CN115403443A - Preparation method of fluorine-containing olefin - Google Patents
Preparation method of fluorine-containing olefin Download PDFInfo
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- CN115403443A CN115403443A CN202210913737.7A CN202210913737A CN115403443A CN 115403443 A CN115403443 A CN 115403443A CN 202210913737 A CN202210913737 A CN 202210913737A CN 115403443 A CN115403443 A CN 115403443A
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 17
- 239000011737 fluorine Substances 0.000 title claims abstract description 17
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 16
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 17
- 239000000376 reactant Substances 0.000 claims description 15
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 229910001515 alkali metal fluoride Inorganic materials 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 4
- 150000003983 crown ethers Chemical group 0.000 claims description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 4
- AHLATJUETSFVIM-UHFFFAOYSA-M rubidium fluoride Chemical compound [F-].[Rb+] AHLATJUETSFVIM-UHFFFAOYSA-M 0.000 claims description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 4
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 2
- VFTFKUDGYRBSAL-UHFFFAOYSA-N 15-crown-5 Chemical compound C1COCCOCCOCCOCCO1 VFTFKUDGYRBSAL-UHFFFAOYSA-N 0.000 claims description 2
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 claims description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 2
- GVNHOISKXMSMPX-UHFFFAOYSA-N 2-[butyl(2-hydroxyethyl)amino]ethanol Chemical compound CCCCN(CCO)CCO GVNHOISKXMSMPX-UHFFFAOYSA-N 0.000 claims description 2
- MWGATWIBSKHFMR-UHFFFAOYSA-N 2-anilinoethanol Chemical compound OCCNC1=CC=CC=C1 MWGATWIBSKHFMR-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N hydroxylamine group Chemical group NO AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 2
- 150000002443 hydroxylamines Chemical class 0.000 claims description 2
- 229940102253 isopropanolamine Drugs 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 235000003270 potassium fluoride Nutrition 0.000 claims description 2
- 239000011698 potassium fluoride Substances 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 6
- 239000000178 monomer Substances 0.000 abstract description 4
- 238000006384 oligomerization reaction Methods 0.000 abstract description 4
- 238000000746 purification Methods 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 3
- 230000001965 increasing effect Effects 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000012295 chemical reaction liquid Substances 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910000039 hydrogen halide Inorganic materials 0.000 description 2
- 239000012433 hydrogen halide Substances 0.000 description 2
- 238000011403 purification operation Methods 0.000 description 2
- NDMMKOCNFSTXRU-UHFFFAOYSA-N 1,1,2,3,3-pentafluoroprop-1-ene Chemical compound FC(F)C(F)=C(F)F NDMMKOCNFSTXRU-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical class NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010792 warming Methods 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
-
- 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
- B01J31/0239—Quaternary ammonium compounds
-
- 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
- B01J31/0247—Imides, amides or imidates (R-C=NR(OR))
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/20—Olefin oligomerisation or telomerisation
Landscapes
- 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 discloses a preparation method of fluorine-containing olefin. The invention uses the monomer fluorine-containing olefin which can be purchased commercially or prepared by the method known in the field to carry out oligomerization under the action of the catalyst to prepare the fluorine-containing olefin; the reaction liquid composed of the main catalyst, the cocatalyst and the solvent has wider action range, and can catalyze oligomerization of various monomers to prepare fluorine-containing olefin compared with other catalytic systems; the method has the advantages of high conversion rate (the conversion rate can be increased from 40% to more than 80%), few byproducts, stable catalyst activity and simple purification process; the target product is prepared with high selectivity.
Description
Technical Field
The invention relates to a preparation method of fluorine-containing olefin, belonging to the technical field of fluorine-containing fine chemical engineering.
Background
The fluoroolefins (HFOs) have Ozone Depletion Potential (ODP) of 0, low Global Warming Potential (GWP), good thermal properties and safety in use, are good substitutes for chlorofluorocarbons (CFCs), hydrochlorocarbons (HCFCs) and Hydrofluorocarbons (HFCs), and can be used for foaming agents, refrigerants, precision device cleaning agents, fluorine chemical raw materials and the like.
Fluorine-containing olefins are produced in a number of ways, and European patent publication No. EP3303435B1 proposes the reaction of perfluorinated vinylamines with hydride reducing agents to give nitrogen-containing hydrofluoroolefins. British patent publication No. WO2008040969A3, european patent EP0726243A1 dehydrohalogenates hydro (halo) fluoroalkanes using starting materials having the same number of carbon atoms as the target product to obtain the target product. The above method has the following disadvantages: 1. the single conversion rate of the monomer is low, the problem of excessive decomposition of materials exists in the reaction process, the selectivity is poor, and the number of byproducts is large. 2. Before the catalyst is used, complex treatment processes such as high-temperature drying, pre-fluorination and the like are required. 3. The existence of hydrogen halide and other azeotrope with similar boiling point in the product requires multi-step purification operation, and has complex process and high cost. Many patents such as chinese patent publication No. CN101573316B and US patent publication No. US20060106263 propose related purification technologies, which do not efficiently solve the separation and purification problems.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of fluorine-containing olefin.
The technical scheme of the invention is as follows:
a preparation method of fluorine-containing olefin comprises the following steps:
1) Adding the dried main catalyst, cocatalyst and solvent into a reaction kettle, cooling to-40 ℃, and replacing with nitrogen; the dosage of the solvent is 20 to 150 weight percent of the molar weight of the reactant, the dosage of the catalyst is 0.1 to 20 percent of the molar weight of the reactant, and the dosage of the cocatalyst is 0 to 20 percent of the molar weight of the reactant;
2) Heating to the reaction temperature, adding a calculated amount of reactants, adjusting the pressure to 0.1-2 MPa, and reacting for 3-8 h; wherein the reaction temperature is-30 to 200 ℃;
the structure of the reactant is
Wherein R is f4 Is F, R f1 、R f2 、R f3 is-F, - (CH) 2 ) n CH 3 、CF 3 (CF 2 CF 2 O) n -、-(CF 2 ) n CF 3 、-(CF 2 ) n CF(CF 3 ) 2 、-(CF 2 ) n CHF 2 、-(CF 2 ) n CH 2 F、-(CF 2 ) n CH 2 Ph、-(CH 2 ) n CH＝CH 2 、-(CH 2 ) n CH＝CH(CH 2 ) n CH 3 One of them; n is an integer of 0 to 10, and when R f2 Or R f3 is-CF 3 When R is f1 R is the above structure other than-F f1 、R f2 、R f3 The above structures of (a) do not distinguish between cis and trans isomerism;
3) And after the reaction is finished, standing, separating liquid and distilling to obtain the product.
Preferably, the reaction temperature in the step 2) is 30 to 70 ℃. Experiments prove that when the reaction temperature is too low, the catalyst activity is weak. Increasing the temperature can increase the reaction rate, but the reaction is exothermic, and too high reaction temperature causes the equilibrium to move reversely, so that the yield is reduced, and the problem of isomerization of the product also exists. The reaction temperature of 30-70 ℃ is the optimum reaction temperature range, and the reaction rate and the yield of the target product can be both considered.
Preferably, if R is f3 、R f4 Overall electronegativity greater than R f1 、R f2 Overall electronegativity, the reaction equation is as follows:
preferably, the solvent is one or a compound of more than one of ethylene glycol dimethyl ether, sulfolane, dimethyl sulfoxide, acetonitrile, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran and methyl formate;
the catalyst is hydroxylamine or alkali metal fluoride; wherein the hydroxylamines comprise 2-hydroxyethylamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-butyldiethanolamine, isopropanolamine, hydroxyethylethylenediamine and N-phenylethanolamine; alkali metal fluorides include potassium fluoride, cesium fluoride, rubidium fluoride, sodium fluoride;
the cocatalyst is crown ether or ammonium salt; specifically, the crown ethers include 12-crown-2, 15-crown-5, and 18-crown-6; enhancing the solubility of the alkali metal compound; ammonium salts include tetrabutylammonium bromide (TBAB), octadecyltrimethylammonium bromide (OTAB), tetramethylammonium bromide (TMAB).
Further preferably, the solvent is N, N dimethylformamide; the catalyst is N-methyldiethanolamine; the cocatalyst is tetramethylammonium bromide (TMAB).
Preferably, the number of carbon atoms of the reactant is 2 to 12.
More preferably, the number of carbon atoms of the reactant is 2 to 6.
The invention has the beneficial effects that:
1. the method of the invention uses commercially available fluorine-containing olefin or fluorine-containing olefin prepared by a method known in the field to carry out oligomerization reaction under the action of a catalyst to prepare fluorine-containing olefin; specifically, the reaction liquid composed of the main catalyst, the cocatalyst and the solvent has a wider action range, and can catalyze oligomerization of various monomers to prepare fluorine-containing olefin compared with other catalytic systems; the method has the advantages of high conversion rate (the conversion rate can be increased from 40% to more than 80%), few byproducts, stable catalyst activity and simple purification process; the target product is prepared with high selectivity;
2. before the catalyst is used, the catalyst can meet the use requirement through drying; the problems of catalyst coking and activity deterioration do not exist in the reaction process;
3. the method does not need multi-step purification operation; the crude product does not contain hydrogen halide, and the high-efficiency separation of the product can be realized through liquid separation and distillation.
Detailed Description
Some embodiments of the invention are described in detail below.
Example 1
A process for preparing fluoroolefin, which comprises charging 2.97g (0.025 mol) of N-methyldiethanolamine, 6g (0.025 mol) of tetramethylammonium bromide and 39.6g of N, N-dimethylformamide into a high-pressure reactor. Stirring at 400r/min, cooling to-40 deg.C, replacing with nitrogen, and discharging oxygen. After the temperature is raised to about 50 ℃, 132g (1 mol) of 1,1,2,3,3-pentafluoropropene are introduced, the reaction temperature is less than or equal to 70 ℃, the pressure is adjusted to about 0.6MPa, and the reaction is carried out for 4 hours. Then cooling to room temperature, standing, separating liquid and distilling to obtain CF 3 CFCF 2 HCF＝CFCF 2 H, yield 85%.
Example 2
A process for producing fluoroolefin as described in example 1, except that 2.97g (0.025 mol) of N-methyldiethanolamine, 6g (0.025 mol) of tetramethylammonium bromide and 75g of N, N-dimethylformamide were charged in an autoclave. Stirring at 400r/min, cooling to-40 deg.C, displacing completely, and discharging oxygen. Then heating to about 50 ℃, adding 250g (1 mol) of perfluoro-2-methyl-2-butylene, reacting at the temperature of less than or equal to 70 ℃, adjusting the pressure to about 0.6MPa by using high-purity nitrogen, and reacting for 5 hours. After the reaction is finished, cooling to room temperature, standing for liquid separation and distilling to obtain (CF) 3 ) 2 C＝CCF 3 C(CF 3 ) 2 CF 2 CF 3 The yield thereof was found to be 82%.
Example 3
A process for producing a fluoroolefin as described in example 1, except that 5.95g (0.05 mol) of N-methyldiethanolamine, 12g (0.05 mol) of tetramethylammonium bromide and 57.6g of N, N-dimethylformamide were charged into the autoclave. Stirring at 400r/min, cooling to-40 deg.C, displacing completely, and discharging oxygen in the system. After the temperature is raised to about 50 ℃,1,1,2-trifluoropropene gas is introduced192g (2 mol), the reaction temperature is less than or equal to 70 ℃, the pressure is adjusted to about 0.6MPa, and the reaction is carried out for 4 hours. Then cooling to room temperature, standing for liquid separation, and distilling to obtain CH 3 CF 3 CFCF＝CFCH 3 The yield thereof was found to be 87%.
The effect of different catalysts, co-catalysts, reaction times and reaction temperatures on the reaction is shown in table 1 below.
As can be seen from the above experimental data, among them, N-methyldiethanolamine is a more preferable catalyst, and tetramethylammonium bromide is a cocatalyst; the optimum reaction temperature is 50 ℃.
It can be seen from comparative examples 1-3 that the reactants also had an effect on the experiment and that the yield of lower olefins was relatively high.
Claims (7)
1. A preparation method of fluorine-containing olefin is characterized by comprising the following steps:
1) Adding the dried main catalyst, cocatalyst and solvent into a reaction kettle, cooling to-40 ℃, and replacing with nitrogen; the dosage of the solvent is 20 to 150 weight percent of the molar weight of the reactant, the dosage of the catalyst is 0.1 to 20 percent of the molar weight of the reactant, and the dosage of the cocatalyst is 0 to 20 percent of the molar weight of the reactant;
2) Heating to the reaction temperature, adding a calculated amount of reactants, adjusting the pressure to 0.1-2 MPa, and reacting for 3-8 h; wherein the reaction temperature is-30-200 ℃;
the structure of the reactant is
Wherein R is f4 Is F, R f1 、R f2 、R f3 is-F, - (CH) 2 ) n CH 3 、CF 3 (CF 2 CF 2 O) n -、-(CF 2 ) n CF 3 、-(CF 2 ) n CF(CF 3 ) 2 、-(CF 2 ) n CHF 2 、-(CF 2 ) n CH 2 F、-(CF 2 ) n CH 2 Ph、-(CH 2 ) n CH＝CH 2 、-(CH 2 ) n CH＝CH(CH 2 ) n CH 3 One of them; n is an integer of 0 to 10, and when R f2 Or R f3 is-CF 3 When R is f1 R is the above structure other than-F f1 、R f2 、R f3 The above structures of (a) do not distinguish between cis and trans isomerism;
3) And after the reaction is finished, standing, separating liquid and distilling to obtain the product.
2. The method according to claim 1, wherein the reaction temperature in the step 2) is 30 to 70 ℃.
3. The method for producing a fluoroolefin according to claim 1, wherein if R is f3 、R f4 Overall electronegativity greater than R f1 、R f2 Overall electronegativity, the reaction equation is as follows:
4. the method for preparing fluoroolefin according to claim 1, wherein the solvent is one or a mixture of more than one of ethylene glycol dimethyl ether, sulfolane, dimethyl sulfoxide, acetonitrile, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran and methyl formate;
the catalyst is hydroxylamine or alkali metal fluoride; wherein the hydroxylamines comprise 2-hydroxyethylamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-butyldiethanolamine, isopropanolamine, hydroxyethylethylenediamine and N-phenylethanolamine; alkali metal fluorides include potassium fluoride, cesium fluoride, rubidium fluoride, sodium fluoride;
the cocatalyst is crown ether or ammonium salt; specifically, the crown ethers include 12-crown-2, 15-crown-5, and 18-crown-6; ammonium salts include tetrabutylammonium bromide (TBAB), octadecyltrimethylammonium bromide (OTAB), tetramethylammonium bromide (TMAB).
5. The method according to claim 4, wherein the solvent is N, N-dimethylformamide; the catalyst is N-methyldiethanolamine; the cocatalyst is tetramethylammonium bromide (TMAB).
6. The method according to claim 1, wherein the number of carbon atoms of the reactant is 2 to 12.
7. The method according to claim 6, wherein the number of carbon atoms of the reactant is 2 to 6.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN113816824A (en) * | 2021-09-07 | 2021-12-21 | 浙江巨化技术中心有限公司 | Preparation method and application of perfluoroolefin oligomer |
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2022
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| JPS51125307A (en) * | 1975-04-17 | 1976-11-01 | Central Glass Co Ltd | Process for preparation of hexafluoropropene oligomers |
| JPS51149210A (en) * | 1975-06-16 | 1976-12-22 | Central Glass Co Ltd | Process for preparation of tetrafluoroethylene oligomers |
| WO2013185626A1 (en) * | 2012-06-15 | 2013-12-19 | 中化蓝天集团有限公司 | Preparation method for perfluoro-2-methyl-3-pentanone and intermediate |
| CN105837398A (en) * | 2016-06-27 | 2016-08-10 | 浙江诺亚氟化工有限公司 | Industrial production method and production apparatus for perfluoro-2-methyl-2-pentene |
| CN106117397A (en) * | 2016-07-20 | 2016-11-16 | 金华永和氟化工有限公司 | A kind of fluoropolymer concentrates dispersion liquid and the method preparing fluoropolymer thereof |
| CN108383681A (en) * | 2018-03-19 | 2018-08-10 | 浙江巨化技术中心有限公司 | A kind of preparation method of perfluoro-2-methyl-2-amylene |
| CN110950734A (en) * | 2019-10-21 | 2020-04-03 | 浙江诺亚氟化工有限公司 | Full-submerged type cleaning fire extinguishing agent used in unmanned place and application thereof |
| CN113816824A (en) * | 2021-09-07 | 2021-12-21 | 浙江巨化技术中心有限公司 | Preparation method and application of perfluoroolefin oligomer |
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