CN111116308B - Preparation method of hexafluoropropylene dimer - Google Patents
Preparation method of hexafluoropropylene dimer Download PDFInfo
- Publication number
- CN111116308B CN111116308B CN201911359822.8A CN201911359822A CN111116308B CN 111116308 B CN111116308 B CN 111116308B CN 201911359822 A CN201911359822 A CN 201911359822A CN 111116308 B CN111116308 B CN 111116308B
- Authority
- CN
- China
- Prior art keywords
- temperature
- metal fluoride
- controlling
- hexafluoropropylene
- hours
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
- B01J31/30—Halides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/20—Olefin oligomerisation or telomerisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/828—Platinum
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to the field of fine chemical engineering, in particular to a preparation method of hexafluoropropylene dimer; the preparation method of hexafluoropropylene dimer is simple, creatively uses a metal fluoride-organic complex catalyst as a catalyst for oligomerization of hexafluoropropylene, can catalyze oligomerization of hexafluoropropylene at a lower temperature, generates hexafluoropropylene dimer with high selectivity, and reduces the content of trimer and polymer; the method finds a simple and feasible production process route with lower cost, higher yield and lower energy consumption, and has very good industrialized prospect.
Description
Technical Field
The invention relates to the field of fine chemical engineering, in particular to a preparation method of hexafluoropropylene dimer.
Background
In recent years, the research and application range of hexafluoropropylene dimer is widened, and the foaming agent of perfluoro compound is synthesized by using hexafluoropropylene dimer as main raw material by the American 3M company DamsRudolf J, and the product can be dissolved or dispersed in fluorocarbon and can be synthesized into oligomerization foam products.
201810567226.8A process for preparing hexafluoropropylene dimer comprises introducing preheated hexafluoropropylene gas into a reaction vessel containing alkyl hexamethylenetetramine fluoride represented by the formula (I), heating and stirring to continuously react, and post-treating the reaction product to obtain hexafluoropropylene dimer, wherein R is alkyl with 1-10 carbon atoms. The invention is used as a new reaction line, and avoids the polymerization reaction by using a catalyst and a solvent in the traditional process; the preparation process is simple, the requirement on equipment is low, and the reaction condition is mild.
201811459941.6 it relates to a process for preparing perfluoro-isobutyryl fluoride from hexafluoropropylene dimer. Comprises the following steps of taking oxygen and hexafluoropropylene as raw materials for dimerization, and reacting under the action of a catalyst; wherein the molar ratio of oxygen to hexafluoropropylene dimer/hexafluoropropylene trimer is 1:10-10:1; the contact reaction time is 0.1s to 200s; the pressure of the reaction is 0-1MPa; the reaction temperature is 150-600 ℃. The method for preparing perfluoro-isobutyryl fluoride from hexafluoropropylene dimer has the advantages of mild reaction conditions, high product yield, no pollution and easy mass production.
201811458143.1 relates to a device for preparing perfluoroisobutyl ether from hexafluoropropylene dimer, which comprises a hexafluoropropylene dimer generating unit, a perfluoroisobutyryl fluoride generating unit and a perfluoroisobutyl ether generating unit; the hexafluoropropylene dimer generating unit comprises a hexafluoropropylene storage tank, a catalytic reaction tube, a condenser and an activation chamber which are connected in sequence; the perfluoro-isobutyryl fluoride generating unit comprises a cracking furnace and a cold trap at the temperature of-2 ℃ which are sequentially connected with an activation chamber; the perfluoro-isobutyl ether generating unit comprises a reaction kettle, a standing layering tower, a drying tower, a rectifying tower and a product storage tank which are sequentially connected; the liquid outlet of the cold trap at-2 ℃ is connected with the reaction kettle. The invention designs a device for preparing perfluoro-isobutyl ether by hexafluoropropylene dimer, which prepares the hydrofluoroether by polymerizing hexafluoropropylene monomer and then cracking the hexafluoropropylene monomer under the action of a catalyst to generate perfluoro-isobutyryl fluoride, and has simple device and easy realization.
The hexafluoropropylene dimer is prepared by oligomerization of hexafluoropropylene gas under certain conditions, and the oligomerization product generally contains two isomers D-1 and D-2 of the hexafluoropropylene dimer, and also contains a plurality of trimers and polymers, and the yield of the hexafluoropropylene dimer is reduced due to the formation of the trimers and the polymers.
Disclosure of Invention
In order to solve the above problems, the present invention provides a method for producing hexafluoropropylene dimer.
Hexafluoropropylene dimer is prepared according to the following method:
adding 0.01-0.15 part of metal fluoride-organic complex catalyst and 45-65 parts of solvent into a reaction kettle according to parts by weight, stirring and mixing uniformly, bubbling for 5-10min by using inert gas, vacuumizing, filling the inert gas for 3 times, filling 18-26 parts of hexafluoropropylene under the vacuum condition, controlling the temperature to 25-45 ℃, stirring and reacting for 1.5-8h, cooling to 5-10 ℃ after the reaction is completed, discharging residual hexafluoropropylene gas, and separating liquid to obtain lower liquid, thus obtaining the hexafluoropropylene dimer.
The organic solvent is acetonitrile or dimethyl sulfoxide or sulfolane.
The inert gas is high-purity nitrogen or high-purity argon.
The preparation method of the metal fluoride-organic complex catalyst comprises the following steps:
according to the parts by weight, 5-10 parts of metal fluoride, 3-10 parts of dimethyl allyl silane, 3-8 parts of copper acrylate and 280-380 parts of N-methyl pyrrolidone are taken, the mixture is stirred and mixed uniformly, argon atmosphere is introduced, then the temperature is controlled to be 60-80 ℃, 2.4-6.8 parts of ammonium persulfate is dissolved in 30-50 parts of isopropanol, and the mixture is slowly dripped into a reaction kettle, and the dripping is controlled to be carried out for 1-5 hours; after the dripping is finished, controlling the temperature to be 50-70 ℃, continuing to react for 1-4 hours, adding 0.5-2 parts of 5, 5-divinyl-2, 2-bipyridine, 0.1-1 part of chloroplatinic acid, controlling the temperature to be 50-70 ℃, continuing to react for 0.5-2 hours, cooling to room temperature, adding 300-500 parts of acetone, extracting, evaporating the obtained solution to dryness to obtain solid, vacuum drying at 40-60 ℃ for 6-10 hours, and crushing to obtain the metal fluoride-organic complex catalyst.
The metal fluoride is cesium fluoride or potassium fluoride or copper fluoride.
The preparation method comprises the steps of preparing a polymer from dimethyl allyl silane and copper acrylate, introducing Si-H bonds into the polymer, enabling metal fluoride to exist in the polymer, performing hydrosilylation reaction with 5, 5-divinyl-2, 2-bipyridine under the action of chloroplatinic acid, and preparing a metal complex from metal ions and bipyridine to obtain the metal fluoride-organic complex catalyst.
The preparation method of hexafluoropropylene dimer is simple, creatively uses a metal fluoride-organic complex catalyst as a catalyst for oligomerization of hexafluoropropylene, can catalyze oligomerization of hexafluoropropylene at a lower temperature, generates hexafluoropropylene dimer with high selectivity, and reduces the content of trimer and polymer; the method finds a simple and feasible production process route with lower cost, higher yield and lower energy consumption, and has very good industrialized prospect.
Drawings
FIG. 1 is a Fourier infrared spectrum of hexafluoropropylene dimer prepared in example 3.
FIG. 2 is a gas chromatographic analysis report of hexafluoropropylene dimer sample prepared in example 2.
Detailed Description
The invention is further illustrated by the following examples:
in the specific embodiment of the invention, the content of hexafluoropropylene dimer is measured by adopting a gas phase analysis method, the capillary column temperature is 150 ℃, the gasification chamber temperature is 200 ℃, the detector temperature is 250 ℃, high-purity nitrogen is used as carrier gas, and the detector is ionized by hydrogen flame. The product yield was calculated as the amount of hexafluoropropylene fed.
Example 1
Hexafluoropropylene dimer is prepared according to the following method:
adding 0.01kg of metal fluoride-organic complex catalyst and 45kg of solvent into a reaction kettle, stirring and mixing uniformly, then bubbling for 5min by using inert gas, vacuumizing, circulating the inert gas for 3 times, charging 18kg of hexafluoropropylene under the vacuum condition, controlling the temperature to 25 ℃, stirring and reacting for 1.5h, cooling to 5 ℃ after the reaction is completed, discharging residual hexafluoropropylene gas, and separating to obtain lower liquid, thus obtaining the hexafluoropropylene dimer.
The organic solvent is acetonitrile.
The inert gas is high-purity nitrogen.
The preparation method of the metal fluoride-organic complex catalyst comprises the following steps:
taking 5Kg of metal fluoride, 3Kg of dimethyl allyl silane, 3Kg of copper acrylate and 280Kg of N-methyl pyrrolidone, stirring and mixing uniformly, introducing argon atmosphere, controlling the temperature to 60 ℃, dissolving 2.4Kg of ammonium persulfate in 30Kg of isopropanol, slowly dropwise adding into a reaction kettle, and controlling dropwise adding for 1h; after the dripping is finished, controlling the temperature to be 50 ℃, continuing to react for 1h, adding 0.5Kg of 5, 5-divinyl-2, 2-dipyridine, 0.1Kg of chloroplatinic acid, controlling the temperature to be 50 ℃, continuing to react for 0.5h, cooling to room temperature, adding 300Kg of acetone, extracting, evaporating the obtained solution to dryness to obtain a solid, drying in vacuum for 6h at the temperature of 40 ℃, and crushing to obtain the metal fluoride-organic complex catalyst.
The metal fluoride is cesium fluoride.
The hexafluoropropylene dimer content in the product prepared in this experiment was 98.79% and the product yield was 87.1%.
Example 2
Hexafluoropropylene dimer is prepared according to the following method:
adding 0.07kg of metal fluoride-organic complex catalyst and 55kg of solvent into a reaction kettle, stirring and mixing uniformly, then bubbling for 8min by using inert gas, vacuumizing, circulating the inert gas for 3 times, charging 22kg of hexafluoropropylene under the vacuum condition, controlling the temperature to 35 ℃, stirring and reacting for 4h, cooling to 8 ℃ after the reaction is completed, discharging residual hexafluoropropylene gas, and separating liquid to obtain lower liquid, thus obtaining the hexafluoropropylene dimer.
The organic solvent is dimethyl sulfoxide.
The inert gas is high-purity argon.
The preparation method of the metal fluoride-organic complex catalyst comprises the following steps:
8Kg of metal fluoride, 5Kg of dimethyl allyl silane, 5Kg of copper acrylate and 300Kg of N-methyl pyrrolidone are taken, the mixture is stirred and mixed uniformly, argon atmosphere is introduced, then the temperature is controlled to 66 ℃, 2.8Kg of ammonium persulfate is dissolved in 35Kg of isopropanol, and the mixture is slowly dripped into a reaction kettle, and the dripping is controlled for 2 hours; after the dripping is finished, controlling the temperature to 55 ℃, continuing to react for 3 hours, adding 1Kg of 5, 5-divinyl-2, 2-dipyridine, 0.2Kg of chloroplatinic acid, controlling the temperature to 55 ℃, continuing to react for 1 hour, cooling to room temperature, adding 360Kg of acetone, extracting, evaporating the obtained solution to dryness, obtaining a solid, drying in vacuum for 8 hours at 45 ℃, and then crushing to obtain the metal fluoride-organic complex catalyst.
The metal fluoride is potassium fluoride.
The hexafluoropropylene dimer content in the product prepared in this experiment was 99.05% and the product yield was 87.3%.
Example 3
Hexafluoropropylene dimer is prepared according to the following method:
adding 0.15kg of metal fluoride-organic complex catalyst and 65kg of solvent into a reaction kettle, stirring and mixing uniformly, then bubbling for 10min by using inert gas, vacuumizing, filling inert gas for circulation for 3 times, filling 26kg of hexafluoropropylene under the vacuum condition, controlling the temperature to 45 ℃, stirring and reacting for 8h, cooling to 10 ℃ after the reaction is completed, discharging residual hexafluoropropylene gas, and separating liquid to obtain lower liquid, thus obtaining the hexafluoropropylene dimer.
The organic solvent is sulfolane.
The inert gas is high-purity argon.
The preparation method of the metal fluoride-organic complex catalyst comprises the following steps:
taking 10Kg of metal fluoride, 10Kg of dimethyl allyl silane, 8Kg of copper acrylate and 380Kg of N-methyl pyrrolidone, stirring and mixing uniformly, introducing argon atmosphere, controlling the temperature to 80 ℃, dissolving 6.8Kg of ammonium persulfate in 50Kg of isopropanol, slowly dropwise adding into a reaction kettle, and controlling dropwise adding for 5 hours; after the dripping is finished, controlling the temperature to 70 ℃, continuing to react for 4 hours, adding 2Kg of 5, 5-divinyl-2, 2-dipyridine, 1Kg of chloroplatinic acid, controlling the temperature to 70 ℃, continuing to react for 2 hours, cooling to room temperature, adding 500Kg of acetone, extracting, evaporating the obtained solution to dryness, obtaining a solid, drying in vacuum for 10 hours at 60 ℃, and then crushing to obtain the metal fluoride-organic complex catalyst.
The metal fluoride is copper fluoride.
The hexafluoropropylene dimer content in the product prepared in this experiment was 99.86% and the product yield was 87.3%.
Example 4
Hexafluoropropylene dimer is prepared according to the following method:
adding 0.01kg of metal fluoride-organic complex catalyst and 45kg of solvent into a reaction kettle, stirring and mixing uniformly, then bubbling for 5min by using inert gas, vacuumizing, circulating the inert gas for 3 times, charging 18kg of hexafluoropropylene under the vacuum condition, controlling the temperature to 25 ℃, stirring and reacting for 1.5h, cooling to 5 ℃ after the reaction is completed, discharging residual hexafluoropropylene gas, and separating to obtain lower liquid, thus obtaining the hexafluoropropylene dimer.
The organic solvent is dimethyl sulfoxide.
The inert gas is high-purity argon.
The preparation method of the metal fluoride-organic complex catalyst comprises the following steps:
taking 5Kg of metal fluoride, 10Kg of dimethyl allyl silane, 3Kg of copper acrylate and 380Kg of N-methyl pyrrolidone, stirring and mixing uniformly, introducing argon atmosphere, controlling the temperature to 60 ℃, dissolving 6.8Kg of ammonium persulfate in 50Kg of isopropanol, slowly dropwise adding into a reaction kettle, and controlling dropwise adding for 5 hours; after the dripping is finished, controlling the temperature to be 50 ℃, continuing to react for 4 hours, adding 0.5Kg of 5, 5-divinyl-2, 2-bipyridine, 0.1-1Kg of chloroplatinic acid, controlling the temperature to be 50 ℃, continuing to react for 2 hours, cooling to room temperature, adding 300Kg of acetone, extracting, evaporating the obtained solution to dryness to obtain a solid, drying in vacuum for 6 hours at the temperature of 60 ℃, and crushing to obtain the metal fluoride-organic complex catalyst.
The metal fluoride is copper fluoride.
The hexafluoropropylene dimer content in the product prepared in this experiment was 96.4% and the product yield was 87.2%.
Comparative example 1
Hexafluoropropylene dimer is prepared according to the following method:
adding 0.01kg of cuprous iodide catalyst and 45kg of solvent into a reaction kettle, stirring and mixing uniformly, bubbling for 5min by using inert gas, vacuumizing, filling the inert gas for 3 times, filling 18kg of hexafluoropropylene under the vacuum condition, controlling the temperature to 25 ℃, stirring and reacting for 1.5h, cooling to 5 ℃ after the reaction is finished, discharging residual hexafluoropropylene gas, and separating liquid to obtain lower liquid, thus obtaining the hexafluoropropylene dimer.
The organic solvent is acetonitrile.
The inert gas is high-purity nitrogen.
The hexafluoropropylene dimer content in the product prepared in this experiment was 87.1% and the product yield was 76.4%.
Comparative example 2
Hexafluoropropylene dimer is prepared according to the following method:
adding 0.07kg of metal fluoride-organic complex catalyst and 55kg of solvent into a reaction kettle, stirring and mixing uniformly, then bubbling for 8min by using inert gas, vacuumizing, circulating the inert gas for 3 times, charging 22kg of hexafluoropropylene under the vacuum condition, controlling the temperature to 35 ℃, stirring and reacting for 4h, cooling to 8 ℃ after the reaction is completed, discharging residual hexafluoropropylene gas, and separating liquid to obtain lower liquid, thus obtaining the hexafluoropropylene dimer.
The organic solvent is dimethyl sulfoxide.
The inert gas is high-purity argon.
The preparation method of the metal fluoride-organic complex catalyst comprises the following steps:
8Kg of metal fluoride and 5Kg of dimethyl allyl silane are taken and added into 300Kg of N-methyl pyrrolidone, argon atmosphere is introduced after stirring and mixing uniformly, then the temperature is controlled at 66 ℃, 2.8Kg of ammonium persulfate is dissolved in 35Kg of isopropanol, and the mixture is slowly dripped into a reaction kettle, and dripping is controlled for 2 hours; after the dripping is finished, controlling the temperature to 55 ℃, continuing to react for 3 hours, adding 1Kg of 5, 5-divinyl-2, 2-dipyridine, 0.2Kg of chloroplatinic acid, controlling the temperature to 55 ℃, continuing to react for 1 hour, cooling to room temperature, adding 360Kg of acetone, extracting, evaporating the obtained solution to dryness, obtaining a solid, drying in vacuum for 8 hours at 45 ℃, and then crushing to obtain the metal fluoride-organic complex catalyst.
The metal fluoride is potassium fluoride.
The hexafluoropropylene dimer content in the product prepared in this experiment was 91.4% and the product yield was 81.7%.
Comparative example 3
Hexafluoropropylene dimer is prepared according to the following method:
adding 0.07kg of metal fluoride-organic complex catalyst and 55kg of solvent into a reaction kettle, stirring and mixing uniformly, then bubbling for 8min by using inert gas, vacuumizing, circulating the inert gas for 3 times, charging 22kg of hexafluoropropylene under the vacuum condition, controlling the temperature to 35 ℃, stirring and reacting for 4h, cooling to 8 ℃ after the reaction is completed, discharging residual hexafluoropropylene gas, and separating liquid to obtain lower liquid, thus obtaining the hexafluoropropylene dimer.
The organic solvent is dimethyl sulfoxide.
The inert gas is high-purity argon.
The preparation method of the metal fluoride-organic complex catalyst comprises the following steps:
8Kg of metal fluoride, 5Kg of dimethyl allyl silane, 5Kg of copper acrylate and 300Kg of N-methyl pyrrolidone are taken, the mixture is stirred and mixed uniformly, argon atmosphere is introduced, then the temperature is controlled to 66 ℃, 2.8Kg of ammonium persulfate is dissolved in 35Kg of isopropanol, and the mixture is slowly dripped into a reaction kettle, and the dripping is controlled for 2 hours; after the dripping is finished, controlling the temperature to 55 ℃, continuing to react for 3 hours, adding 0.2Kg of chloroplatinic acid, controlling the temperature to 55 ℃, continuing to react for 1 hour, cooling to room temperature, adding 360Kg of acetone, extracting, evaporating the obtained solution to dryness, obtaining a solid, drying in vacuum for 8 hours at 45 ℃, and then crushing to obtain the metal fluoride-organic complex catalyst.
The metal fluoride is potassium fluoride.
The hexafluoropropylene dimer content in the product prepared in this experiment was 89.7% and the product yield was 79.1%.
Comparative example 4
Hexafluoropropylene dimer is prepared according to the following method:
adding 0.07kg of metal fluoride-organic complex catalyst and 55kg of solvent into a reaction kettle, stirring and mixing uniformly, then bubbling for 8min by using inert gas, vacuumizing, circulating the inert gas for 3 times, charging 22kg of hexafluoropropylene under the vacuum condition, controlling the temperature to 35 ℃, stirring and reacting for 4h, cooling to 8 ℃ after the reaction is completed, discharging residual hexafluoropropylene gas, and separating liquid to obtain lower liquid, thus obtaining the hexafluoropropylene dimer.
The organic solvent is dimethyl sulfoxide.
The inert gas is high-purity argon.
The preparation method of the metal fluoride-organic complex catalyst comprises the following steps:
taking 8Kg of metal fluoride, 5Kg of copper acrylate, adding into 300Kg of N-methylpyrrolidone, stirring and uniformly mixing, introducing argon atmosphere, controlling the temperature to 66 ℃, dissolving 2.8Kg of ammonium persulfate into 35Kg of isopropanol, slowly dropwise adding into a reaction kettle, and controlling dropwise adding for 2 hours; after the dripping is finished, controlling the temperature to 55 ℃, continuing to react for 3 hours, adding 1Kg of 5, 5-divinyl-2, 2-dipyridine, 0.2Kg of chloroplatinic acid, controlling the temperature to 55 ℃, continuing to react for 1 hour, cooling to room temperature, adding 360Kg of acetone, extracting, evaporating the obtained solution to dryness, obtaining a solid, drying in vacuum for 8 hours at 45 ℃, and then crushing to obtain the metal fluoride-organic complex catalyst.
The metal fluoride is potassium fluoride.
The hexafluoropropylene dimer content in the product prepared in this experiment was 89.2% and the product yield was 80.3%.
Claims (6)
1. A method for preparing hexafluoropropylene dimer, which is characterized in that: adding 0.01-0.15 part of metal fluoride-organic complex catalyst and 45-65 parts of organic solvent into a reaction kettle according to parts by weight, stirring and mixing uniformly, bubbling for 5-10min by using inert gas, vacuumizing, filling the inert gas for circulation for 3 times, filling 18-26 parts of hexafluoropropylene under the vacuum condition, controlling the temperature to 25-45 ℃, stirring and reacting for 1.5-8h, cooling to 5-10 ℃ after the reaction is completed, discharging residual hexafluoropropylene gas, and separating liquid to obtain lower liquid, thus obtaining the hexafluoropropylene dimer;
the preparation method of the metal fluoride-organic complex catalyst comprises the following steps:
according to the parts by weight, 5-10 parts of metal fluoride, 3-10 parts of dimethyl allyl silane, 3-8 parts of copper acrylate and 280-380 parts of N-methyl pyrrolidone are taken, the mixture is stirred and mixed uniformly, argon atmosphere is introduced, then the temperature is controlled to be 60-80 ℃, 2.4-6.8 parts of ammonium persulfate is dissolved in 30-50 parts of isopropanol, and the mixture is slowly dripped into a reaction kettle, and the dripping is controlled to be carried out for 1-5 hours; after the dripping is finished, controlling the temperature to be 50-70 ℃, continuing to react for 1-4 hours, adding 0.5-2 parts of 5, 5-divinyl-2, 2-bipyridine, 0.1-1 part of chloroplatinic acid, controlling the temperature to be 50-70 ℃, continuing to react for 0.5-2 hours, cooling to room temperature, adding 300-500 parts of acetone, extracting, evaporating the obtained solution to dryness to obtain a solid, drying in vacuum for 6-10 hours at 40-60 ℃, and then crushing to obtain the metal fluoride-organic complex catalyst;
the metal fluoride is cesium fluoride or potassium fluoride or copper fluoride.
2. A process for the preparation of hexafluoropropylene dimer as claimed in claim 1, wherein: the organic solvent is acetonitrile or dimethyl sulfoxide or sulfolane.
3. A process for the preparation of hexafluoropropylene dimer as claimed in claim 1, wherein: the inert gas is high-purity nitrogen or high-purity argon.
4. A process for the preparation of hexafluoropropylene dimer as claimed in claim 1, wherein: the preparation method of the metal fluoride-organic complex catalyst comprises the following steps:
taking 5Kg of metal fluoride, 3Kg of dimethyl allyl silane, 3Kg of copper acrylate and 280Kg of N-methyl pyrrolidone, stirring and mixing uniformly, introducing argon atmosphere, controlling the temperature to 60 ℃, dissolving 2.4Kg of ammonium persulfate in 30Kg of isopropanol, slowly dropwise adding into a reaction kettle, and controlling dropwise adding for 1h; after the dripping is finished, controlling the temperature to be 50 ℃, continuing to react for 1h, adding 0.5Kg of 5, 5-divinyl-2, 2-bipyridine, 0.1Kg of chloroplatinic acid, controlling the temperature to be 50 ℃, continuing to react for 0.5h, cooling to room temperature, adding 300Kg of acetone, extracting, evaporating the obtained solution to dryness to obtain a solid, drying in vacuum for 6h at the temperature of 40 ℃, and crushing to obtain the metal fluoride-organic complex catalyst;
the metal fluoride is cesium fluoride.
5. A process for the preparation of hexafluoropropylene dimer as claimed in claim 1, wherein: the preparation method of the metal fluoride-organic complex catalyst comprises the following steps:
8Kg of metal fluoride, 5Kg of dimethyl allyl silane, 5Kg of copper acrylate and 300Kg of N-methyl pyrrolidone are taken, the mixture is stirred and mixed uniformly, argon atmosphere is introduced, then the temperature is controlled to 66 ℃, 2.8Kg of ammonium persulfate is dissolved in 35Kg of isopropanol, and the mixture is slowly dripped into a reaction kettle, and the dripping is controlled for 2 hours; after the dripping is finished, controlling the temperature to 55 ℃, continuing to react for 3 hours, then adding 1Kg of 5, 5-divinyl-2, 2-dipyridine, 0.2Kg of chloroplatinic acid, controlling the temperature to 55 ℃, continuing to react for 1 hour, then cooling to room temperature, adding 360Kg of acetone, extracting, evaporating the obtained solution to dryness to obtain a solid, drying the solid in vacuum at 45 ℃ for 8 hours, and then crushing to obtain the metal fluoride-organic complex catalyst;
the metal fluoride is potassium fluoride.
6. A process for the preparation of hexafluoropropylene dimer as claimed in claim 1, wherein: the preparation method of the metal fluoride-organic complex catalyst comprises the following steps:
taking 10Kg of metal fluoride, 10Kg of dimethyl allyl silane, 8Kg of copper acrylate and 380Kg of N-methyl pyrrolidone, stirring and mixing uniformly, introducing argon atmosphere, controlling the temperature to 80 ℃, dissolving 6.8Kg of ammonium persulfate in 50Kg of isopropanol, slowly dropwise adding into a reaction kettle, and controlling dropwise adding for 5 hours; after the dripping is finished, controlling the temperature to 70 ℃, continuing to react for 4 hours, then adding 2Kg of 5, 5-divinyl-2, 2-dipyridine, 1Kg of chloroplatinic acid, controlling the temperature to 70 ℃, continuing to react for 2 hours, then cooling to room temperature, adding 500Kg of acetone, extracting, evaporating the obtained solution to dryness to obtain a solid, drying in vacuum for 10 hours at 60 ℃, and then crushing to obtain the metal fluoride-organic complex catalyst;
the metal fluoride is copper fluoride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911359822.8A CN111116308B (en) | 2019-12-25 | 2019-12-25 | Preparation method of hexafluoropropylene dimer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911359822.8A CN111116308B (en) | 2019-12-25 | 2019-12-25 | Preparation method of hexafluoropropylene dimer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111116308A CN111116308A (en) | 2020-05-08 |
| CN111116308B true CN111116308B (en) | 2023-07-25 |
Family
ID=70502439
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911359822.8A Active CN111116308B (en) | 2019-12-25 | 2019-12-25 | Preparation method of hexafluoropropylene dimer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111116308B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112851466B (en) * | 2020-12-31 | 2022-04-08 | 中国科学院过程工程研究所 | Method for catalyzing hexafluoropropylene oligomerization reaction by fluorine-containing negative ion room temperature ionic liquid |
| CN113929554B (en) * | 2021-11-05 | 2023-10-20 | 浙江巨化汉正新材料有限公司 | Preparation method of hexafluoropropylene dimer with D2 structure |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1095367A (en) * | 1992-12-28 | 1994-11-23 | 美国3M公司 | The preparation of hexafluoropropene oligomers |
| CN102503767A (en) * | 2011-11-22 | 2012-06-20 | 中国科学技术大学 | Preparation method of hexafluoropropylene dimer |
| CN108727154A (en) * | 2018-06-05 | 2018-11-02 | 浙江利化新材料科技有限公司 | A kind of preparation method of hexafluoropropylene dimmer |
-
2019
- 2019-12-25 CN CN201911359822.8A patent/CN111116308B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1095367A (en) * | 1992-12-28 | 1994-11-23 | 美国3M公司 | The preparation of hexafluoropropene oligomers |
| CN102503767A (en) * | 2011-11-22 | 2012-06-20 | 中国科学技术大学 | Preparation method of hexafluoropropylene dimer |
| CN108727154A (en) * | 2018-06-05 | 2018-11-02 | 浙江利化新材料科技有限公司 | A kind of preparation method of hexafluoropropylene dimmer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111116308A (en) | 2020-05-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111116308B (en) | Preparation method of hexafluoropropylene dimer | |
| CN104261369B (en) | Preparation method of high purity phosphorus pentafluoride | |
| CN112745445B (en) | Perfluoro sulfonyl fluororesin, preparation method thereof and perfluoro sulfonic acid resin prepared from perfluoro sulfonyl fluororesin | |
| CN106349293B (en) | The preparation method of high-purity antimony triethyl | |
| CN112830863A (en) | Method for continuously and controllably preparing hexafluoropropylene dimer/trimer | |
| CN100543001C (en) | 2, the preparation method of 5-norbornadiene | |
| CN113004518B (en) | Phthalonitrile resin prepolymer and preparation method thereof | |
| Sheng et al. | Polymerization mechanism of 4-APN and a new catalyst for phthalonitrile resin polymerization | |
| CN103664470A (en) | Method for preparing norbornene | |
| CN102167828A (en) | Preparation method of R-122-based episulfide resin | |
| CN115785056B (en) | Synthetic method of fluoroethylene carbonate | |
| CN111269081B (en) | Preparation method of hexafluoropropylene tripolymer | |
| CN102491319B (en) | Process for producing graphite fluoride by low-temperature intercalation method | |
| CN106380368B (en) | Method for preparing 1, 5-cyclooctadiene by cyclizing butadiene | |
| CN109939734B (en) | Perfluorosulfonic acid resin catalyst, preparation method and application in preparation of dichlorofluoromethane | |
| CN101544587A (en) | Preparation method of alpha, alpha'-bis(tert-butyl peroxy) diisopropylbenzene | |
| CN112939902A (en) | Preparation process of raw material furan for preparing 2-acetylfuran | |
| CN103420777A (en) | Method for continuously synthesizing 1, 5, 9-cyclododecatriene | |
| CN113912473A (en) | Method for preparing hexafluoropropylene trimer by liquid phase method | |
| CN112851466A (en) | Method for catalyzing hexafluoropropylene oligomerization reaction by fluorine-containing negative ion room temperature ionic liquid | |
| CN108190858B (en) | Preparation method of graphite fluoride | |
| CN111389424A (en) | Catalyst, preparation method and application in hexafluoropropylene oligomerization reaction | |
| CN115181004B (en) | Preparation method of trifluoroiodomethane | |
| CN114634397B (en) | Method for preparing hexafluoropropylene dimer by gas phase method | |
| CN109503365A (en) | The method for preparing perfluor acetylfluoride and perfluor butyryl fluorine simultaneously |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |