CN107473929B - Method for co-producing perfluoro-2-methyl-2-pentene and perfluoro-4-methyl-2-pentene - Google Patents
Method for co-producing perfluoro-2-methyl-2-pentene and perfluoro-4-methyl-2-pentene Download PDFInfo
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Abstract
The invention discloses a method for coproducing perfluoro-2-methyl-2-pentene and perfluoro-4-methyl-2-pentene, which comprises a recycling process. Has the characteristics of high conversion rate and selectivity, mild and controllable reaction conditions, circularly applying catalyst and solvent in a reaction kettle, simple separation of reaction products and the like.
Description
Technical Field
The invention relates to an oligomerization reaction, in particular to a method for preparing perfluoro-2-methyl-2-pentene and perfluoro-4-methyl-2-pentene by oligomerization of hexafluoropropylene.
Background
The oligomerization reaction refers to a certain olefin monomer (C)2-C14) Under the action of catalyst, the reaction process of polymerizing to generate one or more structural units and repeating connected compounds. Since 1935 the catalytic reaction has been widely used in chemical industry such as petroleum refining. The oligomerization reaction is distinguished from the general polymerization reaction in that the molecular weight of the product of the polymerization reaction is a polymer with a large number, and the oligomerization reaction mainly produces di-, tri-, tetra-and pentamers of olefin monomers.
The dipolymer and tripolymer obtained by oligomerization of hexafluoropropylene are very useful chemical raw materials, and can be used for deriving a plurality of fluorine-containing surfactants. The hydrophobic perfluorocarbon chain has high branching degree, and has some special physical performance compared with common linear perfluoro surfactant.
Hexafluoropropylene dimer has two structures, perfluoro-2-methyl-2-pentene and perfluoro-4-methyl-2-pentene, and for their preparation the following are reported in the prior art:
U.S. Pat. No. 4,4377717 discloses a method for preparing perfluoro-2-methyl-2-pentene by gas-phase catalytic polymerization of hexafluoropropylene, wherein activated carbon is used as a catalyst, the reaction temperature is 410-420 ℃, the retention time is 13 seconds, the yield is 29.6%, and the selectivity is 64.5%. The method has high reaction temperature and low reaction conversion rate and selectivity.
U.S. Pat. No. 5,5387728 discloses a method for preparing perfluoro-4-methyl-2-pentene by liquid phase catalytic polymerization of hexafluoropropylene, in the presence of nonpolar solvents such as diethylene glycol diethyl ether, tetrahydrofuran and acetonitrile, and in the presence of catalysts such as amine compounds such as N, N, N ', N' -tetramethylethylenediamine and fluorides such as potassium fluoride and cesium fluoride, perfluoro-4-methyl-2-pentene is prepared by violent stirring reaction at 30-40 ℃. The method has the advantages of complex catalyst solvent system, difficult product separation and easy leakage of stirring dynamic seal under high pressure.
Chinese patent CN1876611A discloses a method for preparing hexafluoropropylene dimer by using nonpolar solvent acetonitrile as solvent and potassium thiocyanate as catalyst and reacting at 10-50 ℃. This patent still discloses the reaction unit of preparation hexafluoropropylene dimer, and the crank connecting rod drives reciprocating motion, makes the material obtain fine stirring, still avoids the dynamic seal simultaneously. Although the device can well stir materials, the device is not beneficial to industrial amplification.
Disclosure of Invention
The invention aims to provide a method for coproducing perfluoro-2-methyl-2-pentene and perfluoro-4-methyl-2-pentene, which has the advantages of high conversion rate and selectivity, mild and controllable reaction conditions, recyclable catalyst and solvent in a reaction kettle, simple separation of reaction products and the like.
The technical scheme adopted by the invention for achieving the aim of the invention is as follows:
a method for preparing perfluoro-2-methyl-2-pentene and perfluoro-4-methyl-2-pentene by coproduction comprises the following recycling process:
(1) in a reaction kettle, under the existence of a solvent and the action of a catalyst, hexafluoropropylene is subjected to oligomerization reaction to prepare perfluoro-2-methyl-2-pentene and perfluoro-4-methyl-2-pentene;
(2) standing, wherein reactants are divided into three layers from top to bottom, namely a solvent layer, a reaction product layer and a catalyst layer;
(3) pressing the intermediate reaction product layer out of the reaction kettle by using nitrogen or inert gas;
(4) adding hexafluoropropylene into the reaction kettle, and repeating the steps (1) to (3);
the solvent is selected from one, two or more than three of N, N-dimethylformamide, N-dimethylacetamide, sulfolane, acetonitrile, tetrahydrofuran, dimethyl sulfoxide, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, ethylene glycol diethyl ether and propylene glycol dimethyl ether;
the catalyst is selected from one, two or more than three of CsF, NaF, LiF, KF and RbF;
the solubility of the catalyst in the solvent is less than or equal to 1 percent, and the solubility of the reaction product in the solvent is less than or equal to 2 percent;
the density of the solvent is less than that of the reaction product and less than that of the catalyst.
According to the invention, by selecting a proper catalyst and a proper solvent, the density difference and solubility difference among the solvent, a reaction product and the catalyst are effectively utilized, after the reaction is finished and the reaction kettle is kept still, reactants in the reaction kettle are divided into three layers from top to bottom, namely a solvent layer, a reaction product layer and a catalyst layer, and then the reaction product is pressed out of the reaction kettle through a suction pipe by adding nitrogen or inert gas into the reaction kettle. The reaction is an intermittent reaction, after the primary reaction is finished, the loss of a reaction solvent and a catalyst is small, the secondary reaction can be realized only by adding hexafluoropropylene into a reaction kettle, the steps of separating the catalyst and the solvent, cleaning the reaction kettle and the like are not needed, and the conversion rate of the raw materials and the selectivity of the product are basically unchanged after the reaction is circularly applied for dozens of times.
Preferably, the solvent is one, two or three selected from the group consisting of diethylene glycol diethyl ether, diethylene glycol dimethyl ether and acetonitrile. The water content in the solvent has influence on the reaction, the higher water content can reduce the reaction speed and prolong the reaction time, the preferable water content of the solvent is less than or equal to 1000PPM, and the more preferable water content is less than or equal to 300 PPM. The amount of the single-pot solvent is preferably 200 to 800kg/1000kg of hexafluoropropylene, and more preferably 400 to 600kg/1000kg of hexafluoropropylene.
The catalyst used in the present invention is required to have a small solubility in the solvent and the reaction product, and suitable catalysts are one, two or more combinations of three or more selected from CsF, NaF, LiF, KF and RbF, and further preferably one, two or three selected from CsF, NaF and KF. The amount of the single-pot catalyst is preferably 2 to 15kg/1000kg of hexafluoropropylene, and more preferably 7 to 10kg/1000kg of hexafluoropropylene.
The reaction temperature is preferably 30-150 ℃, and more preferably 50-100 ℃. Too low a temperature will slow the reaction rate, too high a temperature will generate other by-products, and will increase the unsafe factors for the reaction.
The pressure of the reaction is preferably 0.1 to 1.5MPa, and more preferably 0.5 to 0.8 MPa. Too low a pressure will reduce the reaction rate, and too high a pressure will not only generate other by-products, but also too fast a reaction rate will easily cause unsafe factors.
In the reaction of the present invention, a discharge pipe is usually disposed in a reaction vessel, a lower end of the discharge pipe is located on a reaction product layer, and an upper end of the discharge pipe is disposed outside the reaction vessel, and the reaction product is pressed out of the reaction vessel through the discharge pipe by a method of adding nitrogen or inert gas into the reaction vessel. Suitable inert gases include helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), and radon (Rn). After the reaction product is pressed out of the reaction kettle through the discharge pipe, the perfluoro-2-methyl-2-pentene and the perfluoro-4-methyl-2-pentene with the purity of more than 99.9 percent can be obtained only through simple rectification operation.
Compared with the prior art, the method of the invention has the following characteristics:
(1) the cyclic application process can realize the cyclic application of the catalyst and the solvent system in the reaction kettle, simplify the post-reaction treatment process, improve the utilization rate and the production efficiency of the catalyst and the solvent, and reduce the production cost;
(2) the joint production preparation of the perfluoro-2-methyl-2-pentene and the perfluoro-4-methyl-2-pentene is realized, the conversion rate and the selectivity are high, and the reaction conditions are mild and controllable;
(3) the separation method of the reaction product is novel, simple and convenient and has high efficiency.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the invention to these embodiments. It will be appreciated by those skilled in the art that the present invention encompasses all alternatives, modifications and equivalents as may be included within the scope of the claims.
Example 1
In the embodiment, CsF is used as a catalyst, and acetonitrile is used as a solvent to carry out liquid-phase oligomerization on hexafluoropropylene to prepare perfluoro-2-methyl-2-pentene and perfluoro-4-methyl-2-pentene.
600kg of acetonitrile and 10kg of CsF were added through feed ports to 2m3And (3) sealing the reaction kettle in the high-pressure reaction kettle, vacuumizing for multiple times, and performing nitrogen replacement to ensure that the oxygen content in the kettle is less than 20 ppm. Then the stirring is started, the temperature is raised to 50 ℃, 1000kg of raw material hexafluoropropylene is continuously and slowly introduced, and the reaction pressure is controlled to be about 0.5 MPa. The reaction speed depends on the speed of feeding the hexafluoropropylene, the speed of feeding the hexafluoropropylene is not too fast, otherwise the reaction temperature is not easy to control. After the raw materials are completely introduced, the temperature in the reaction kettle is kept at 50 ℃ until the pressure of the reaction kettle is reduced to 0.16 MPa. And then cooling and standing for 3 hours, standing, putting the perfluoro-2-methyl-2-pentene and the perfluoro-4-methyl-2-pentene crude product in an intermediate reaction product layer, pressing high-purity nitrogen into the reaction kettle, pressing the reaction product layer out of a product tank through a discharge pipe, and reserving a solvent layer and a catalyst layer for the next reaction. The product data are shown in Table 1, after gas chromatography.
Example 2
In the embodiment, the NaF is used as a catalyst, and the diethylene glycol diethyl ether is used as a solvent to carry out liquid-phase oligomerization of hexafluoropropylene to prepare perfluoro-2-methyl-2-pentene and perfluoro-4-methyl-2-pentene.
600kg of diethylene glycol diethyl ether and 8kg of NaF were added through feed ports to 2m3The high-pressure reaction kettle is sealed and vacuumized for a plurality of times,nitrogen replacement is carried out to ensure that the oxygen content in the kettle is less than 20 ppm. Then the stirring is started, the temperature is raised to 50 ℃, 1000kg of raw material hexafluoropropylene is continuously and slowly introduced, and the reaction pressure is controlled to be about 0.5 MPa. The reaction speed depends on the speed of feeding the hexafluoropropylene, the speed of feeding the hexafluoropropylene is not too fast, otherwise the reaction temperature is not easy to control. After the raw materials are completely introduced, the temperature in the reaction kettle is kept at 50 ℃ until the pressure of the reaction kettle is reduced to 0.16 MPa. And then cooling and standing for 3 hours, standing, putting the perfluoro-2-methyl-2-pentene and the perfluoro-4-methyl-2-pentene crude product in an intermediate reaction product layer, pressing high-purity nitrogen into the reaction kettle, pressing the reaction product layer out of a product tank through a discharge pipe, and reserving a solvent layer and a catalyst layer for the next reaction. The product data are shown in Table 1, after gas chromatography.
Example 3
In the embodiment, CsF is used as a catalyst, and diethylene glycol dimethyl ether is used as a solvent to carry out liquid-phase oligomerization of hexafluoropropylene to prepare perfluoro-2-methyl-2-pentene and perfluoro-4-methyl-2-pentene.
600kg of diethylene glycol dimethyl ether and 8kg of CsF were fed through feed ports to 2m3And (3) sealing the reaction kettle in the high-pressure reaction kettle, vacuumizing for multiple times, and performing nitrogen replacement to ensure that the oxygen content in the kettle is less than 20 ppm. Then the stirring is started, the temperature is raised to 50 ℃, 1000kg of raw material hexafluoropropylene is continuously and slowly introduced, and the reaction pressure is controlled to be about 0.5 MPa. The reaction speed depends on the speed of feeding the hexafluoropropylene, the speed of feeding the hexafluoropropylene is not too fast, otherwise the reaction temperature is not easy to control. After the raw materials are completely introduced, the temperature in the reaction kettle is kept at 50 ℃ until the pressure of the reaction kettle is reduced to 0.16 MPa. And then cooling and standing for 3 hours, standing, putting the perfluoro-2-methyl-2-pentene and the perfluoro-4-methyl-2-pentene crude product in an intermediate reaction product layer, pressing high-purity nitrogen into the reaction kettle, pressing the reaction product layer out of a product tank through a discharge pipe, and reserving a solvent layer and a catalyst layer for the next reaction. The product data are shown in Table 1, after gas chromatography.
Example 4
In the embodiment, KF is used as a catalyst, and acetonitrile is used as a solvent to carry out liquid-phase oligomerization on hexafluoropropylene to prepare perfluoro-2-methyl-2-pentene and perfluoro-4-methyl-2-pentene.
400kg of acetonitrile and 7kg of KF were fed through feed ports at 2m3And (3) sealing the reaction kettle in the high-pressure reaction kettle, vacuumizing for multiple times, and performing nitrogen replacement to ensure that the oxygen content in the kettle is less than 20 ppm. Then the stirring is started, the temperature is raised to 50 ℃, 1000kg of raw material hexafluoropropylene is continuously and slowly introduced, and the reaction pressure is controlled to be about 0.5 MPa. The reaction speed depends on the speed of feeding the hexafluoropropylene, the speed of feeding the hexafluoropropylene is not too fast, otherwise the reaction temperature is not easy to control. After the raw materials are completely introduced, the temperature in the reaction kettle is kept at 50 ℃ until the pressure of the reaction kettle is reduced to 0.16 MPa. And then cooling and standing for 3 hours, standing, putting the perfluoro-2-methyl-2-pentene and the perfluoro-4-methyl-2-pentene crude product in an intermediate reaction product layer, pressing high-purity nitrogen into the reaction kettle, pressing the reaction product layer out of a product tank through a discharge pipe, and reserving a solvent layer and a catalyst layer for the next reaction. The product data are shown in Table 1, after gas chromatography.
Example 5
In the embodiment, CsF is used as a catalyst, and diethylene glycol diethyl ether is used as a solvent to carry out liquid-phase oligomerization on hexafluoropropylene to prepare perfluoro-2-methyl-2-pentene and perfluoro-4-methyl-2-pentene.
500kg of diethylene glycol diethyl ether and 10kg of CsF were added through feed ports to 2m3And (3) sealing the reaction kettle in the high-pressure reaction kettle, vacuumizing for multiple times, and performing nitrogen replacement to ensure that the oxygen content in the kettle is less than 20 ppm. Then the stirring is started, the temperature is raised to 50 ℃, 1000kg of raw material hexafluoropropylene is continuously and slowly introduced, and the reaction pressure is controlled to be about 0.5 MPa. The reaction speed depends on the speed of feeding the hexafluoropropylene, the speed of feeding the hexafluoropropylene is not too fast, otherwise the reaction temperature is not easy to control. After the raw materials are completely introduced, the temperature in the reaction kettle is kept at 50 ℃ until the pressure of the reaction kettle is reduced to 0.16 MPa. And then cooling and standing for 3 hours, standing, putting the perfluoro-2-methyl-2-pentene and the perfluoro-4-methyl-2-pentene crude product in an intermediate reaction product layer, pressing high-purity nitrogen into the reaction kettle, pressing the reaction product layer out of a product tank through a discharge pipe, and reserving a solvent layer and a catalyst layer for the next reaction. The product data are shown in Table 1, after gas chromatography.
Example 6
In the embodiment, CsF is used as a catalyst, and diethylene glycol dimethyl ether is used as a solvent to carry out liquid-phase oligomerization of hexafluoropropylene to prepare perfluoro-2-methyl-2-pentene and perfluoro-4-methyl-2-pentene.
400kg of diethylene glycol dimethyl ether and 10kg of CsF were fed through the feed port at 2m3And (3) sealing the reaction kettle in the high-pressure reaction kettle, vacuumizing for multiple times, and performing nitrogen replacement to ensure that the oxygen content in the kettle is less than 20 ppm. Then the stirring is started, the temperature is raised to 60 ℃, 1000kg of raw material hexafluoropropylene is continuously and slowly introduced, and the reaction pressure is controlled to be about 0.5 MPa. The reaction speed depends on the speed of feeding the hexafluoropropylene, the speed of feeding the hexafluoropropylene is not too fast, otherwise the reaction temperature is not easy to control. After the raw materials are completely introduced, the temperature in the reaction kettle is kept at 60 ℃ until the pressure of the reaction kettle is reduced to 0.16 MPa. And then cooling and standing for 3 hours, standing, putting the perfluoro-2-methyl-2-pentene and the perfluoro-4-methyl-2-pentene crude product in an intermediate reaction product layer, pressing high-purity nitrogen into the reaction kettle, pressing the reaction product layer out of a product tank through a discharge pipe, and reserving a solvent layer and a catalyst layer for the next reaction. The product data are shown in Table 1, after gas chromatography.
Example 7
In the embodiment, KF is used as a catalyst, and acetonitrile is used as a solvent to carry out liquid-phase oligomerization on hexafluoropropylene to prepare perfluoro-2-methyl-2-pentene and perfluoro-4-methyl-2-pentene.
600kg of acetonitrile and 8kg of KF were fed through feed ports at 2m3And (3) sealing the reaction kettle in the high-pressure reaction kettle, vacuumizing for multiple times, and performing nitrogen replacement to ensure that the oxygen content in the kettle is less than 20 ppm. Then the stirring is started, the temperature is raised to 60 ℃, 1000kg of hexafluoropropylene which is used as a raw material is continuously and slowly introduced, and the reaction pressure is controlled to be about 0.7 MPa. The reaction speed depends on the speed of feeding the hexafluoropropylene, the speed of feeding the hexafluoropropylene is not too fast, otherwise the reaction temperature is not easy to control. After the raw materials are completely introduced, the temperature in the reaction kettle is kept at 60 ℃ until the pressure of the reaction kettle is reduced to 0.16 MPa. Then cooling and standing for 3 hours, after standing, putting the perfluoro-2-methyl-2-pentene and the perfluoro-4-methyl-2-pentene crude product into an intermediate reaction product layer, pressing high-purity nitrogen into the reaction kettle, and allowing the reaction product layer to pass throughThe discharge pipe is pressed out to a product tank, and the solvent layer and the catalyst layer are reserved for the next reaction. The product data are shown in Table 1, after gas chromatography.
Example 8
In the embodiment, KF is used as a catalyst, and acetonitrile is used as a solvent to carry out liquid-phase oligomerization on hexafluoropropylene to prepare perfluoro-2-methyl-2-pentene and perfluoro-4-methyl-2-pentene.
800kg of acetonitrile and 10kg of KF were fed through feed ports at 2m3And (3) sealing the reaction kettle in the high-pressure reaction kettle, vacuumizing for multiple times, and performing nitrogen replacement to ensure that the oxygen content in the kettle is less than 20 ppm. Then the stirring is started, the temperature is raised to 100 ℃, 1000kg of raw material hexafluoropropylene is continuously and slowly introduced, and the reaction pressure is controlled to be about 0.8 MPa. The reaction speed depends on the speed of feeding the hexafluoropropylene, the speed of feeding the hexafluoropropylene is not too fast, otherwise the reaction temperature is not easy to control. After the raw materials are completely introduced, the temperature in the reaction kettle is kept at 100 ℃ until the pressure of the reaction kettle is reduced to 0.16 MPa. And then cooling and standing for 3 hours, standing, putting the perfluoro-2-methyl-2-pentene and the perfluoro-4-methyl-2-pentene crude product in an intermediate reaction product layer, pressing high-purity nitrogen into the reaction kettle, pressing the reaction product layer out of a product tank through a discharge pipe, and reserving a solvent layer and a catalyst layer for the next reaction. The product data are shown in Table 1, after gas chromatography.
Example 9
In the embodiment, CsF is used as a catalyst, and diethylene glycol diethyl ether is used as a solvent to carry out liquid-phase oligomerization on hexafluoropropylene to prepare perfluoro-2-methyl-2-pentene and perfluoro-4-methyl-2-pentene.
500kg of diethylene glycol diethyl ether and 10kg of CsF were added through feed ports to 2m3And (3) sealing the reaction kettle in the high-pressure reaction kettle, vacuumizing for multiple times, and performing nitrogen replacement to ensure that the oxygen content in the kettle is less than 20 ppm. Then the stirring is started, the temperature is increased to 80 ℃, 1000kg of raw material hexafluoropropylene is continuously and slowly introduced, and the reaction pressure is controlled to be about 0.6 MPa. The reaction speed depends on the speed of feeding the hexafluoropropylene, the speed of feeding the hexafluoropropylene is not too fast, otherwise the reaction temperature is not easy to control. After the raw materials are completely introduced, the temperature in the reaction kettle is kept at 80 ℃ until the pressure in the reaction kettle is reduced to 0.16 MPa.And then cooling and standing for 3 hours, standing, putting the perfluoro-2-methyl-2-pentene and the perfluoro-4-methyl-2-pentene crude product in an intermediate reaction product layer, pressing high-purity nitrogen into the reaction kettle, pressing the reaction product layer out of a product tank through a discharge pipe, and reserving a solvent layer and a catalyst layer for the next reaction. The product data are shown in Table 1, after gas chromatography.
Example 10
In the embodiment, CsF is used as a catalyst, and diethylene glycol diethyl ether is used as a solvent to carry out liquid-phase oligomerization on hexafluoropropylene to prepare perfluoro-2-methyl-2-pentene and perfluoro-4-methyl-2-pentene.
600kg of diethylene glycol diethyl ether and 10kg of CsF were added through feed ports to 2m3And (3) sealing the reaction kettle in the high-pressure reaction kettle, vacuumizing for multiple times, and performing nitrogen replacement to ensure that the oxygen content in the kettle is less than 20 ppm. Then the stirring is started, the temperature is raised to 100 ℃, 1000kg of raw material hexafluoropropylene is continuously and slowly introduced, and the reaction pressure is controlled to be about 0.8 MPa. The reaction speed depends on the speed of feeding the hexafluoropropylene, the speed of feeding the hexafluoropropylene is not too fast, otherwise the reaction temperature is not easy to control. After the raw materials are completely introduced, the temperature in the reaction kettle is kept at 100 ℃ until the pressure of the reaction kettle is reduced to 0.16 MPa. And then cooling and standing for 3 hours, standing, putting the perfluoro-2-methyl-2-pentene and the perfluoro-4-methyl-2-pentene crude product in an intermediate reaction product layer, pressing high-purity nitrogen into the reaction kettle, pressing the reaction product layer out of a product tank through a discharge pipe, and reserving a solvent layer and a catalyst layer for the next reaction. The product data are shown in Table 1, after gas chromatography.
TABLE 1 results of reactions with different catalysts and solvents
Example 11
In this example, the solvent and catalyst after the reaction of example 1 were used, and the influence of the solvent and catalyst used in circulation on the reaction was examined, and the reaction results are shown in Table 2, except that the reaction conditions were the same as in example 1.
TABLE 2 catalyst and solvent recycle results
From the analysis of the results of example 11, the conversion and selectivity of the reaction were substantially unchanged after the solvent and catalyst were recycled in the autoclave for 18 times, which indicates that the recycling process of the solvent and catalyst of the present invention is feasible.
Claims (7)
1. A method for jointly preparing perfluoro-2-methyl-2-pentene and perfluoro-4-methyl-2-pentene is characterized by comprising the following cyclic application processes:
(1) in a reaction kettle, under the existence of a solvent and the action of a catalyst, hexafluoropropylene is subjected to oligomerization reaction to prepare perfluoro-2-methyl-2-pentene and perfluoro-4-methyl-2-pentene;
(2) standing, wherein reactants are divided into three layers from top to bottom, namely a solvent layer, a reaction product layer and a catalyst layer;
(3) pressing the intermediate reaction product layer out of the reaction kettle by using nitrogen or inert gas;
(4) adding hexafluoropropylene into the reaction kettle, and repeating the steps (1) to (3);
the solvent is selected from ethylene glycol diethyl ether and/or propylene glycol dimethyl ether;
the catalyst is selected from one, two or more than three of CsF, NaF, LiF, KF and RbF;
the solubility of the catalyst in the solvent is less than or equal to 1 percent, and the solubility of the reaction product in the solvent is less than or equal to 2 percent;
the density of the solvent is less than that of the reaction product and less than that of the catalyst;
the reaction temperature is 50-100 ℃, and the reaction pressure is 0.5-0.8 MPa.
2. The method for coproducing perfluoro-2-methyl-2-pentene and perfluoro-4-methyl-2-pentene in the claim 1, wherein the water content of the solvent is less than or equal to 1000PPM, and the amount of the single-kettle solvent is 200-800 kg/1000kg of hexafluoropropylene.
3. The co-production method for preparing perfluoro-2-methyl-2-pentene and perfluoro-4-methyl-2-pentene according to claim 2, wherein the water content of the solvent is less than or equal to 300PPM, and the amount of the single-kettle solvent is 400-600 kg/1000kg of hexafluoropropylene.
4. The co-production method for preparing perfluoro-2-methyl-2-pentene and perfluoro-4-methyl-2-pentene according to claim 1, wherein the catalyst is one, two or three selected from CsF, NaF and KF, and the amount of the single-pot catalyst is 2-15 kg/1000kg of hexafluoropropylene.
5. The co-production method for preparing perfluoro-2-methyl-2-pentene and perfluoro-4-methyl-2-pentene according to claim 4, wherein the amount of the single-pot catalyst is 7 to 10kg/1000kg of hexafluoropropylene.
6. The process for co-producing perfluoro-2-methyl-2-pentene and perfluoro-4-methyl-2-pentene according to claim 1, wherein in the step (3), an outlet pipe is used, a lower end of the outlet pipe is located at the reaction product layer, an upper end of the outlet pipe is disposed outside the reaction vessel, and the reaction product is pressed out of the reaction vessel through the outlet pipe by feeding nitrogen or an inert gas into the reaction vessel.
7. The process for co-producing perfluoro-2-methyl-2-pentene and perfluoro-4-methyl-2-pentene as claimed in claim 1, wherein the oxygen content in the reaction vessel is less than 20 ppm.
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| 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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| 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 |
| 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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| 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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| 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 |
| 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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| 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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| 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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| CN103787824B (en) | 2018-01-02 |
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