in the presence of solvent, under catalyst action, hexafluoropropene occurs oligomerisation reaction and perfluor -2- is made
Methyl -2- amylenes and perfluor -4- methyl -2- amylenes；
(2) stand, reactant is divided into three layers from top to bottom, solvent layer, reaction product layer and catalyst layer；
(3) intermediate reaction product layer is extruded from reactor using nitrogen or inert gas；
(4) hexafluoropropene, repeat step (1) to (3) are added toward reactor；
The solvent is selected from DMF, DMA, sulfolane, acetonitrile, tetrahydrofuran, dimethyl
One kind in sulfoxide, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, ethylene glycol diethyl ether and Propylene Glycol Dimethyl Ether, two kinds or
Three kinds of combination of the above；
One kind, two or three combination of the above of the catalyst in CsF, NaF, LiF, KF and RbF；
Solubility≤1% of the catalyst in a solvent, solubility≤2% of reaction product in a solvent；
The solvent density ＜ reaction products density ＜ density of catalyst.
2. the side of perfluoro-2-methyl-2-amylene and perfluor -4- methyl -2- amylenes is prepared according to the coproduction described in claim 1
Method, it is characterised in that one kind in diethylene glycol diethyl ether, diethylene glycol dimethyl ether and acetonitrile of the solvent, two kinds or three
Kind.
3. the side of perfluoro-2-methyl-2-amylene and perfluor -4- methyl -2- amylenes is prepared according to the coproduction described in claim 1
Method, it is characterised in that the solvent water content≤1000PPM, the dosage of one-pot solvent is 200~800kg/1000kg hexafluoros
Propylene.
4. the side of perfluoro-2-methyl-2-amylene and perfluor -4- methyl -2- amylenes is prepared according to the coproduction described in claim 3
Method, it is characterised in that the solvent water content≤300PPM, the dosage of one-pot solvent is 400~600kg/1000kg hexafluoros third
Alkene.
5. the side of perfluoro-2-methyl-2-amylene and perfluor -4- methyl -2- amylenes is prepared according to the coproduction described in claim 1
Method, it is characterised in that one kind in CsF, NaF and KF of the catalyst, two or three, the dosage of one-pot catalyst is 2
~15kg/1000kg hexafluoropropenes.
6. the side of perfluoro-2-methyl-2-amylene and perfluor -4- methyl -2- amylenes is prepared according to the coproduction described in claim 5
Method, it is characterised in that the dosage of the one-pot catalyst is 7~10kg/1000kg hexafluoropropenes.
7. the side of perfluoro-2-methyl-2-amylene and perfluor -4- methyl -2- amylenes is prepared according to the coproduction described in claim 1
Method, it is characterised in that reaction temperature is 30~150 DEG C, and reaction pressure is 0.1~1.5MPa.
8. the side of perfluoro-2-methyl-2-amylene and perfluor -4- methyl -2- amylenes is prepared according to the coproduction described in claim 7
Method, it is characterised in that reaction temperature is 50~100 DEG C, and reaction pressure is 0.5~0.8MPa.
9. the side of perfluoro-2-methyl-2-amylene and perfluor -4- methyl -2- amylenes is prepared according to the coproduction described in claim 1
Method, it is characterised in that discharge nozzle is used in the step (3), discharge nozzle lower end is located at reaction product layer, and discharge nozzle upper end is set
Outside reactor, reaction product is extruded into reactor via discharge nozzle by adding nitrogen or inert gas to reactor.
10. the side of perfluoro-2-methyl-2-amylene and perfluor -4- methyl -2- amylenes is prepared according to the coproduction described in claim 1
Method, it is characterised in that oxygen content is less than 20ppm in the reactor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710616035.1A CN107473929B (en) | 2012-10-26 | 2012-10-26 | Method for co-producing perfluoro-2-methyl-2-pentene and perfluoro-4-methyl-2-pentene |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710616035.1A CN107473929B (en) | 2012-10-26 | 2012-10-26 | Method for co-producing perfluoro-2-methyl-2-pentene and perfluoro-4-methyl-2-pentene |
| CN201210418766.2A CN103787824B (en) | 2012-10-26 | 2012-10-26 | A kind of method that coproduction prepares the amylene of 2 methyl of perfluor 2 and the amylene of 4 methyl of perfluor 2 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210418766.2A Division CN103787824B (en) | 2012-10-26 | 2012-10-26 | A kind of method that coproduction prepares the amylene of 2 methyl of perfluor 2 and the amylene of 4 methyl of perfluor 2 |
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| Publication Number | Publication Date |
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| CN107473929A true CN107473929A (en) | 2017-12-15 |
| CN107473929B CN107473929B (en) | 2020-10-30 |
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| CN201710616035.1A Active CN107473929B (en) | 2012-10-26 | 2012-10-26 | Method for co-producing perfluoro-2-methyl-2-pentene and perfluoro-4-methyl-2-pentene |
| CN201210418766.2A Active CN103787824B (en) | 2012-10-26 | 2012-10-26 | A kind of method that coproduction prepares the amylene of 2 methyl of perfluor 2 and the amylene of 4 methyl of perfluor 2 |
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| CN201210418766.2A Active CN103787824B (en) | 2012-10-26 | 2012-10-26 | A kind of method that coproduction prepares the amylene of 2 methyl of perfluor 2 and the amylene of 4 methyl of perfluor 2 |
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| CN112745191A (en) * | 2020-12-31 | 2021-05-04 | 中国科学院过程工程研究所 | Method for catalyzing dimerization reaction of hexafluoropropylene by ionic liquid |
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| TWI694066B (en) * | 2014-05-27 | 2020-05-21 | 德商拜耳動物保健有限公司 | Process for the preparation of 5-fluoro-1h-pyrazoles starting from hexafluoropropene |
| CN104478653B (en) * | 2014-12-30 | 2016-04-27 | 上海三爱富新材料股份有限公司 | The preparation method of perfluoro-2-methyl-2-amylene |
| CN105837398B (en) * | 2016-06-27 | 2018-05-22 | 浙江诺亚氟化工有限公司 | The industrialized preparing process and process units of a kind of perfluoro-2-methyl-2-amylene |
| CN108383681B (en) * | 2018-03-19 | 2021-05-18 | 浙江巨化技术中心有限公司 | Preparation method of perfluoro-2-methyl-2-pentene |
| CN109574812B (en) * | 2018-12-24 | 2021-08-13 | 天津长芦新材料研究院有限公司 | Method for preparing perfluoroolefin with high selectivity |
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| GB910371A (en) * | 1958-02-27 | 1962-11-14 | Du Pont | Production of perfluoroolefines by isomerization or polymerization |
| JPS49134614A (en) * | 1973-05-08 | 1974-12-25 |
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| US3917724A (en) * | 1973-02-09 | 1975-11-04 | Hoechst Ag | Process for preparing oligomers of hexafluoropropene |
| JPS51125307A (en) * | 1975-04-17 | 1976-11-01 | Central Glass Co Ltd | Process for preparation of hexafluoropropene oligomers |
| JPS52108911A (en) * | 1976-03-05 | 1977-09-12 | Central Glass Co Ltd | Isomerization of hexafluoropropene oligomers |
| CN1030406A (en) * | 1987-06-29 | 1989-01-18 | 上海市有机氟材料研究所 | Make the method for the oligomerization of hexafluoropropylene that contains freonll-11 |
| US5254774A (en) * | 1992-12-28 | 1993-10-19 | Minnesota Mining And Manufacturing Company | Preparation of hexafluoropropene oligomers |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB910371A (en) * | 1958-02-27 | 1962-11-14 | Du Pont | Production of perfluoroolefines by isomerization or polymerization |
| JPS49134614A (en) * | 1973-05-08 | 1974-12-25 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112745191A (en) * | 2020-12-31 | 2021-05-04 | 中国科学院过程工程研究所 | Method for catalyzing dimerization reaction of hexafluoropropylene by ionic liquid |
| CN112745191B (en) * | 2020-12-31 | 2022-04-05 | 中国科学院过程工程研究所 | Method for catalyzing dimerization reaction of hexafluoropropylene by ionic liquid |
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| CN103787824B (en) | 2018-01-02 |
| CN103787824A (en) | 2014-05-14 |
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