CN113912473B - Method for preparing hexafluoropropylene trimer by liquid phase method - Google Patents
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- CN113912473B CN113912473B CN202111328947.1A CN202111328947A CN113912473B CN 113912473 B CN113912473 B CN 113912473B CN 202111328947 A CN202111328947 A CN 202111328947A CN 113912473 B CN113912473 B CN 113912473B
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- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000013638 trimer Substances 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000007791 liquid phase Substances 0.000 title claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- 229910001512 metal fluoride Inorganic materials 0.000 claims abstract description 29
- 239000012747 synergistic agent Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 63
- 239000003960 organic solvent Substances 0.000 claims description 42
- 239000002904 solvent Substances 0.000 claims description 26
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- 238000001354 calcination Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 12
- -1 vinyl guanamine Chemical compound 0.000 claims description 12
- PBVZTJDHQVIHFR-UHFFFAOYSA-N 1,1,2,3,3,3-hexafluoroprop-1-ene Chemical compound FC(F)=C(F)C(F)(F)F.FC(F)=C(F)C(F)(F)F PBVZTJDHQVIHFR-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- UJTPZISIAWDGFF-UHFFFAOYSA-N ethenylsulfonylbenzene Chemical compound C=CS(=O)(=O)C1=CC=CC=C1 UJTPZISIAWDGFF-UHFFFAOYSA-N 0.000 claims description 10
- 229920002554 vinyl polymer Polymers 0.000 claims description 10
- HCZMHWVFVZAHCR-UHFFFAOYSA-N 2-[2-(2-sulfanylethoxy)ethoxy]ethanethiol Chemical compound SCCOCCOCCS HCZMHWVFVZAHCR-UHFFFAOYSA-N 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical group [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 5
- 235000003270 potassium fluoride Nutrition 0.000 claims description 4
- 239000011698 potassium fluoride Substances 0.000 claims description 4
- 235000013024 sodium fluoride Nutrition 0.000 claims description 4
- 239000011775 sodium fluoride Substances 0.000 claims description 4
- KCTAHLRCZMOTKM-UHFFFAOYSA-N tripropylphosphane Chemical compound CCCP(CCC)CCC KCTAHLRCZMOTKM-UHFFFAOYSA-N 0.000 claims description 4
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 2
- 238000003889 chemical engineering Methods 0.000 abstract description 3
- 239000012847 fine chemical Substances 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 239000006227 byproduct Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 5
- 238000006845 Michael addition reaction Methods 0.000 description 3
- 101100030361 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-3 gene Proteins 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- FAEGGADNHFKDQX-UHFFFAOYSA-N 1,1,1,3,4,4,5,5,5-nonafluoro-2-(trifluoromethyl)pent-2-ene Chemical compound FC(F)(F)C(C(F)(F)F)=C(F)C(F)(F)C(F)(F)F FAEGGADNHFKDQX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000002939 oilproofing Substances 0.000 description 2
- 238000006384 oligomerization reaction Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical group F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- PGFXOWRDDHCDTE-UHFFFAOYSA-N hexafluoropropylene oxide Chemical compound FC(F)(F)C1(F)OC1(F)F PGFXOWRDDHCDTE-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
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
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/12—Fluorides
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0245—Nitrogen containing compounds being derivatives of carboxylic or carbonic acids
- B01J31/0251—Guanidides (R2N-C(=NR)-NR2)
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0271—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0231
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of fine chemical engineering, in particular to a method for preparing hexafluoropropylene trimer by a liquid phase method; the invention provides a method for preparing hexafluoropropylene trimer by a liquid phase method, which can improve the interaction of a synergistic agent and metal fluoride, stabilize the valence state of metal, improve the catalytic activity, realize the high dispersion of active components in a catalyst and greatly improve the overall efficiency of the catalyst.
Description
Technical Field
The invention relates to the technical field of fine chemical engineering, in particular to a method for preparing hexafluoropropylene trimer by a liquid phase method.
Background
The hexafluoropropylene trimer has three structural forms of T-1, T-2 and T-3, and the boiling point is 110-115 ℃. Hexafluoropropylene trimer is used in the application of fluorosilicone modified polyurethane, and perfluoro olefin, hydroxyl silicone oil, epoxy ethane and diisocyanate are used as raw materials to be mixed into emulsion with emulsifying property for water and oil proofing treatment of plants, leather and the like, so that the water and oil proofing effect is excellent, and the softness and smoothness can be greatly increased. Also, researchers have prepared hexafluoropropylene oxide polymers of weight average molecular weight, as well as novel methacrylate copolymers.
The applicant's prior application, CN202010172248.1, adopts the gas phase catalytic synthesis method to prepare hexafluoropropylene trimer, has the advantages of no solvent and catalyst residue; the method adopts a method of adding hexafluoropropylene gas in multiple stages, is favorable for the full conversion of hexafluoropropylene dimer, and avoids the generation of polymers caused by excessive hexafluoropropylene gas concentration; the catalyst can catalyze the reaction of hexafluoropropylene and hexafluoropropylene dimer to generate hexafluoropropylene trimer with high selectivity, and the content of polymers is reduced; the method has higher yield and high purity of the prepared hexafluoropropylene trimer, and has very good industrialized prospect.
CN201910905170.7 discloses a process for preparing hexafluoropropylene trimer. The preparation method comprises the following steps: in an aprotic polar solvent, under the action of a catalyst, perfluoro-2-methyl-2-pentene and hexafluoropropylene are added to form hexafluoropropylene trimer in one step, wherein the catalyst consists of a main catalyst and a cocatalyst in a mass ratio of 0.1-10:1, and the molar ratio of perfluoro-2-methyl-2-pentene to hexafluoropropylene is 0.1-10:1.
However, the hexafluoropropylene trimer in the prior art is mainly synthesized by adopting a liquid phase method, the catalyst and the additive thereof are dissolved in an aprotic polar solvent in the liquid phase method hexafluoropropylene oligomerization process, and then hexafluoropropylene is introduced for oligomerization reaction, and the product produced by the method necessarily contains a small amount of solvent and catalyst.
Disclosure of Invention
The invention discloses a method for preparing hexafluoropropylene trimer by a liquid phase method, and belongs to the technical field of fine chemical engineering. The method is favorable for forward reaction under the low-temperature condition, ensures the stability of raw materials and products, greatly reduces the decomposition rate, and simultaneously generates byproducts which are separated out by smaller particles, and a small amount of liquid remained on the solid after filtration can be directly ignored.
A method for preparing hexafluoropropylene trimer by liquid phase method, which is characterized by comprising the following steps:
the weight portions are as follows: adding 0.01-5 parts of metal fluoride, 0.01-3 parts of synergist, 150-300 parts of hexafluoropropylene dimer and 100-200 parts of organic solvent into a high-pressure reaction kettle, introducing inert gas, starting stirring, slowly introducing 100-150 parts of hexafluoropropylene, and reacting for 1-4h at 30-100 ℃; and cooling to room temperature after the reaction is finished, discharging materials in the reaction kettle from the bottom of the reaction kettle, and obtaining a lower-layer reaction product hexafluoropropylene trimer through liquid separation operation because the product and the catalyst solvent system are not mutually soluble.
Further, the metal fluoride is cesium fluoride or potassium fluoride or sodium fluoride;
further, the metal fluoride is 0.5-2 parts;
further, the metal fluoride is ground into powder after being calcined;
further, the calcination temperature is 400-600 ℃, and the calcination time is 4-10 hours;
further, the synergist is 0.3-1.8 parts;
further, the preparation method of the synergist comprises the following steps:
according to the mass parts, adding 1-6 parts of phenyl vinyl sulfone, 0.01-2 parts of vinyl guanamine, 8-15 parts of 3, 6-dioxa-1, 8-octanedithiol (EDT), 100-120 parts of organic solvent, adding 1.5-3.2 parts of catalyst, stirring at 60-77 ℃, maintaining the pressure at 1-3Mpa, reacting for 1-4 hours, and evaporating the solvent and the excessive EDT under reduced pressure to obtain the synergist.
Further, the synergistic agent uses one of ethanol, chloroform or N, N-dimethylformamide as an organic solvent;
further, the catalyst is one or more of triphenylphosphine (PPh 3), tripropylphosphine (P-n-Pr 3), triethylamine or dipropylamine;
further, the organic solvent is an anhydrous solvent;
further, the organic solvent is one or a plurality of compositions of acetonitrile, ethylene glycol dimethyl ether, tetrahydrofuran, diethylene glycol dimethyl ether and dimethyl sulfoxide;
further, the organic solvent is acetonitrile or dimethyl sulfoxide;
further, the reaction temperature is 30-60 ℃;
further, the reaction pressure is 0.5-5Mpa.
The reaction mechanism is as follows:
phenyl vinyl sulfone, vinyl guanamine and 3, 6-dioxa-1, 8-octanedithiol (EDT) are subjected to a mercapto-Michael addition reaction to obtain a compound containing sulfonyl and guanamine as a synergist.
The technical effects are as follows:
(1) The interaction between the synergist and the metal fluoride can be improved, the valence state of the metal is stabilized, the catalytic activity is improved, and the high dispersion of the active components in the catalyst is realized; helping to increase the overall effectiveness of the catalyst.
(2) The sulfhydryl-Michael addition reaction is carried out on phenyl vinyl sulfone, vinyl guanamine and 3, 6-dioxa-1, 8-octadithiol (EDT), and the sulfhydryl-Michael addition reaction and the metal fluoride form a metal complex, so that the free degree of fluorine anions is reduced.
Drawings
FIG. 1 is a gas chromatogram of the hexafluoropropylene trimer prepared in example 1 after further rectification.
Detailed Description
The detection method comprises the following steps:
in the specific embodiment of the invention, the content of hexafluoropropylene trimer 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 invention is further illustrated by the following examples:
comparative example 1
5g of metal fluoride, 0.01g of synergist, 150g of hexafluoropropylene dimer and 100g of organic solvent are added into a high-pressure reaction kettle, inert gas is introduced, stirring is started, and 100g of hexafluoropropylene is slowly introduced for reaction for 1h at 30 ℃; cooling to room temperature after the reaction is finished, and distilling under reduced pressure to remove the solvent; filtering to obtain hexafluoropropylene trimer.
The metal fluoride is cesium fluoride;
the metal fluoride is ground into powder after being calcined;
the calcination temperature is 400 ℃, and the calcination time is 4 hours;
the synergist is 0.3g;
the preparation method of the synergist comprises the following steps:
1g of phenyl vinyl sulfone, 0.01g of vinyl guanamine, 8g of 3, 6-dioxa-1, 8-octanedithiol (EDT), 100g of organic solvent, 1.5g of catalyst and stirring at 60 ℃, maintaining the pressure at 1Mpa, reacting for 1h, and evaporating the solvent and the excess EDT under reduced pressure to obtain the synergist.
The organic solvent used for the synergistic agent is ethanol;
the catalyst is triphenylphosphine (PPh 3);
the organic solvent is an anhydrous solvent;
the organic solvent is acetonitrile;
the reaction temperature is 30 ℃;
the reaction pressure was 0.5Mpa.
Results: the trimer content was 61.76%, the by-product content was 0.512%, the hexafluoropropylene conversion was 97.23%, and the trimer yield was 55.07%.
Comparative example 2
Adding 0.01g of metal fluoride, 3g of synergist, 300g of hexafluoropropylene dimer and 100g of organic solvent into a high-pressure reaction kettle, introducing inert gas, starting stirring, slowly introducing 100g of hexafluoropropylene, and reacting for 4 hours at 100 ℃; and cooling to room temperature after the reaction is finished, discharging materials in the reaction kettle from the bottom of the reaction kettle, and obtaining a lower-layer reaction product hexafluoropropylene trimer through liquid separation operation because the product and the catalyst solvent system are not mutually soluble.
The metal fluoride is potassium fluoride;
the metal fluoride is ground into powder after being calcined;
the calcination temperature is 600 ℃, and the calcination time is 10 hours;
the preparation method of the synergist comprises the following steps:
6g of phenyl vinyl sulfone, 2g of vinyl guanamine, 15g of 3, 6-dioxa-1, 8-octanedithiol (EDT), 120g of organic solvent, 3.2g of catalyst, stirring at 77 ℃, maintaining the pressure at 3Mpa, reacting for 4h, and evaporating the solvent and the excess EDT under reduced pressure to obtain the synergist.
The organic solvent for the synergistic agent is chloroform;
the catalyst is tripropylphosphine (P-n-Pr 3);
the organic solvent is an anhydrous solvent;
the organic solvent is ethylene glycol dimethyl ether;
the reaction temperature is 60 ℃;
the reaction pressure was 5Mpa.
Results: the trimer content was 73.55%, the by-product content was 0.350%, the hexafluoropropylene conversion was 98.82%, and the trimer yield was 70.01%.
Example 3
Adding 0.5g of metal fluoride, 0.3g of synergist, 180g of hexafluoropropylene dimer and 150g of organic solvent into a high-pressure reaction kettle, introducing inert gas, starting stirring, slowly introducing 120g of hexafluoropropylene, and reacting for 3 hours at 80 ℃; and cooling to room temperature after the reaction is finished, discharging materials in the reaction kettle from the bottom of the reaction kettle, and obtaining a lower-layer reaction product hexafluoropropylene trimer through liquid separation operation because the product and the catalyst solvent system are not mutually soluble.
The metal fluoride is sodium fluoride;
the metal fluoride is ground into powder after being calcined;
the calcination temperature is 500 ℃, and the calcination time is 8 hours;
the preparation method of the synergist comprises the following steps:
3g of phenyl vinyl sulfone, 0.5g of vinyl guanamine, 10g of 3, 6-dioxa-1, 8-octanedithiol (EDT), 120g of organic solvent, 2.0g of catalyst and stirring at 67 ℃, maintaining the pressure at 2Mpa, reacting for 3h, and evaporating the solvent and the excess EDT under reduced pressure to obtain the synergist.
The organic solvent used for the synergistic agent is ethanol;
the catalyst is triphenylphosphine (PPh 3);
the organic solvent is an anhydrous solvent;
the organic solvent is acetonitrile;
the reaction temperature is 55 ℃;
the reaction pressure was 4.2MPa.
Results: the trimer content was 90.48%, the by-product content was 0.187%, the hexafluoropropylene conversion was 99.93%, and the trimer yield was 80.82%.
Example 4
Adding 1.0g of metal fluoride, 0.9g of synergist, 240g of hexafluoropropylene dimer and 180g of organic solvent into a high-pressure reaction kettle, introducing inert gas, starting stirring, slowly introducing 130g of hexafluoropropylene, and reacting for 3 hours at 80 ℃; and cooling to room temperature after the reaction is finished, discharging materials in the reaction kettle from the bottom of the reaction kettle, and obtaining a lower-layer reaction product hexafluoropropylene trimer through liquid separation operation because the product and the catalyst solvent system are not mutually soluble.
The metal fluoride is sodium fluoride;
the metal fluoride is ground into powder after being calcined;
the calcination temperature is 500 ℃, and the calcination time is 80 hours;
the preparation method of the synergist comprises the following steps:
4g of phenyl vinyl sulfone, 1.0g of vinyl guanamine, 12g of 3, 6-dioxa-1, 8-octanedithiol (EDT), 120g of organic solvent, 2.4g of catalyst and 67 ℃ are added into a closed high-pressure reaction kettle, stirring is carried out at 67 ℃, the pressure is kept at 2Mpa, the reaction is carried out for 3 hours, and the solvent and the excessive EDT are distilled off under reduced pressure, thus obtaining the synergist.
The synergistic agent uses N, N-dimethylformamide as an organic solvent;
the catalyst is triethylamine;
the organic solvent is an anhydrous solvent;
the organic solvent is dimethyl sulfoxide;
the reaction temperature is 50 ℃;
the reaction pressure was 4.8MPa.
Results: the trimer content was 92.11%, the by-product content was 0.123%, the hexafluoropropylene conversion was 99.95%, and the trimer yield was 82.82%.
Example 5
Adding 1.5g of metal fluoride, 1.6g of synergist, 280g of hexafluoropropylene dimer and 200g of organic solvent into a high-pressure reaction kettle, introducing inert gas, starting stirring, slowly introducing 140g of hexafluoropropylene, and reacting for 3 hours at 80 ℃; and cooling to room temperature after the reaction is finished, discharging materials in the reaction kettle from the bottom of the reaction kettle, and obtaining a lower-layer reaction product hexafluoropropylene trimer through liquid separation operation because the product and the catalyst solvent system are not mutually soluble.
The metal fluoride is cesium fluoride;
the metal fluoride is ground into powder after being calcined;
the calcination temperature is 500 ℃, and the calcination time is 8 hours;
the preparation method of the synergist comprises the following steps:
5g of phenyl vinyl sulfone, 1.5g of vinyl guanamine, 14g of 3, 6-dioxa-1, 8-octanedithiol (EDT), 120g of organic solvent, 2.8g of catalyst and 67 ℃ are added into a closed high-pressure reaction kettle, stirring is carried out at 67 ℃, the pressure is kept at 2Mpa, the reaction is carried out for 3 hours, and the solvent and the excessive EDT are distilled off under reduced pressure, so that the synergist is obtained.
The organic solvent for the synergistic agent is chloroform;
the catalyst is dipropylamine;
the organic solvent is an anhydrous solvent;
the organic solvent is tetrahydrofuran;
the reaction temperature is 55 ℃;
the reaction pressure was 4.2MPa.
Results: the trimer content was 92.19%, the by-product content was 0.105%, the hexafluoropropylene conversion was 99.96%, and the trimer yield was 84.32%.
Example 6
Adding 2g of metal fluoride, 1.8g of synergist, 300g of hexafluoropropylene dimer and 200g of organic solvent into a high-pressure reaction kettle, introducing inert gas, starting stirring, slowly introducing 150g of hexafluoropropylene, and reacting for 4 hours at 80 ℃; and cooling to room temperature after the reaction is finished, discharging materials in the reaction kettle from the bottom of the reaction kettle, and obtaining a lower-layer reaction product hexafluoropropylene trimer through liquid separation operation because the product and the catalyst solvent system are not mutually soluble.
The metal fluoride is potassium fluoride;
the metal fluoride is ground into powder after being calcined;
the calcination temperature is 600 ℃, and the calcination time is 6 hours;
the preparation method of the synergist comprises the following steps:
6g of phenyl vinyl sulfone, 2g of vinyl guanamine, 15g of 3, 6-dioxa-1, 8-octanedithiol (EDT), 120g of organic solvent, 3.2g of catalyst and 67 ℃ are added into a closed high-pressure reaction kettle, stirring is carried out at 67 ℃, the pressure is kept at 2Mpa, the reaction is carried out for 3 hours, and the solvent and the excessive EDT are distilled off under reduced pressure to obtain the synergist.
The organic solvent used for the synergistic agent is ethanol;
the catalyst is tripropylphosphine (P-n-Pr 3);
the organic solvent is an anhydrous solvent;
the organic solvent is acetonitrile;
the reaction temperature is 55 ℃;
the reaction pressure was 4.2MPa.
Results: the trimer content was 94.33%, the by-product content was 0.101%, the hexafluoropropylene conversion was 99.99%, and the trimer yield was 86.12%.
Claims (12)
1. A method for preparing hexafluoropropylene trimer by liquid phase method comprises the following steps: the weight portions are as follows: adding 0.01-5 parts of metal fluoride, 0.01-3 parts of synergist, 150-300 parts of hexafluoropropylene dimer and 100-200 parts of organic solvent 1 into a high-pressure reaction kettle, introducing inert gas, starting stirring, slowly introducing 100-150 parts of hexafluoropropylene, and reacting for 1-4 hours at 30-100 ℃; cooling to room temperature after the reaction is finished, discharging materials in the reaction kettle from the bottom of the reaction kettle, and obtaining a lower-layer reaction product hexafluoropropylene trimer through liquid separation operation because the product and the catalyst solvent system are not mutually soluble;
the preparation method of the synergist comprises the following steps: adding 1-6 parts by mass of phenyl vinyl sulfone, 0.01-2 parts by mass of vinyl guanamine, 8-15 parts by mass of 3, 6-dioxa-1, 8-octanedithiol (EDT), 100-120 parts by mass of organic solvent 2, adding 1.5-3.2 parts by mass of catalyst, stirring at 60-77 ℃, maintaining the pressure at 1-3Mpa, reacting for 1-4h, and evaporating the solvent and the excessive EDT under reduced pressure to obtain a synergistic agent;
the synergist catalyst is one or more of triphenylphosphine, tripropylphosphine, triethylamine or dipropylamine.
2. A process for preparing hexafluoropropylene trimer by liquid phase method as claimed in claim 1, characterized in that: the metal fluoride is cesium fluoride or potassium fluoride or sodium fluoride.
3. A process for preparing hexafluoropropylene trimer by liquid phase method as claimed in claim 1, characterized in that: 0.5-2 parts of metal fluoride.
4. A process for preparing hexafluoropropylene trimer by liquid phase method as claimed in claim 1, characterized in that: the metal fluoride is calcined and ground into powder.
5. A process for preparing hexafluoropropylene trimer by liquid phase method as set forth in claim 4, wherein: the calcination temperature is 400-600 ℃, and the calcination time is 4-10h.
6. A process for preparing hexafluoropropylene trimer by liquid phase method as claimed in claim 1, characterized in that: the synergist is 0.3-1.8 parts.
7. A process for preparing hexafluoropropylene trimer by liquid phase method as claimed in claim 1, characterized in that: the synergistic agent uses one of ethanol, chloroform or N, N-dimethylformamide as the organic solvent 2.
8. A process for preparing hexafluoropropylene trimer by liquid phase method as claimed in claim 1, characterized in that: the organic solvent 1 is an anhydrous solvent.
9. A process for preparing hexafluoropropylene trimer by liquid phase method as claimed in claim 1, characterized in that: the organic solvent 1 is one or a combination of a plurality of acetonitrile, ethylene glycol dimethyl ether, tetrahydrofuran, diethylene glycol dimethyl ether and dimethyl sulfoxide.
10. A process for preparing hexafluoropropylene trimer by liquid phase method as claimed in claim 9, characterized in that: the organic solvent 1 is acetonitrile or dimethyl sulfoxide.
11. A process for preparing hexafluoropropylene trimer by liquid phase method as claimed in claim 1, characterized in that: the reaction temperature is 30-60 ℃.
12. A process for preparing hexafluoropropylene trimer by liquid phase method as claimed in claim 1, characterized in that: the reaction pressure is 0.5-5Mpa.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US3917724A (en) * | 1973-02-09 | 1975-11-04 | Hoechst Ag | Process for preparing oligomers of hexafluoropropene |
| JPS53144508A (en) * | 1977-05-20 | 1978-12-15 | Neos Kk | Process for preparing perfluoroolefin oligomer |
| CN111269081A (en) * | 2020-03-12 | 2020-06-12 | 浙江巨化汉正新材料有限公司 | Preparation method of hexafluoropropylene tripolymer |
| CN111606778A (en) * | 2020-06-29 | 2020-09-01 | 厦门名大科技有限公司 | Catalytic synthesis method of hexafluoropropylene oligomer |
| CN112830863A (en) * | 2021-01-04 | 2021-05-25 | 山东华夏神舟新材料有限公司 | Method for continuously and controllably preparing hexafluoropropylene dimer/trimer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US3917724A (en) * | 1973-02-09 | 1975-11-04 | Hoechst Ag | Process for preparing oligomers of hexafluoropropene |
| JPS53144508A (en) * | 1977-05-20 | 1978-12-15 | Neos Kk | Process for preparing perfluoroolefin oligomer |
| CN111269081A (en) * | 2020-03-12 | 2020-06-12 | 浙江巨化汉正新材料有限公司 | Preparation method of hexafluoropropylene tripolymer |
| CN111606778A (en) * | 2020-06-29 | 2020-09-01 | 厦门名大科技有限公司 | Catalytic synthesis method of hexafluoropropylene oligomer |
| CN112830863A (en) * | 2021-01-04 | 2021-05-25 | 山东华夏神舟新材料有限公司 | Method for continuously and controllably preparing hexafluoropropylene dimer/trimer |
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