CN113912473A - Method for preparing hexafluoropropylene trimer by liquid phase method - Google Patents
Method for preparing hexafluoropropylene trimer by liquid phase method Download PDFInfo
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- CN113912473A CN113912473A CN202111328947.1A CN202111328947A CN113912473A CN 113912473 A CN113912473 A CN 113912473A CN 202111328947 A CN202111328947 A CN 202111328947A CN 113912473 A CN113912473 A CN 113912473A
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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 61
- 239000013638 trimer Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000007791 liquid phase Substances 0.000 title claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- 229910001512 metal fluoride Inorganic materials 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims description 71
- 239000003960 organic solvent Substances 0.000 claims description 42
- 239000002904 solvent Substances 0.000 claims description 26
- 238000001354 calcination Methods 0.000 claims description 22
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- 230000008569 process Effects 0.000 claims description 13
- 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 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 11
- 238000003756 stirring Methods 0.000 claims description 11
- HCZMHWVFVZAHCR-UHFFFAOYSA-N 2-[2-(2-sulfanylethoxy)ethoxy]ethanethiol Chemical compound SCCOCCOCCS HCZMHWVFVZAHCR-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
- 238000002360 preparation method Methods 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- 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
- 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
- 239000000463 material 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
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- 238000007599 discharging Methods 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
- 239000000203 mixture Substances 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 5
- 101100030361 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-3 gene Proteins 0.000 claims description 4
- 229960001701 chloroform Drugs 0.000 claims description 4
- 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
- -1 vinyl guanamine Chemical compound 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
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000003889 chemical engineering Methods 0.000 abstract description 3
- 239000012847 fine chemical Substances 0.000 abstract description 3
- 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
- 238000000227 grinding Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 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
- 238000006845 Michael addition reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects 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
- 238000004078 waterproofing Methods 0.000 description 2
- ZTNJGMFHJYGMDR-UHFFFAOYSA-N 1,2-diisocyanatoethane Chemical compound O=C=NCCN=C=O ZTNJGMFHJYGMDR-UHFFFAOYSA-N 0.000 description 1
- 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
- QAAXRTPGRLVPFH-UHFFFAOYSA-N [Bi].[Cu] Chemical compound [Bi].[Cu] QAAXRTPGRLVPFH-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
- 239000000839 emulsion Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 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
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 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
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
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- 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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- 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 between a synergist and a 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 tripolymer has three structural forms of T-1, T-2 and T-3, and the boiling point is 110-115 ℃. The hexafluoropropylene tripolymer is applied to the application of the fluorine-silicon modified polyurethane, perfluoroolefin, hydroxyl silicone oil, ethylene oxide and diisocyanate are used as raw materials to be mixed into emulsified emulsion applied to the aspects of water-proofing and oil-proofing treatment of plants, leather and the like, the water-proofing and oil-proofing effects are excellent, and the softness and the smooth feeling can be greatly increased. Meanwhile, researchers have prepared hexafluoropropylene oxide polymers with weight average molecular weight, and novel methacrylate copolymers.
The prior application of the applicant, CN202010172248.1, adopts a gas phase catalytic synthesis method to prepare hexafluoropropylene trimer, and has the advantages of no solvent and catalyst residue; the method adopts a method of adding hexafluoropropylene gas in multiple stages, which is beneficial to the full conversion of hexafluoropropylene dimer and avoids the generation of polymer caused by excessive hexafluoropropylene gas concentration; the copper bismuth doped complex catalytic material is creatively used as a catalyst for the reaction of hexafluoropropylene and hexafluoropropylene dimer, the catalyst can be used for catalyzing the reaction of hexafluoropropylene and hexafluoropropylene dimer with high selectivity to generate hexafluoropropylene trimer, and the content of polymer is reduced; the method has high yield, high purity of the prepared hexafluoropropylene tripolymer and very good industrial prospect.
CN201910905170.7 discloses a preparation method of hexafluoropropylene tripolymer. 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 subjected to one-step addition to generate hexafluoropropylene trimer, 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, hexafluoropropylene tripolymer in the prior art is mainly synthesized by a liquid phase method, the hexafluoropropylene oligomerization process by the liquid phase method is to dissolve a catalyst and an additive thereof in an aprotic polar solvent and then introduce hexafluoropropylene for oligomerization, and a product produced by the method necessarily contains a small amount of the solvent and the catalyst.
Disclosure of Invention
The invention discloses a method for preparing hexafluoropropylene trimer by a liquid phase method, belonging to the technical field of fine chemical engineering. The method is beneficial to the forward reaction under the low-temperature condition, ensures the stability of raw materials and products, greatly reduces the decomposition rate, simultaneously separates out generated byproducts in smaller particles, and directly ignores a small amount of liquid remained on the solid after filtration.
A method for preparing hexafluoropropylene trimer by a liquid phase method is characterized by comprising the following steps:
according to the mass parts: adding 0.01-5 parts of metal fluoride, 0.01-3 parts of synergist, 150-containing-silicon-300 parts of hexafluoropropylene dimer and 100-containing-silicon-200 parts of organic solvent into a high-pressure reaction kettle, introducing inert gas, starting stirring, slowly introducing 100-containing-silicon-150 parts of hexafluoropropylene, and reacting for 1-4 hours at 30-100 ℃; and cooling to room temperature after the reaction is finished, discharging the 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 immiscible.
Further, the metal fluoride is cesium fluoride or potassium fluoride or sodium fluoride;
further, 0.5-2 parts of metal fluoride;
further, the metal fluoride is calcined and then ground into powder;
further, the calcination temperature is 400-600 ℃, and the calcination time is 4-10 h;
further, 0.3-1.8 parts of a synergist;
further, the preparation method of the synergist comprises the following steps:
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) and 120 parts of 100-3.2 parts of organic solvent into a closed high-pressure reaction kettle by mass, adding 1.5-3.2 parts of catalyst, stirring at the temperature of 60-77 ℃, keeping the pressure at 1-3Mpa, reacting for 1-4h, and evaporating the solvent and excessive EDT under reduced pressure to obtain the synergist.
Further, the organic solvent for the synergist is one of ethanol, chloroform or N, N-dimethylformamide;
further, the catalyst is one or more than two of triphenylphosphine (PPh3), tripropylphosphine (P-n-Pr3), triethylamine or dipropylamine;
further, the organic solvent is an anhydrous solvent;
further, the organic solvent is one or a combination 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 0.5-5 Mpa.
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 a sulfone group 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 component in the catalyst is realized; contributing to the improvement of the overall efficiency of the catalyst.
(2) The free degree of fluorine anions is reduced by carrying out mercapto-Michael addition reaction on phenyl vinyl sulfone, vinylguanamine and 3, 6-dioxa-1, 8-octanedithiol (EDT) and generating a metal complex with metal fluoride.
Drawings
FIG. 1 is a gas chromatogram of a product of rectification of hexafluoropropylene trimer prepared in example 1.
Detailed Description
The detection method comprises the following steps:
in the specific embodiment of the invention, the content of hexafluoropropylene trimer is measured by a gas phase analysis method, the temperature of a capillary column is 150 ℃, the temperature of a gasification chamber is 200 ℃, the temperature of a detector is 250 ℃, high-purity nitrogen is used as a carrier gas, and the detector is a hydrogen flame ionization detector.
The invention is further illustrated by the following specific examples:
comparative example 1
Adding 5g of metal fluoride, 0.01g of synergist, 150g 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 1h at 30 ℃; after the reaction is finished, cooling to room temperature, and distilling under reduced pressure to remove the solvent; and filtering to obtain hexafluoropropylene trimer.
The metal fluoride is cesium fluoride;
calcining the metal fluoride and grinding into powder;
the calcining temperature is 400 ℃, and the calcining time is 4 hours;
the synergist is 0.3 g;
the preparation method of the synergist comprises the following steps:
1g of phenyl vinyl sulfone, 0.01g of vinylguanamine, 8g of 3, 6-dioxa-1, 8-octanedithiol (EDT) and 100g of organic solvent are added into a closed high-pressure reaction kettle, 1.5g of catalyst is added, the mixture is stirred at the temperature of 60 ℃, the pressure is kept at 1Mpa, the reaction is carried out for 1h, and the solvent and the excessive EDT are evaporated under reduced pressure to obtain the synergist.
The organic solvent for the synergist 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 0.5 Mpa.
As a result: 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 the 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 immiscible.
The metal fluoride is potassium fluoride;
calcining the metal fluoride and grinding into powder;
the calcining temperature is 600 ℃, and the calcining time is 10 hours;
the preparation method of the synergist comprises the following steps:
6g of phenyl vinyl sulfone, 2g of vinylguanamine, 15g of 3, 6-dioxa-1, 8-octanedithiol (EDT) and 120g of organic solvent are added into a closed high-pressure reaction kettle, 3.2g of catalyst is added, the mixture is stirred at 77 ℃, the pressure is kept at 3Mpa, the reaction is carried out for 4 hours, and the solvent and the excessive EDT are evaporated under reduced pressure to obtain the synergist.
The organic solvent for the synergist is trichloromethane;
the catalyst is tripropyl phosphine (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 is 5 Mpa.
As a result: 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 the 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 immiscible.
The metal fluoride is sodium fluoride;
calcining the metal fluoride and grinding into powder;
the calcining temperature is 500 ℃, and the calcining time is 8 hours;
the preparation method of the synergist comprises the following steps:
3g of phenyl vinyl sulfone, 0.5g of vinylguanamine, 10g of 3, 6-dioxa-1, 8-octanedithiol (EDT), 120g of organic solvent and 2.0g of catalyst are added into a closed high-pressure reaction kettle, the mixture is stirred at 67 ℃, the pressure is kept at 2MPa, the reaction is carried out for 3h, and the solvent and the excessive EDT are evaporated under reduced pressure to obtain the synergist.
The organic solvent for the synergist 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 4.2 Mpa.
As a result: 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 the 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 immiscible.
The metal fluoride is sodium fluoride;
calcining the metal fluoride and grinding into powder;
the calcining temperature is 500 ℃, and the calcining time is 80 hours;
the preparation method of the synergist comprises the following steps:
4g of phenyl vinyl sulfone, 1.0g of vinylguanamine, 12g of 3, 6-dioxa-1, 8-octanedithiol (EDT), 120g of organic solvent and 2.4g of catalyst are added into a closed high-pressure reaction kettle, the mixture is stirred at 67 ℃, the pressure is kept at 2MPa, the reaction is carried out for 3h, and the solvent and the excessive EDT are evaporated under reduced pressure to obtain the synergist.
The organic solvent for the synergist is N, N-dimethylformamide;
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 4.8 Mpa.
As a result: 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 the 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 immiscible.
The metal fluoride is cesium fluoride;
calcining the metal fluoride and grinding into powder;
the calcining temperature is 500 ℃, and the calcining time is 8 hours;
the preparation method of the synergist comprises the following steps:
5g of phenyl vinyl sulfone, 1.5g of vinylguanamine, 14g of 3, 6-dioxa-1, 8-octanedithiol (EDT), 120g of organic solvent and 2.8g of catalyst are added into a closed high-pressure reaction kettle, the mixture is stirred at the temperature of 67 ℃, the pressure is kept at 2MPa, the reaction is carried out for 3 hours, and the solvent and the excessive EDT are evaporated under reduced pressure to obtain the synergist.
The organic solvent for the synergist is trichloromethane;
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 4.2 Mpa.
As a result: 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 the 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 immiscible.
The metal fluoride is potassium fluoride;
calcining the metal fluoride and grinding into powder;
the calcining temperature is 600 ℃, and the calcining time is 6 hours;
the preparation method of the synergist comprises the following steps:
6g of phenyl vinyl sulfone, 2g of vinylguanamine, 15g of 3, 6-dioxa-1, 8-octanedithiol (EDT) and 120g of organic solvent are added into a closed high-pressure reaction kettle, 3.2g of catalyst is added, stirring is carried out at 67 ℃, the pressure is kept at 2Mpa, reaction is carried out for 3h, and the solvent and excessive EDT are evaporated under reduced pressure to obtain the synergist.
The organic solvent for the synergist is ethanol;
the catalyst is tripropyl phosphine (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 4.2 Mpa.
As a result: 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 (14)
1. A method for preparing hexafluoropropylene trimer by a liquid phase method comprises the following operation steps:
according to the mass parts: adding 0.01-5 parts of metal fluoride, 0.01-3 parts of synergist, 150-containing-silicon-300 parts of hexafluoropropylene dimer and 100-containing-silicon-200 parts of organic solvent into a high-pressure reaction kettle, introducing inert gas, starting stirring, slowly introducing 100-containing-silicon-150 parts of hexafluoropropylene, and reacting for 1-4 hours at 30-100 ℃; and cooling to room temperature after the reaction is finished, discharging the 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 immiscible.
2. The liquid-phase process for producing a hexafluoropropylene trimer according to claim 1, wherein: the metal fluoride is cesium fluoride or potassium fluoride or sodium fluoride.
3. The liquid-phase process for producing a hexafluoropropylene trimer according to claim 1, wherein: 0.5-2 parts of metal fluoride.
4. The liquid-phase process for producing a hexafluoropropylene trimer according to claim 1, wherein: the metal fluoride is calcined and then ground into a powder.
5. The method for preparing hexafluoropropylene trimer according to claim 4, wherein: the calcination temperature is 400-600 ℃, and the calcination time is 4-10 h.
6. The liquid-phase process for producing a hexafluoropropylene trimer according to claim 1, wherein: 0.3-1.8 parts of synergist.
7. The liquid-phase process for producing a hexafluoropropylene trimer according to claim 1, wherein: the preparation method of the synergist comprises the following steps:
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) and 120 parts of 100-3.2 parts of organic solvent into a closed high-pressure reaction kettle by mass, adding 1.5-3.2 parts of catalyst, stirring at the temperature of 60-77 ℃, keeping the pressure at 1-3Mpa, reacting for 1-4h, and evaporating the solvent and excessive EDT under reduced pressure to obtain the synergist.
8. The liquid-phase process for producing a hexafluoropropylene trimer according to claim 7, wherein: the organic solvent used for the synergist is one of ethanol, trichloromethane or N, N-dimethylformamide.
9. The liquid-phase process for producing a hexafluoropropylene trimer according to claim 7, wherein: the catalyst is one or more than two of triphenylphosphine (PPh3), tripropylphosphine (P-n-Pr3), triethylamine or dipropylamine.
10. The liquid-phase process for producing a hexafluoropropylene trimer according to claim 1, wherein: the organic solvent is an anhydrous solvent.
11. The liquid-phase process for producing a hexafluoropropylene trimer according to claim 1, wherein: the organic solvent is one or a composition of more of acetonitrile, ethylene glycol dimethyl ether, tetrahydrofuran, diethylene glycol dimethyl ether and dimethyl sulfoxide.
12. The liquid-phase process for producing a hexafluoropropylene trimer according to claim 11, wherein: the organic solvent is acetonitrile or dimethyl sulfoxide.
13. The liquid-phase process for producing a hexafluoropropylene trimer according to claim 1, wherein: the reaction temperature is 30-60 ℃.
14. The liquid-phase process for producing a hexafluoropropylene trimer according to claim 1, wherein: the reaction pressure is 0.5-5 Mpa.
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| 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 |
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| 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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| 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 |
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| CN117160497A (en) * | 2023-11-03 | 2023-12-05 | 北京宇极科技发展有限公司 | Catalyst and method for preparing hexafluoropropylene dimer |
| CN117160497B (en) * | 2023-11-03 | 2024-03-08 | 北京宇极科技发展有限公司 | Catalyst and method for preparing hexafluoropropylene dimer |
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