CN117342922A - Method for preparing 2, 3-tetrafluoropropene and 1, 3-tetrafluoropropene - Google Patents
Method for preparing 2, 3-tetrafluoropropene and 1, 3-tetrafluoropropene Download PDFInfo
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- CN117342922A CN117342922A CN202311130298.3A CN202311130298A CN117342922A CN 117342922 A CN117342922 A CN 117342922A CN 202311130298 A CN202311130298 A CN 202311130298A CN 117342922 A CN117342922 A CN 117342922A
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- tetrafluoropropene
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- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 61
- FFTOUVYEKNGDCM-OWOJBTEDSA-N (e)-1,3,3-trifluoroprop-1-ene Chemical compound F\C=C\C(F)F FFTOUVYEKNGDCM-OWOJBTEDSA-N 0.000 claims abstract description 34
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 claims abstract description 18
- HMAHQANPHFVLPT-UHFFFAOYSA-N 1,3,3-trifluoroprop-1-yne Chemical compound FC#CC(F)F HMAHQANPHFVLPT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000003682 fluorination reaction Methods 0.000 claims abstract description 10
- 239000007791 liquid phase Substances 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 6
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical group C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims abstract description 5
- 238000007259 addition reaction Methods 0.000 claims abstract description 3
- 239000000460 chlorine Substances 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- -1 dodecyltrimethylammonium cation Chemical class 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000012670 alkaline solution Substances 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000003444 phase transfer catalyst Substances 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 4
- 150000003983 crown ethers Chemical group 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 claims description 3
- 229920002584 Polyethylene Glycol 6000 Polymers 0.000 claims description 3
- 229920002594 Polyethylene Glycol 8000 Polymers 0.000 claims description 3
- 239000004353 Polyethylene glycol 8000 Substances 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 3
- YSSSPARMOAYJTE-UHFFFAOYSA-N dibenzo-18-crown-6 Chemical compound O1CCOCCOC2=CC=CC=C2OCCOCCOC2=CC=CC=C21 YSSSPARMOAYJTE-UHFFFAOYSA-N 0.000 claims description 3
- BBGKDYHZQOSNMU-UHFFFAOYSA-N dicyclohexano-18-crown-6 Chemical compound O1CCOCCOC2CCCCC2OCCOCCOC2CCCCC21 BBGKDYHZQOSNMU-UHFFFAOYSA-N 0.000 claims description 3
- 229940057838 polyethylene glycol 4000 Drugs 0.000 claims description 3
- 229940093429 polyethylene glycol 6000 Drugs 0.000 claims description 3
- 235000019446 polyethylene glycol 8000 Nutrition 0.000 claims description 3
- 229940085678 polyethylene glycol 8000 Drugs 0.000 claims description 3
- REACWASHYHDPSQ-UHFFFAOYSA-N 1-butylpyridin-1-ium Chemical compound CCCC[N+]1=CC=CC=C1 REACWASHYHDPSQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000003985 15-crown-5 derivatives Chemical group 0.000 claims description 2
- 229910015900 BF3 Inorganic materials 0.000 claims description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 claims description 2
- GPWHDDKQSYOYBF-UHFFFAOYSA-N ac1l2u0q Chemical compound Br[Br-]Br GPWHDDKQSYOYBF-UHFFFAOYSA-N 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- OHMBHFSEKCCCBW-UHFFFAOYSA-N hexane-2,5-diol Chemical compound CC(O)CCC(C)O OHMBHFSEKCCCBW-UHFFFAOYSA-N 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 claims description 2
- 150000003608 titanium Chemical class 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims 2
- 238000002360 preparation method Methods 0.000 abstract description 17
- 239000001257 hydrogen Substances 0.000 abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 5
- 150000002500 ions Chemical class 0.000 description 18
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 12
- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropene Chemical compound FC(=C)C(F)(F)F FXRLMCRCYDHQFW-UHFFFAOYSA-N 0.000 description 8
- 238000012512 characterization method Methods 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- 238000007033 dehydrochlorination reaction Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- SMCNZLDHTZESTK-UHFFFAOYSA-N 2-chloro-1,1,1,2-tetrafluoropropane Chemical compound CC(F)(Cl)C(F)(F)F SMCNZLDHTZESTK-UHFFFAOYSA-N 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- GVVUPGXFVJLPDE-OWOJBTEDSA-N (e)-1,3,3,3-tetrachloroprop-1-ene Chemical compound Cl\C=C\C(Cl)(Cl)Cl GVVUPGXFVJLPDE-OWOJBTEDSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 150000001793 charged compounds Chemical class 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000006298 dechlorination reaction Methods 0.000 description 2
- 238000005796 dehydrofluorination reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- SUAMPXQALWYDBK-UHFFFAOYSA-N 1,1,1,2,2,3-hexafluoropropane Chemical compound FCC(F)(F)C(F)(F)F SUAMPXQALWYDBK-UHFFFAOYSA-N 0.000 description 1
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 1
- VFTFKUDGYRBSAL-UHFFFAOYSA-N 15-crown-5 Chemical compound C1COCCOCCOCCOCCO1 VFTFKUDGYRBSAL-UHFFFAOYSA-N 0.000 description 1
- OQISUJXQFPPARX-UHFFFAOYSA-N 2-chloro-3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C(Cl)=C OQISUJXQFPPARX-UHFFFAOYSA-N 0.000 description 1
- PLTIOZOVDUUXDQ-UHFFFAOYSA-N 3,3-dichloro-1,1,1-trifluoropropane Chemical compound FC(F)(F)CC(Cl)Cl PLTIOZOVDUUXDQ-UHFFFAOYSA-N 0.000 description 1
- 229910016569 AlF 3 Inorganic materials 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 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
- C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
- C07C17/087—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/23—Preparation of halogenated hydrocarbons by dehalogenation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a process for preparing 2, 3-tetrafluoropropene and 1, 3-tetrafluoropropene comprising: step one, in the presence of an aliphatic alcohol proton solvent, 1, 2-dichloro-3, 3-trifluoropropene reacts with metal to prepare trifluoropropyne; step two, under the action of a liquid phase fluorination catalyst, performing addition reaction on trifluoropropyne and HF to prepare 2, 3-tetrafluoropropene and 1, 3-tetrafluoropropene. The preparation method of the invention has mild reaction conditions and does not involve hydrogen. The selectivity of the product prepared by the method is higher: the selectivity of trifluoropropyne reaches 99.5%, and the total selectivity of 2, 3-tetrafluoropropene and 1, 3-tetrafluoropropene reaches 98.5%.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, relates to hydrofluoroolefin, and in particular relates to a method for preparing 2, 3-tetrafluoropropene and 1, 3-tetrafluoropropene.
Background
Hydrofluoroolefins (HFOs) have zero ozone depletion potential and low greenhouse effect potential, and have become a hot spot for research in the fluorocarbon industry in various countries. 2, 3-tetrafluoropropene (HFO-1234 yf) and 1, 3-tetrafluoropropene (HFO-1234 ze) are useful refrigerants, blowing agents, fire extinguishing agents, heat transfer media, propellants, gaseous dielectrics, sterilant carriers, power cycle working fluids, polymeric monomers and pharmaceutical, pesticide intermediates by virtue of their excellent physicochemical and environmental properties.
WO2009153493 discloses a process for preparing HFO-1234yf starting from 1,2, 3-hexafluoropropane (HFC-236 cb) by first reacting hydrogen with a catalyst Ni-Cr/AlF 3 In the presence of HFC-236cb to produce 1,2, 3-pentafluoropropene (HFO-1225 ye), then hydrogenating HFO-1225ye to produce 1,2, 3-pentafluoropropane (HFC-245 eb), and finally dehydrofluorinating in the presence of hydrogen to produce HFO-1234yf.
US20110190554 discloses a process for the synthesis of HFO-1234yf from 1,2, 3-Hexafluoropropylene (HFP) as starting material by four steps of hydrogenation, dehydrofluorination, hydrogenation, dehydrofluorination.
In the above synthesis process, the raw material cost is high, stoichiometric hydrogen needs to be introduced, and the hydrogenation step needs to use a higher molar ratio to control the reaction heat, and introducing excessive hydrogen at a higher temperature increases the related safety risk.
US2011207975 discloses a process for the preparation of 1,2, 3-Tetrachloropropene (TCP) or 1,2, 3-pentachloropropane (HCC-240 db)A method of synthesizing HFO-1234yf. The method comprises the steps of firstly adding Cr to the steel 2 O 3 In the presence of a catalyst, HF gas phase fluorination of TCP or HCC-240db is carried out in a first reactor to give 2-chloro-3, 3-trifluoropropene (HCFC-1233 xf), followed by SbCl 5 Under the action, HCFC-1233xf is liquid-phase fluorinated in the second reactor to obtain 2-chloro-1, 2-tetrafluoropropane (HCFC-244 bb), and finally HCFC-244bb dehydrochlorination is carried out in the third reactor to obtain HFO-1234yf. CN200980163128.7 discloses a process for preparing HFO-1234yf from 2, 3-dichloro-1, 1-trifluoropropane (HCFC-243 db) via HCFC-1233xf, HCFC-244 bb. In the preparation method, firstly, the used chromium-based catalyst can cause damage to human bodies, and particularly, high-valence chromium has strong carcinogenic action and can cause serious damage; secondly, the method relates to intermediates HCFC-1233xf and HCFC-244bb which have similar boiling points and azeotropic properties, and the two substances are easy to form azeotropes with HF, so that the three separation processes are extremely complex and the separation difficulty is extremely high; finally, when HCFC-244bb is dehydrochlorinated to produce HFO-1234yf, the presence of HCFO-1233xf and HF impurities can severely impact the life of the dehydrochlorination catalyst and product selectivity.
In view of the above, the current process for preparing HFO-1234yf has disadvantages such as expensive raw materials, unfriendly catalyst, difficult separation of reaction intermediates, low selectivity of target products, and the like, and thus continuous improvement is required to obtain a more efficient preparation process.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a method for preparing 2, 3-tetrafluoropropene and 1, 3-tetrafluoropropene, which solves the technical problems that the reaction condition of the preparation method in the prior art is not mild enough and the intermediate is not easy to separate.
In order to solve the technical problems, the invention adopts the following technical scheme:
a process for preparing 2, 3-tetrafluoropropene and 1, 3-tetrafluoropropene comprising the steps of:
step one, in the presence of aliphatic alcohol proton solvent, 1, 2-dichloro-3, 3-trifluoropropene reacts with metal to prepare trifluoropropyne.
Step two, under the action of a liquid phase fluorination catalyst, performing addition reaction on trifluoropropyne and HF to prepare 2, 3-tetrafluoropropene and 1, 3-tetrafluoropropene.
The invention also has the following technical characteristics:
specifically, in the first step, the reaction temperature is 40-100 ℃; in the second step, the reaction temperature is 20-50 ℃.
Preferably, in the first step, the reaction time is 1-24 hours; in the second step, the reaction time is 1-10 h.
Specifically, in the first step, the metal is zinc powder, magnesium powder or aluminum powder; the aliphatic alcohol proton solvent is methanol, ethanol, ethylene glycol, 2, 5-hexanediol, glycerol or 2, 2-trifluoroethanol.
Specifically, in the first step, the molar ratio of the metal to the 1, 2-dichloro-3, 3-trifluoropropene is 1-2:1.
Specifically, in the second step, the liquid phase fluorination catalyst is a fluorine-containing titanium salt catalyst, and the general formula is Q + [Ti x Cl y F 4x-y+1 ] - Cation Q + Is quaternary ammonium cation, x is more than 1 and less than or equal to 2, and y is more than or equal to 0 and less than or equal to 2.
Preferably, in the second step, the quaternary ammonium cation is a dialkyl imidazolium cation or an N-alkyl pyridinium cation.
More preferably, in the second step, the quaternary ammonium cation is tetraethylammonium cation, dodecyltrimethylammonium cation, phenyltrimethylammonium cation, 1-butyl-3-methylimidazolium cation or N-butylpyridinium cation.
Specifically, in the second step, the dosage of the liquid phase fluorination catalyst is 1-20wt% of the mass of trifluoropropyne; the molar ratio of HF to trifluoropropyne is 2-4:1.
Further, in the first step, the preparation method of the 1, 2-dichloro-3, 3-trifluoropropene comprises the following steps:
step 101,2-chloro-3, 3-trifluoropropene reacts by introducing chlorine gas in the presence of a Lewis catalyst to synthesize 1, 2-trichloro-3, 3-trifluoropropane.
Step 102, under the action of a phase transfer catalyst, dehydrochlorinating 1, 2-trichloro-3, 3-trifluoropropene in an alkaline solution to prepare 1, 2-dichloro-3, 3-trifluoropropene.
The phase transfer catalyst is crown ether or polyethylene glycol.
The alkaline solution is aqueous solution of sodium hydroxide or aqueous solution of potassium hydroxide.
Specifically, in step 101, the reaction temperature is 40-80 ℃; in step 102, the reaction temperature is 50-80 ℃.
Specifically, in step 101, the reaction time is 2-5 hours; in step 102, the reaction time is 2-4 h.
Specifically, in step 101, the lewis catalyst is ferric trichloride, ferric tribromide, aluminum trichloride or boron trifluoride.
Specifically, in step 101, the amount of the Lewis catalyst is 1 to 2 weight percent of the mass of the 2-chloro-3, 3-trifluoropropene; the mol ratio of the chlorine to the 2-chlorine-3, 3-trifluoropropene is 1.5-2:1.
Specifically, in step 102, the crown ether is 15-crown-5, dicyclohexyl-18-crown-6 or dibenzo-18-crown-6; the polyethylene glycol is polyethylene glycol-4000, polyethylene glycol-6000 or polyethylene glycol-8000.
Specifically, in step 102, the dosage of the phase transfer catalyst is 1wt% -3 wt% of the mass of the 1, 2-trichloro-3, 3-trifluoropropane; the molar ratio of the alkali to the 1, 2-trichloro-3, 3-trifluoropropane is 1.5-2:1.
Compared with the prior art, the invention has the following technical effects:
the preparation method of the invention has mild reaction conditions and does not involve hydrogen.
(II) the selectivity of the product prepared by the method is higher: the selectivity of trifluoropropyne reaches 99.5%, and the total selectivity of 2, 3-tetrafluoropropene and 1, 3-tetrafluoropropene reaches 98.5%.
The invention provides a simple and efficient method for preparing raw material 1, 2-dichloro-3, 3-trifluoropropene, which is easy to implement industrialization.
Drawings
FIG. 1 is a GC-MS spectrum of 3, 3-trifluoropropyne prepared in example 1.
FIG. 2 is a GC-MS spectrum of 2, 3-tetrafluoropropene (product 1) prepared in example 7.
FIG. 3 is a GC-MS spectrum of 1, 3-tetrafluoropropene (product 2) prepared in example 7.
FIG. 4 is a GC-MS spectrum of 1, 2-trichloro-3, 3-trifluoropropane prepared in example 16 of the present invention.
FIG. 5 is a GC-MS spectrum of 1, 2-dichloro-3, 3-trifluoropropene prepared in example 26 of the present invention.
The following examples illustrate the invention in further detail.
Detailed Description
All the raw materials in the present invention, unless otherwise specified, are known in the art.
Unless specifically stated otherwise, scientific and technical terms herein have been understood based on the knowledge of one of ordinary skill in the relevant art. It should also be understood that the temperature, concentration referred to herein are approximations for purposes of illustration. Although methods and materials similar or equivalent to those described herein can be used in the practice of the present disclosure, some suitable methods and materials are described below. Publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety to the extent that any conflict arises. In addition, the materials, methods, solution concentrations, and examples are illustrative only and are not intended to be limiting. In a specific scheme, a person skilled in the art can optimize the material proportion, concentration and operation parameter values involved in the method according to the disclosure of the invention by adopting a conventional experimental period so as to achieve the purpose of the invention.
In the present invention, the operating pressure of the reaction is controlled mainly by the saturated vapor pressure of the reactants at the reaction temperature, and is not generally strictly controlled, and may be conducted at a pressure lower than, equal to, or higher than the atmospheric pressure, preferably at a pressure higher than the atmospheric pressure. In addition, the reaction of the invention can be operated intermittently or continuously, and the reaction itself has no obvious requirement on the reaction form.
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The conversion and selectivity of the reactants in the examples below were measured by GC-MS.
The following specific embodiments of the present invention are given according to the above technical solutions, and it should be noted that the present invention is not limited to the following specific embodiments, and all equivalent changes made on the basis of the technical solutions of the present application fall within the protection scope of the present invention.
Example 1:
this example shows a process for the dechlorination of 3, 3-trifluoropropyne comprising the steps of:
to a 250mL stainless steel belt condenser equipped with a stirring reactor, 50mL of ethanol, 23.4g of zinc powder (300 mesh) and 49.5g of 1, 2-dichloro-3, 3-trifluoropropene were added in this order under stirring, the condensation temperature was set to-20℃and after the temperature was raised to 100℃the reaction was carried out for 12 hours, after the reaction was completed, the sample was sampled and analyzed by gas chromatography, the conversion of 1, 2-dichloro-3, 3-trifluoropropene was 81.7% and the selectivity of 3, 3-trifluoropropyne was 99.5%.
GC-MS detection of the product 3, 3-trifluoropropyne gave the mass spectrum as shown in FIG. 1.
The correlation peak is attributed as follows: m/z94 is CF 3 Ion peak of C.ident.CH molecule, m/z75 is CF 3 Ion peak after F removal of C.ident.CH, m/z69 is trifluoromethyl and m/z56 is CF 3 Ion peaks after removal of two F's from C.ident.CH. The data demonstrate that the product is 3, 3-trifluoropropyne.
Examples 2 to 6:
this example shows a method for preparing 3, 3-trifluoropropyne by dechlorination, which is substantially the same as the preparation method in example 1, except that the metal, metal to raw material molar ratio, solvent, reaction temperature and reaction time are changed in examples 2 to 6, and the reaction results are shown in Table 1.
Table 1 reaction results for examples 2 to 6
Characterization of the product 3, 3-trifluoropropyne in examples 2 to 6 is essentially the same as in example 1.
Example 7:
this example shows a process for the preparation of 2, 3-tetrafluoropropene and 1, 3-tetrafluoropropene by fluorination comprising the steps of:
was performed in a 250mL stainless steel autoclave with stirring. 40g of hydrogen fluoride and 4.7g of [ NEt ] are sequentially added into a reaction kettle 4 ][Ti 2 Cl 0.5 F 8.5 ]Stirring is started, the reaction temperature is controlled at 40 ℃, trifluoropropyne is introduced from a liquid phase port at a speed of 47g/h by using a mass flowmeter, after 1 hour is completed, the reaction is maintained for 5 hours, the reaction is cooled to room temperature, the product is collected by an air bag after being washed by water through a gas phase port, and the result shows that the conversion rate of the trifluoropropyne is 99.5%, and the total selectivity of 2, 3-tetrafluoropropene and 1, 3-tetrafluoropropene is 99.5%.
The sample (product 1) having a boiling point of-28℃was collected by rectifying the reaction liquid, and the result of the detection by GC-MS was shown in FIG. 2. The correlation peak is attributed as follows: m/z114 is CF 3 CF＝CH 2 Molecular ion peak, m/z95 is CF 3 CF＝CH 2 Ion peak after F removal, m/z69 is CF 3 Ion peaks.
The reaction mixture was distilled to collect a sample (product 2) having a boiling point of-18℃and the result of GC-MS analysis was shown in FIG. 3. The correlation peak is attributed as follows: m/z114 is CF 3 CH=CHF molecular ion peak, m/z95 is CF 3 Ion peak after ch= CHF elimination, m/z82 is CF 3 CH ion peak, m/z69 is CF 3 Ion peaks.
Under the same gas conditions, the peak time of the product 1 was 5.288 minutes and the peak time of the product 2 was 5.706 minutes.
Detection by GC-MS: product 1 is 2, 3-tetrafluoropropene and product 2 is 1, 3-tetrafluoropropene.
Examples 8 to 11:
this example shows a process for preparing 2, 3-tetrafluoropropene and 1, 3-tetrafluoropropene by fluorination, which is substantially the same as the preparation process in example 7, except that the catalyst and the amount thereof were changed in examples 8 to 11, and the reaction results are shown in Table 2.
TABLE 2 reaction results for examples 8 to 11
| Examples | Catalyst | Catalyst usage (%) | Conversion of raw material (%) | Total selectivity of product (%) |
| 8 | [NDoMe 3 ][Ti 2 F 9 ] | 1 | 98.1 | 99.3 |
| 9 | [NPhMe 3 ][Ti 1.5 Cl 2 F 5 ] | 5 | 99.4 | 99.5 |
| 10 | [BMIm][Ti 1.5 ClF 6 ] | 10 | 99.5 | 99.5 |
| 11 | [BPy][Ti 1.25 F 6 ] | 20 | 99.5 | 99.0 |
Characterization of the products 2, 3-tetrafluoropropene (product 1) and 1, 3-tetrafluoropropene (product 2) in examples 8 to 11 was substantially the same as in example 7.
Examples 12 to 15:
this example shows a process for preparing 2, 3-tetrafluoropropene and 1, 3-tetrafluoropropene by fluorination, which is substantially the same as in example 7, except that the molar ratio of HF to trifluoropropyne, the reaction temperature and the reaction time were changed in examples 12 to 15, and the reaction results are shown in table 3.
TABLE 3 reaction results for examples 12 to 15
Characterization of the products 2, 3-tetrafluoropropene (product 1) and 1, 3-tetrafluoropropene (product 2) in examples 12 to 15 was substantially the same as in example 7.
Example 16:
this example shows a process for the preparation of 1, 2-trichloro-3, 3-trifluoropropane comprising the steps of:
adding 65.25g of 2-chloro-3, 3-trifluoropropene and 1.31g of aluminum trichloride into a 250mL stainless steel belt stirring high-pressure reaction kettle, heating to a reaction temperature of 40 ℃, starting stirring, introducing 71g of chlorine, maintaining a reaction pressure of 0.3MPa, and reacting for 5 hours; the reaction was stopped by cooling, and a sample was taken for GC analysis, with a conversion of 100% for 2-chloro-3, 3-trifluoropropene and a selectivity of 98.5% for 1, 2-trichloro-3, 3-trifluoropropane.
GC-MS detection of the product 1, 2-trichloro-3, 3-trifluoropropane shows the mass spectrum result as shown in FIG. 4, and the correlation peaks belong to the following steps:
m/z200 is the molecular ion peak and m/z165 is CF 3 CCl 2 CH 2 Ion peak after Cl removal, m/z151 is CF 3 CCl 2 CH 2 Cl is removed from CH 2 Ion peak after Cl, m/z131 is CF 3 CCl 2 CH 2 Cl-removal CF 3 Post ion peak, m/z95 is CCl 2 CH ion peak, m/z69 is CF 3 Ion peak, m/z49 is CH 2 Cl ion peak.
The data above demonstrate that the product obtained is 1, 2-trichloro-3, 3-trifluoropropane.
Examples 17 to 20:
this example shows a process for preparing 1, 2-trichloro-3, 3-trifluoropropane which is substantially the same as the preparation process in example 16, except that the catalyst and the amount thereof were changed in examples 17 to 20, and the reaction results are shown in Table 4.
TABLE 4 reaction results for examples 17 to 20
Characterization of the product 1, 2-trichloro-3, 3-trifluoropropane of examples 17-20 was substantially the same as that of example 16.
Examples 21 to 25:
this example shows a process for preparing 1, 2-trichloro-3, 3-trifluoropropane which is substantially the same as the preparation process in example 16, except that the molar ratio of chlorine to 2-chloro-3, 3-trifluoropropene, the reaction temperature and the reaction time were changed in examples 21 to 25, and the reaction results are shown in Table 5.
TABLE 5 reaction results for examples 21 to 25
Characterization of the product 1, 2-trichloro-3, 3-trifluoropropane of examples 21-25 was substantially the same as that of example 16.
Example 26:
this example shows a process for the preparation of 1, 2-dichloro-3, 3-trifluoropropene by dehydrochlorination in an alkaline solution comprising the steps of:
42g of 40% (mass percent) KOH aqueous solution, 40.3g of 1, 2-trichloro-3, 3-trifluoropropane and 0.4g of polyethylene glycol-4000 (1 wt%) were successively charged into a reaction vessel equipped with a stirrer; the stirring is started, the reaction temperature is controlled at 80 ℃, after the reaction is carried out for 4 hours, the reaction material is cooled to room temperature, the organic matters are collected after phase separation for gas chromatography analysis, and the result shows that the conversion rate of 1, 2-trichloro-3, 3-trifluoropropene is 100 percent and the (cis+trans) 1, 2-dichloro-3, 3-trifluoropropene is 99.5 percent.
GC-MS detection of the product 1, 2-dichloro-3, 3-trifluoropropene shows a mass spectrum result as shown in FIG. 5, and correlation peaks belong to the following steps: m/z164 is the molecular ion peak and m/z145 is CF 3 ccl=post-CHCl def ion peak, m/z129 is CF 3 Ccl=chcl ion peak after decl, m/z95 is CF 3 Ccl=chcl decf 3 Post ion peak, m/z69 is CF 3 Ion peaks.
1 H NMR(500MHz,CDCl 3 )δ7.16(d,J＝1.2Hz,1H)；
13 C NMR(126MHz,CDCl 3 )δ125.65(q,J＝5.6Hz),124.68(q,J＝38.0Hz),119.87(q,J＝272.5Hz)；
19 F NMR(471MHz,CDCl 3 )δ-68.31。
The data demonstrate that the product is 1, 2-dichloro-3, 3-trifluoropropene.
Example 27:
this example shows a process for the preparation of 1, 2-dichloro-3, 3-trifluoropropene by dehydrochlorination in an alkaline solution comprising the steps of:
to a stirred reaction vessel were successively charged 40g of an aqueous NaOH (40 wt.%) solution, 40.3g of 1, 2-trichloro-3, 3-trifluoropropane and 0.2g of dicyclohexyl-18-crown-6 (0.5 wt.%); the stirring is started, the reaction temperature is controlled at 120 ℃, after the reaction is carried out for 4 hours, the reaction material is cooled to room temperature, the organic matters are collected after phase separation for gas chromatography analysis, and the result shows that the conversion rate of 1, 2-trichloro-3, 3-trifluoropropene is 100 percent and the (cis+trans) 1, 2-dichloro-3, 3-trifluoropropene is 98.5 percent.
Characterization of the product 1, 2-dichloro-3, 3-trifluoropropene in example 27 was essentially the same as in example 26.
Examples 28 to 31:
this example shows a process for preparing 1, 2-dichloro-3, 3-trifluoropropene by dehydrochlorination in an alkaline solution, which is substantially the same as the preparation process of example 26, except that the catalyst and the amount of the catalyst are changed in examples 28 to 31, and the reaction results are shown in Table 6.
TABLE 6 reaction results for examples 28 to 31
| Examples | Catalyst | Catalyst usage (%) | Conversion of raw material (%) | Product selectivity (%) |
| 28 | 15-crown-5 | 1 | 100 | 98.9 |
| 29 | Dibenzo-18-crown-6 | 3 | 100 | 99.1 |
| 30 | Polyethylene glycol-6000 | 3 | 100 | 99.3 |
| 31 | Polyethylene glycol-8000 | 10 | 100 | 97.2 |
Characterization of the products 1, 2-dichloro-3, 3-trifluoropropene in examples 28-31 was essentially the same as in example 26.
Examples 32 to 36:
this example shows a process for preparing 1, 2-dichloro-3, 3-trifluoropropene by dehydrochlorination in an alkaline solution, which is substantially the same as the preparation process of example 26, except that the molar ratio of the base to 1, 2-trichloro-3, 3-trifluoropropane, the reaction temperature and the reaction time were changed in examples 32 to 36, and the reaction results are shown in Table 7.
TABLE 7 reaction results for examples 32 to 36
Characterization of the products 1, 2-dichloro-3, 3-trifluoropropene in examples 32-36 was essentially the same as in example 26.
The foregoing description is only a few examples of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent variations and modification of the above-described examples according to the technical principles of the present invention are within the scope of the present invention.
Claims (10)
1. A process for preparing 2, 3-tetrafluoropropene and 1, 3-tetrafluoropropene, comprising the steps of:
step one, in the presence of an aliphatic alcohol proton solvent, 1, 2-dichloro-3, 3-trifluoropropene reacts with metal to prepare trifluoropropyne;
step two, under the action of a liquid phase fluorination catalyst, performing addition reaction on trifluoropropyne and HF to prepare 2, 3-tetrafluoropropene and 1, 3-tetrafluoropropene.
2. The process for producing 2, 3-tetrafluoropropene and 1, 3-tetrafluoropropene as claimed in claim 1, wherein in the first step, the reaction temperature is 40 to 100 ℃; in the second step, the reaction temperature is 20-50 ℃.
3. The process for preparing 2, 3-tetrafluoropropene and 1, 3-tetrafluoropropene as claimed in claim 1, wherein in the first step, the metal is zinc powder, magnesium powder or aluminum powder; the aliphatic alcohol proton solvent is methanol, ethanol, ethylene glycol, 2, 5-hexanediol, glycerol or 2, 2-trifluoroethanol.
4. The process for preparing 2, 3-tetrafluoropropene and 1, 3-tetrafluoropropene as claimed in claim 1, wherein in the second step, said liquid phase fluorination catalyst is a fluorine-containing titanium salt catalyst having the general formula of Q + [Ti x Cl y F 4x-y+1 ] - Cations ofQ + Is quaternary ammonium cation, x is more than 1 and less than or equal to 2, and y is more than or equal to 0 and less than or equal to 2.
5. The process for preparing 2, 3-tetrafluoropropene and 1, 3-tetrafluoropropene as claimed in claim 4, wherein in the second step, said quaternary ammonium cation is a dialkylimidazolium cation or an N-alkylpyridinium cation.
6. The process for preparing 2, 3-tetrafluoropropene and 1, 3-tetrafluoropropene as claimed in claim 5, wherein in the second step, the quaternary ammonium cation is tetraethylammonium cation, dodecyltrimethylammonium cation, phenyltrimethylammonium cation, 1-butyl-3-methylimidazolium cation or N-butylpyridinium cation.
7. The process for producing 2, 3-tetrafluoropropene and 1, 3-tetrafluoropropene according to claim 1, wherein in step one, the process for producing 1, 2-dichloro-3, 3-trifluoropropene comprises the steps of:
step 101,2-chloro-3, 3-trifluoropropene reacts by introducing chlorine gas in the presence of a Lewis catalyst to synthesize 1, 2-trichloro-3, 3-trifluoropropane;
step 102, under the action of a phase transfer catalyst, dehydrochlorinating 1, 2-trichloro-3, 3-trifluoropropane in an alkaline solution to prepare 1, 2-dichloro-3, 3-trifluoropropene;
the phase transfer catalyst is crown ether or polyethylene glycol;
the alkaline solution is aqueous solution of sodium hydroxide or aqueous solution of potassium hydroxide.
8. The process for producing 2, 3-tetrafluoropropene and 1, 3-tetrafluoropropene as claimed in claim 7, wherein in step 101, the reaction temperature is 40 to 80 ℃; in step 102, the reaction temperature is 50-80 ℃.
9. The process for preparing 2, 3-tetrafluoropropene and 1, 3-tetrafluoropropene as claimed in claim 7, wherein in step 101, said lewis catalyst is ferric trichloride, ferric tribromide, aluminum trichloride or boron trifluoride.
10. The process for preparing 2, 3-tetrafluoropropene and 1, 3-tetrafluoropropene as claimed in claim 7, wherein in step 102 said crown ether is 15-crown-5, dicyclohexyl-18-crown-6 or dibenzo-18-crown-6; the polyethylene glycol is polyethylene glycol-4000, polyethylene glycol-6000 or polyethylene glycol-8000.
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