CN113968770A - A kind of synthetic method of hexafluoropropylene trimer with low proportion of T1 isomer - Google Patents
A kind of synthetic method of hexafluoropropylene trimer with low proportion of T1 isomer Download PDFInfo
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- CN113968770A CN113968770A CN202111302629.8A CN202111302629A CN113968770A CN 113968770 A CN113968770 A CN 113968770A CN 202111302629 A CN202111302629 A CN 202111302629A CN 113968770 A CN113968770 A CN 113968770A
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- hexafluoropropylene
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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 43
- 238000010189 synthetic method Methods 0.000 title 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 36
- -1 alkali metal salt Chemical class 0.000 claims abstract description 19
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 17
- 239000003880 polar aprotic solvent Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 238000006384 oligomerization reaction Methods 0.000 claims abstract description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 150000003983 crown ethers Chemical class 0.000 claims description 6
- GKKCIDNWFBPDBW-UHFFFAOYSA-M potassium cyanate Chemical compound [K]OC#N GKKCIDNWFBPDBW-UHFFFAOYSA-M 0.000 claims description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims description 4
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 2
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 claims description 2
- CRWNQZTZTZWPOF-UHFFFAOYSA-N 2-methyl-4-phenylpyridine Chemical compound C1=NC(C)=CC(C=2C=CC=CC=2)=C1 CRWNQZTZTZWPOF-UHFFFAOYSA-N 0.000 claims description 2
- 229910001508 alkali metal halide Inorganic materials 0.000 claims description 2
- 150000008045 alkali metal halides Chemical class 0.000 claims description 2
- 125000005360 alkyl sulfoxide group Chemical group 0.000 claims description 2
- QUPYHCHUQVNFJW-UHFFFAOYSA-M cesium;thiocyanate Chemical compound [Cs+].[S-]C#N QUPYHCHUQVNFJW-UHFFFAOYSA-M 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 claims description 2
- ZVCDLGYNFYZZOK-UHFFFAOYSA-M sodium cyanate Chemical group [Na]OC#N ZVCDLGYNFYZZOK-UHFFFAOYSA-M 0.000 claims description 2
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical group [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 claims description 2
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical group [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 abstract description 9
- 238000001308 synthesis method Methods 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 239000007789 gas Substances 0.000 description 9
- 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 description 7
- 230000003213 activating effect Effects 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 238000004817 gas chromatography Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- RMHCWMIZBMGHKV-UHFFFAOYSA-N 1,1,2,3,3,4,4,5,5,6,6,6-dodecafluorohex-1-ene Chemical compound FC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F RMHCWMIZBMGHKV-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000000539 dimer Substances 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000012038 nucleophile Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- UAFOIVDGAVVKTE-UHFFFAOYSA-N 1,1,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-octadecafluoronon-1-ene Chemical compound FC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F UAFOIVDGAVVKTE-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A synthesis method of hexafluoropropylene trimer with a low T1 isomer ratio comprises the steps of adding tetrahydrofuran in a certain proportion into a polar aprotic solvent, introducing hexafluoropropylene gas at the reaction temperature of 60-120 ℃ and the pressure of 0.2-1 MPa by taking an alkali metal salt as a catalyst to carry out oligomerization reaction, wherein the mass ratio of the tetrahydrofuran to the polar aprotic solvent is 1: 1-20. The invention has the advantages that the reaction product is mainly hexafluoropropylene trimer, and the proportion of an isomer T1 in the trimer can be greatly reduced, so that the selectivity of T2 and T3 isomers is correspondingly improved.
Description
Technical Field
The invention relates to the field of catalysis, in particular to a method for synthesizing hexafluoropropylene tripolymer with low proportion of T1 isomer.
Background
Hexafluoropropylene trimer (a species of perfluorononene) is an important fluorochemical with a relative molecular mass of 450.07 and formula C9F18The boiling point is 110-115 ℃, the density is 1.83g/mL (25 ℃), and the flash point is 24 ℃. The hexafluoropropylene trimer has three structural forms of T1, T2 and T3, wherein T1 has a highly branched structure and has electronegative substituent groups, so that the hexafluoropropylene trimer has very special reactivity. T2 is more reactive with nucleophiles and T1 is less active, whereas T3 has no ability to react with nucleophiles but is capable of isomerizing to T2 in the presence of triethylamine. The hexafluoropropylene trimer can be used as a perfluorinated solvent, such as a diluent for AF coating, a raw material for preparing fluorine-containing monomers, fluorine-containing surfactants, water and oil repellent finishing agents and the like. Among them, the diluent for AF coating is a main application field, and when used in this field, the content of T1 isomer having strong activity is required to be as low as possible.
At present, hexafluoropropylene tripolymer has various synthesis modes, most of the hexafluoropropylene tripolymer is prepared by a gas phase and liquid phase method containing various solvents and catalysts, and the hexafluoropropylene tripolymer with a higher proportion is obtained, but how to synthesize the hexafluoropropylene tripolymer with a low proportion of T1 isomer is not reported. In the prior literature reports, the product selectivity of hexafluoropropylene oligomerization reaction is generally limited to the discussion between dimer and trimer, and few research reports about the selective regulation and control between respective isomers of dimer or trimer exist.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provide a hexafluoropropylene oligomerization method which mainly takes trimer selectivity and has low proportion of T1 isomer in the trimer, wherein the proportion of T1 isomer is not more than 5%.
In order to achieve the purpose, the invention adopts the following technical scheme:
a synthesis method of hexafluoropropylene trimer with a low T1 isomer ratio comprises the steps of adding tetrahydrofuran in a certain proportion into a polar aprotic solvent, introducing hexafluoropropylene gas at the reaction temperature of 60-120 ℃ and the pressure of 0.2-1 MPa by taking an alkali metal salt as a catalyst to carry out oligomerization reaction, wherein the mass ratio of the tetrahydrofuran to the polar aprotic solvent is 1: 1-20. The main products of hexafluoropropylene oligomerization in these solvents are hexafluoropropylene trimer and perfluorohexene.
The alkali metal salt comprises an alkali metal cyanide, an alkali metal cyanate, an alkali metal thiocyanate, or a catalyst combination of an alkali metal halide and a crown ether.
The alkali metal cyanide is selected from NaCN, KCN and CsCN; the alkali metal cyanate is selected from NaOCN, KOCN and CsOCN; the alkali metal thiocyanate is selected from NaSCN, KSCN and CsSCN.
The polar aprotic solvent is at least one selected from ethers, alkyl nitriles, alkyl sulfoxides, and alkylamides.
The polar aprotic solvent comprises at least one of acetonitrile, dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, ethylene glycol dimethyl ether, sulfolane, diethylene glycol monomethyl ether, propylene glycol monomethyl ether and diethylene glycol dibutyl ether.
The polar aprotic solvent is N, N-dimethylacetamide.
The mass ratio of tetrahydrofuran to polar aprotic solvent is 1:10, with a high proportion of tetrahydrofuran reducing the proportion of T1 to a very low level but increasing the proportion of perfluorohexene.
The reaction temperature is 100 ℃, too low a temperature increases the proportion of perfluorohexene, and too high a temperature increases the proportion of T1.
The pressure is 0.5MPa, the reaction rate is slow when the pressure is too low, the proportion of generated perfluorohexene is high, and the reaction rate is too high when the pressure is too high, so that the heat release is large, the danger is caused, and the number of byproducts is large.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
according to the invention, tetrahydrofuran in a certain proportion is added into a common aprotic polar solvent to serve as a mixed solvent, so that the catalytic effects of high trimer selectivity and low T1 selectivity in trimer can be simultaneously obtained. The addition of tetrahydrofuran modulates the polarity of the mixed solvent, and the selectivity of T2 and T3 isomers is more matched with the polarity of the mixed solvent, thereby promoting the increase of the selectivity of T2 and T3 and inhibiting the selectivity of T1.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention clearer and more obvious, the present invention is further described in detail below with reference to the following embodiments.
Example 1
After 15ml of N, N-dimethylformamide, 5ml of tetrahydrofuran and 2g of KOCN were added to a 100ml autoclave with stirring and heating, the autoclave was sealed with a lid, the air in the autoclave was removed by a vacuum extractor, nitrogen gas was introduced, vacuum was again applied, and the pressure in the autoclave was made zero after three times of replacement. Raising the temperature to 100 ℃, stirring at the speed of 600 revolutions per minute, activating for 1h, and introducing hexafluoropropylene gas under the gauge pressure of 0.5 MPa. After 10min, the air inlet valve is closed, stirring is continued to normal pressure at 100 ℃, and then stirring and cooling are stopped. And transferring the reaction product to a separating funnel, standing and separating a lower layer of light yellow transparent hexafluoropropylene oligomer, and washing and drying the hexafluoropropylene oligomer. Through gas chromatography analysis, the mass content of the hexafluoropropylene dimer is 7.9%, and the content of the trimer is 93.1%. The mass content of T1 isomer in the hexafluoropropylene trimer was 4.2%.
Example 2
After 15ml of dimethyl sulfoxide, 5ml of tetrahydrofuran and 2g of KOCN were added to a 100ml stirred and heated autoclave, the autoclave was sealed, the air in the autoclave was removed by a vacuum extractor, nitrogen gas was introduced, vacuum was again applied, and the pressure in the autoclave was made zero after three times of replacement. Raising the temperature to 100 ℃, stirring at the speed of 600 revolutions per minute, activating for 1h, and introducing hexafluoropropylene gas under the gauge pressure of 0.5 MPa. After 10min, the air inlet valve is closed, stirring is continued to normal pressure at 100 ℃, and then stirring and cooling are stopped. And transferring the reaction product to a separating funnel, standing and separating a lower layer of light yellow transparent hexafluoropropylene oligomer, and washing and drying the hexafluoropropylene oligomer. Through gas chromatography analysis, the mass content of the hexafluoropropylene dimer is 9.1%, and the trimer content is 90.9%. The hexafluoropropylene trimer contained 3.2% by mass of the T1 isomer.
Example 3
After 15ml of N, N-dimethylacetamide, 5ml of tetrahydrofuran, 2gKF and 1g of crown ether were added to a 100ml autoclave heated with stirring, the autoclave was sealed. After the air in the kettle is removed by a vacuumizing device, nitrogen is introduced, the kettle is vacuumized again, and the pressure in the kettle is zero after three times of replacement. Raising the temperature to 100 ℃, stirring at the speed of 600 revolutions per minute, activating for 1h, and introducing hexafluoropropylene gas under the gauge pressure of 0.5 MPa. After 10min, the air inlet valve is closed, stirring is continued to normal pressure at 100 ℃, and then stirring and cooling are stopped. And transferring the reaction product to a separating funnel, standing and separating a lower layer of light yellow transparent hexafluoropropylene oligomer, and washing and drying the hexafluoropropylene oligomer. Through gas chromatography analysis, the mass content of the hexafluoropropylene dimer is 8.4%, and the trimer content is 91.6%. The mass content of T1 isomer in the hexafluoropropylene trimer was 1.6%.
Example 4
After 15ml of DMSO, 5ml of tetrahydrofuran and 2gKF and 1g of crown ether were added to a 100ml volume autoclave heated with stirring, the autoclave was sealed. After the air in the kettle is removed by a vacuumizing device, nitrogen is introduced, the kettle is vacuumized again, and the pressure in the kettle is zero after three times of replacement. Raising the temperature to 100 ℃, stirring at the speed of 600 revolutions per minute, activating for 1h, and introducing hexafluoropropylene gas under the gauge pressure of 0.5 MPa. After 10min, the air inlet valve is closed, stirring is continued to normal pressure at 100 ℃, and then stirring and cooling are stopped. And transferring the reaction product to a separating funnel, standing and separating a lower layer of light yellow transparent hexafluoropropylene oligomer, and washing and drying the hexafluoropropylene oligomer. Through gas chromatography analysis, the mass content of the hexafluoropropylene dimer is 8.8%, and the trimer content is 91.2%. The mass content of the T1 isomer in the hexafluoropropylene trimer was 2.2%.
Comparative example 1
After 15ml of N, N-dimethylformamide and 2g of KOCN were added to a 100ml stirred and heated autoclave, the autoclave was sealed, the air in the autoclave was removed by a vacuum extractor, nitrogen gas was introduced, and the autoclave was evacuated again to zero the pressure after three times of replacement. Raising the temperature to 100 ℃, stirring at the speed of 600 revolutions per minute, activating for 1h, and introducing hexafluoropropylene gas under the gauge pressure of 0.5 MPa. After 10min, the air inlet valve is closed, stirring is continued to normal pressure at 100 ℃, and then stirring and cooling are stopped. And transferring the reaction product to a separating funnel, standing and separating a lower layer of light yellow transparent hexafluoropropylene oligomer, and washing and drying the hexafluoropropylene oligomer. Through gas chromatography analysis, the mass content of hexafluoropropylene dimer is 7.5%, and the trimer content is 92.5%. The mass content of the T1 isomer in the hexafluoropropylene trimer was 47%.
Comparative example 2
After 15ml of N, N-dimethylacetamide, 2gKF and 1g of crown ether were added to a 100ml volume autoclave heated with stirring, the autoclave was sealed. After the air in the kettle is removed by a vacuumizing device, nitrogen is introduced, the kettle is vacuumized again, and the pressure in the kettle is zero after three times of replacement. Raising the temperature to 100 ℃, stirring at the speed of 600 revolutions per minute, activating for 1h, and introducing hexafluoropropylene gas under the gauge pressure of 0.5 MPa. After 10min, the air inlet valve is closed, stirring is continued to normal pressure at 100 ℃, and then stirring and cooling are stopped. And transferring the reaction product to a separating funnel, standing and separating a lower layer of light yellow transparent hexafluoropropylene oligomer, and washing and drying the hexafluoropropylene oligomer. Through gas chromatography analysis, the mass content of the hexafluoropropylene dimer is 8.3%, and the trimer content is 91.7%. The mass content of the T1 isomer in the hexafluoropropylene trimer was 39%.
Comparative example 3
After 15ml of tetrahydrofuran, 2gKF and 1g of crown ether were introduced into a 100ml autoclave heated with stirring and sealed. After the air in the kettle is removed by a vacuumizing device, nitrogen is introduced, the kettle is vacuumized again, and the pressure in the kettle is zero after three times of replacement. Raising the temperature to 100 ℃, stirring at the speed of 600 revolutions per minute, activating for 1h, and introducing hexafluoropropylene gas under the gauge pressure of 0.5 MPa. After 10min, the air inlet valve is closed, stirring is continued to normal pressure at 100 ℃, and then stirring and cooling are stopped. And transferring the reaction product to a separating funnel, standing and separating a lower layer of light yellow transparent hexafluoropropylene oligomer, and washing and drying the hexafluoropropylene oligomer. Through gas chromatography analysis, the mass content of the hexafluoropropylene dimer is 54.1%, and the trimer content is 45.9%. The mass content of the T1 isomer in the hexafluoropropylene trimer was 0.5%.
From the above examples and comparative examples, it is clear that the selectivity for dimer is higher, reaching 54.1%, although the selectivity for T1 is lower (1.2%) using pure tetrahydrofuran as the reaction solvent. The selectivity of the trimer is excellent by using aprotic polar solvents commonly used in the field, such as dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and the like, but the selectivity of T1 is higher at the moment, and is generally more than 20%. However, the current patents and literature reports that it is difficult to simultaneously obtain a catalytic result with high trimer selectivity and low T1 selectivity in the trimer. According to the invention, tetrahydrofuran is added into the aprotic polar solvent, so that a reaction product is mainly hexafluoropropylene trimer, the proportion of an isomer T1 in the trimer can be greatly reduced, and the selectivity of T2 and T3 isomers is correspondingly improved.
Claims (8)
1. A method for synthesizing hexafluoropropylene trimer with low T1 isomer ratio, which is characterized in that: adding tetrahydrofuran in a certain proportion into a polar aprotic solvent, introducing hexafluoropropylene gas at the reaction temperature of 60-120 ℃ and under the pressure of 0.2-1 MPa by taking an alkali metal salt as a catalyst to perform oligomerization reaction, wherein the mass ratio of the tetrahydrofuran to the polar aprotic solvent is 1: 1-20.
2. A process for the synthesis of hexafluoropropylene trimers of low percentage of T1 isomers according to claim 1, wherein: the alkali metal salt comprises an alkali metal cyanide, an alkali metal cyanate, an alkali metal thiocyanate, or a catalyst combination of an alkali metal halide and a crown ether.
3. A process for the synthesis of hexafluoropropylene trimers of low percentage of T1 isomers according to claim 2, wherein: the alkali metal cyanide is selected from NaCN, KCN and CsCN; the alkali metal cyanate is selected from NaOCN, KOCN and CsOCN; the alkali metal thiocyanate is selected from NaSCN, KSCN and CsSCN.
4. A process for the synthesis of hexafluoropropylene trimers of low percentage of T1 isomers according to claim 1, wherein: the polar aprotic solvent is at least one selected from ethers, alkyl nitriles, alkyl sulfoxides, and alkylamides.
5. The process for the synthesis of hexafluoropropylene trimers of low proportion of T1 isomers according to claim 4, wherein: the polar aprotic solvent comprises at least one of acetonitrile, dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, ethylene glycol dimethyl ether, sulfolane, diethylene glycol monomethyl ether, propylene glycol monomethyl ether and diethylene glycol dibutyl ether.
6. The process for the synthesis of hexafluoropropylene trimers of low proportion of T1 isomers according to claim 4, wherein: the polar aprotic solvent is N, N-dimethylacetamide.
7. A process for the synthesis of hexafluoropropylene trimers of low percentage of T1 isomers according to claim 1, wherein: the mass ratio of the tetrahydrofuran to the polar aprotic solvent is 1: 10.
8. A process for the synthesis of hexafluoropropylene trimers of low percentage of T1 isomers according to claim 1, wherein: the reaction temperature is 100 ℃, and the pressure is 0.5 MPa.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116102398A (en) * | 2023-02-23 | 2023-05-12 | 齐鲁中科光物理与工程技术研究院 | Preparation method of hexafluoropropylene trimer with T-2 configuration |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1944360A (en) * | 2006-10-17 | 2007-04-11 | 山东东岳高分子材料有限公司 | Process for preparing perfluoro nonene |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1944360A (en) * | 2006-10-17 | 2007-04-11 | 山东东岳高分子材料有限公司 | Process for preparing perfluoro nonene |
Non-Patent Citations (1)
| Title |
|---|
| DMOWSKI, WOJCIECH 等: "The Use of Crown Ethers in the Synthesis of Hexafluoropropene and Tetrafluoroethylene Oligomers", 《JOURNAL OF FLUORINE CHEMISTRY》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116102398A (en) * | 2023-02-23 | 2023-05-12 | 齐鲁中科光物理与工程技术研究院 | Preparation method of hexafluoropropylene trimer with T-2 configuration |
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