CN107032946A - A kind of method that phase transfer catalysis (PTC) prepares bromotrifluoroethylene - Google Patents
A kind of method that phase transfer catalysis (PTC) prepares bromotrifluoroethylene Download PDFInfo
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- CN107032946A CN107032946A CN201710351682.4A CN201710351682A CN107032946A CN 107032946 A CN107032946 A CN 107032946A CN 201710351682 A CN201710351682 A CN 201710351682A CN 107032946 A CN107032946 A CN 107032946A
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- CN
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- Prior art keywords
- bromotrifluoroethylene
- bromo
- phase transfer
- preparing
- bis
- Prior art date
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- AYCANDRGVPTASA-UHFFFAOYSA-N 1-bromo-1,2,2-trifluoroethene Chemical group FC(F)=C(F)Br AYCANDRGVPTASA-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000003408 phase transfer catalysis Methods 0.000 title description 10
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 21
- 238000007269 dehydrobromination reaction Methods 0.000 claims abstract description 7
- 230000000694 effects Effects 0.000 claims abstract description 7
- UJPMYEOUBPIPHQ-UHFFFAOYSA-N 1,1,1-trifluoroethane Chemical compound CC(F)(F)F UJPMYEOUBPIPHQ-UHFFFAOYSA-N 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 84
- 239000003513 alkali Substances 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 5
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 5
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 claims description 4
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical compound FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 claims description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 claims description 3
- AJSHDAOMUKXVDC-UHFFFAOYSA-N butan-1-amine;sulfuric acid Chemical compound CCCC[NH3+].OS([O-])(=O)=O AJSHDAOMUKXVDC-UHFFFAOYSA-N 0.000 claims description 3
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 3
- PLMFYJJFUUUCRZ-UHFFFAOYSA-M decyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCC[N+](C)(C)C PLMFYJJFUUUCRZ-UHFFFAOYSA-M 0.000 claims description 3
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
- 238000005660 chlorination reaction Methods 0.000 claims description 2
- UHCBBWUQDAVSMS-UHFFFAOYSA-N fluoroethane Chemical compound CCF UHCBBWUQDAVSMS-UHFFFAOYSA-N 0.000 claims 1
- GLFDLEXFOHUASB-UHFFFAOYSA-N trimethyl(tetradecyl)azanium Chemical compound CCCCCCCCCCCCCC[N+](C)(C)C GLFDLEXFOHUASB-UHFFFAOYSA-N 0.000 claims 1
- 230000036632 reaction speed Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 125000000950 dibromo group Chemical group Br* 0.000 abstract 1
- 150000002429 hydrazines Chemical class 0.000 description 56
- 239000002994 raw material Substances 0.000 description 47
- 238000006243 chemical reaction Methods 0.000 description 34
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 30
- 239000000047 product Substances 0.000 description 16
- 238000003756 stirring Methods 0.000 description 15
- 238000010792 warming Methods 0.000 description 14
- UREJNEBJDURREH-UHFFFAOYSA-N 1,2-dibromo-1,1,2-trifluoroethane Chemical compound FC(Br)C(F)(F)Br UREJNEBJDURREH-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000008346 aqueous phase Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- RWNKSTSCBHKHTB-UHFFFAOYSA-N Hexachloro-1,3-butadiene Chemical compound ClC(Cl)=C(Cl)C(Cl)=C(Cl)Cl RWNKSTSCBHKHTB-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 description 2
- SUTQSIHGGHVXFK-UHFFFAOYSA-N 1,2,2-trifluoroethenylbenzene Chemical compound FC(F)=C(F)C1=CC=CC=C1 SUTQSIHGGHVXFK-UHFFFAOYSA-N 0.000 description 1
- IYZKEAIYJSVBRR-UHFFFAOYSA-N C(CCCCCCCCCCCCC)[N+](C)(C)C.[Cl+] Chemical compound C(CCCCCCCCCCCCC)[N+](C)(C)C.[Cl+] IYZKEAIYJSVBRR-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- CTISCMCFPOFTKK-UHFFFAOYSA-N ethene;trifluoro-$l^{3}-chlorane Chemical compound C=C.FCl(F)F CTISCMCFPOFTKK-UHFFFAOYSA-N 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- FQFKTKUFHWNTBN-UHFFFAOYSA-N trifluoro-$l^{3}-bromane Chemical compound FBr(F)F FQFKTKUFHWNTBN-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound 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
- C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of method for preparing bromotrifluoroethylene, in aqueous slkali, under phase transfer catalyst effect, dehydrobromination reaction generation bromotrifluoroethylene occurs for the HFC-143a of 1,2 dibromo 1,1,2.Preparation method reaction speed that the present invention is provided is fast, combined coefficient is high, cost is low, environmental protection.
Description
Technical field
The present invention relates to a kind of preparation method of bromotrifluoroethylene, more particularly to a kind of phase transfer catalysis (PTC) prepares trifluoro bromine
The method of ethene.
Background technology
Bromotrifluoroethylene has the property of Fluorine containing olefine, including halogenation, hydrogenation, necleophilic reaction, is mainly used in polymerization anti-
Should, it can also be used as chemical intermediate.Its metal organic intermediate is the reagent for synthesizing trifluoro-ethylene based compound, such as
The raw material trifluorostyrene of the sub- battery ions exchange membrane of synthetic fuel, or synthesis with superior etch performance, low GWP value it is green
Color etching gas hexachlorobutadiene etc..Bromotrifluoroethylene telomer can be used as high-precision navigation system liquid floated gyroscope and accelerometer
Supernatant liquid and damping fluid, these liquid are expensive, are widely used in aerospace industry.In addition, bromotrifluoroethylene is also to prepare
One of three kinds of monomers (tetrafluoroethene, perfluoro-methyl perfluoroalkyl vinyl ether, bromotrifluoroethylene) needed for solidification fluorubber.
The synthesis technique of bromotrifluoroethylene mainly has two lines, using trifluoro-ethylene as initiation material route and with trifluoro chlorine
Ethene is initiation material route.Late nineteenth century chemist is just by adding Br2To CF2=CFH first prepares CF2BrCHFBr
(K2CO3 and KOAc are in ethanol solution), then by product 1,2- bis- bromo- 1,1,2- HFC-143a is in alkali (sodium hydroxide, hydroxide
In the presence of potassium etc., removing hydrogen bromide obtains product bromotrifluoroethylene.Reaction equation is as follows：
Bromotrifluoroethylene is prepared using CTFE as raw material, it is necessary to by four steps, total recovery about 60%, reaction side
Formula is as follows：
CF2=CFCl+HBr → CF2BrCFClH (2)
CF2BrCFClH+Zn→CF2=CHF+ZnBrCl
CF2=CHF+Br2→CF2BrCHFBr
CF2BrCHFBr+KOH→CF2=CFBr+KBr+H2O
Above two lines intermediate product is 1,2- bis- bromo- 1,1,2- HFC-143a, subsequently by 1,2- bis- bromo- 1,1,2-
It is identical that HFC-143a dehydrobromination prepares bromotrifluoroethylene step, wherein 1,2- bis- bromo- 1,1,2- HFC-143a dehydrobromination step
Suddenly it is the committed step for restricting bromotrifluoroethylene combined coefficient.Traditional alkali lye dehydrobromination technique, due to raw material 1,2- bis- is bromo-
1,1,2- HFC-143a does not dissolve in alkali lye, there is poor mass transfer effect, reaction time length, the low problem of efficiency.
Therefore need exploitation is a kind of new to prepare bromotrifluoroethylene side by the bromo- 1,1,2- HFC-143as dehydrobrominations of 1,2- bis-
Method.
The content of the invention
It is an object of the invention to provide a kind of method that phase transfer catalysis (PTC) prepares bromotrifluoroethylene, with reaction speed
Hurry up, combined coefficient height, low cost, environmental protection the advantages of.
To reach that goal of the invention the technical solution adopted by the present invention is：
A kind of method for preparing bromotrifluoroethylene, in aqueous slkali, under phase transfer catalyst effect, 1,2- bis- bromo- 1,
Dehydrobromination reaction generation bromotrifluoroethylene occurs for 1,2- HFC-143a, wherein：
The aqueous slkali is the aqueous solution or alkali alcosol of alkali, and the alkali is selected from KOH and/or NaOH, and the alcohol is selected from
One kind, two or three of combination of the above in methanol, ethanol, normal propyl alcohol, isopropanol, n-butanol and cyclohexanol；
The phase transfer catalyst is selected from 4 bromide, tetraethylammonium bromide, TBAB, tetrabutyl chlorination
Ammonium, 4-butyl ammonium hydrogen sulfate, DTAC, DTAB, tetradecyltrimethylammonium chlorine
Change ammonium, TTAB and one kind, two or three of combination of the above in cetyl trimethylammonium bromide.
The aqueous slkali that the present invention is used both can be the aqueous solution or alkali alcosol of alkali；The quality of aqueous slkali
Percentage concentration is preferably 5.0~40.0%, and more preferably 15.0~30.0%.Suitable alcohol is preferably selected from methanol, second
One kind, two or three of combination of the above in alcohol, normal propyl alcohol, isopropanol, n-butanol and cyclohexanol, more preferably selected from second
One kind in alcohol, normal propyl alcohol and isopropanol, two or three.
The present invention improves alkali and 1 using phase transfer catalyst, and 2- bis- bromo- 1, effective contact of 1,2- HFC-143a changes
Kind mass transfer effect, greatly speeds up reaction rate, shortens the reaction time.Suitable phase transfer catalyst be selected from 4 bromide,
Tetraethylammonium bromide, TBAB, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate, DTAC, ten
Dialkyl group trimethylammonium bromide, tetradecyl trimethyl ammonium chloride, TTAB and cetyl trimethyl
One kind, two or three of combination of the above in ammonium bromide；It is preferably selected from 4 bromide, tetraethylammonium bromide, dodecane
One kind, two or three of combination of the above in base trimethylammonium bromide and cetyl trimethylammonium bromide.
The addition for the phase transfer catalyst that the present invention is used is preferably the bromo- 1,1,2- HFC-143as quality of 1,2- bis-
0.1~5.0%, more preferably the addition of phase transfer catalyst be 1,2- bis- bromo- 1,1,2- HFC-143a amount 0.5~
2.0%.The addition for the alkali that the present invention is used is preferably 1,2- bis- bromo- 1,0.5~4.0 times of 1,2- HFC-143a mole,
More preferably the addition of alkali is 1.5~2.0 times of the bromo- 1,1,2- HFC-143as moles of 1,2- bis-.
In the method for the present invention for preparing bromotrifluoroethylene, the aqueous solution or alkali of used phase transfer catalyst and alkali
Alcoholic solution can recycled, the yield of bromotrifluoroethylene is not influenceed.
The raw material 1 that the present invention is used, 2- bis- bromo- 1,1,2- HFC-143a can be by trifluoro-ethylene or CTFE system
It is standby.
Present invention also offers a kind of processing step for preparing bromotrifluoroethylene, including：
(1) a certain amount of aqueous slkali input reactor is configured, the mass percentage concentration of aqueous slkali is 5.0~40.0%；
(2) a certain proportion of phase transfer catalyst is added into reactor, addition phase transfer catalysis (PTC) dosage is that 1,2- bis- is bromo-
The 0.1~5.0% of 1,1,2- HFC-143a quality；
(3) stirring and condensation reflux unit are opened, 40~120 DEG C of reaction temperature is risen to；
(4) raw material 1 is added dropwise into reactor, 2- bis- bromo- 1,1,2- HFC-143a controls the addition of alkali for 1,2- bis-
0.5~4.0 times of bromo- 1,1,2- HFC-143a mole, product is collected using low temperature cold hydrazine；
(5) 1~8h is incubated after the bromo- 1,1,2- HFC-143as completion of dropwise addition of 1,2- bis-；
(6) room temperature is down to, is filtered, point liquid obtains organic phase and aqueous phase, and wherein organic phase is bromotrifluoroethylene.
For the aqueous phase obtained in reaction, by that toward a certain amount of alkali is added in aqueous phase, Bromide solid can be separated out, carried out
Filtering, liquid can be used as the alkali lye of next secondary response, realize the recycled of spent lye, substantially reduce three-protection design amount.
Compared with prior art, the present invention has advantages below：Do not changing the feelings of original reaction system and reaction condition
Under condition, by adding phase transfer catalyst, promote effective contact of reaction mass, improve mass transfer effect, reaction speed can be accelerated
Rate, shortens the reaction time, improves production efficiency；The recycled of phase transfer catalyst and alkali lye can be realized simultaneously, reduce the three wastes,
Reduce production cost.
Embodiment
The present invention is further described with reference to specific embodiment, but does not limit the invention to these tools
Body embodiment.One skilled in the art would recognize that present invention encompasses potentially included in Claims scope
All alternatives, improvement project and equivalents.
Embodiment 1
250ml three-necked flasks are placed in oil bath pan, 1# cold hydrazines are filled on three-necked flask is used for flow back unreacted raw material, 1#
Cold hydrazine temperature is -2 DEG C, and 2# cold hydrazines are refilled after 1# cold hydrazines is used for the collection of product, and 2# cold hydrazines temperature is -20 DEG C.In three-necked flask
It is 30%KOH and 0.9g DTACs to add 69g concentration, and by 60g raw materials 1,2- bis- bromo- 1,1,2- trifluoro
Ethane loads constant pressure funnel (NaOH：CF2BrCHFBr=1.5:1 mol ratio).When oil bath pan is warming up to 70 DEG C, while stirring
Raw material CF is added dropwise into three-necked flask2BrCHFBr, is added dropwise to complete follow-up continuation of insurance temperature 5h.Reaction result is shown in Table 1.
Embodiment 2
250ml three-necked flasks are placed in oil bath pan, 1# cold hydrazines are filled on three-necked flask is used for flow back unreacted raw material, 1#
Cold hydrazine temperature is -2 DEG C, and 2# cold hydrazines are refilled after 1# cold hydrazines is used for the collection of product, and 2# cold hydrazines temperature is -20 DEG C.In three-necked flask
It is 30%KOH and 0.9g DTACs to add 69g concentration, and by 60g raw materials 1,2- bis- bromo- 1,1,2- trifluoro
Ethane loads constant pressure funnel (NaOH：CF2BrCHFBr=1.5:1 mol ratio).When oil bath pan is warming up to 70 DEG C, while stirring
Raw material CF is added dropwise into three-necked flask2BrCHFBr, is added dropwise to complete follow-up continuation of insurance temperature 4h.Reaction result is shown in Table 1.
Embodiment 3
250ml three-necked flasks are placed in oil bath pan, 1# cold hydrazines are filled on three-necked flask is used for flow back unreacted raw material, 1#
Cold hydrazine temperature is -2 DEG C, and 2# cold hydrazines are refilled after 1# cold hydrazines is used for the collection of product, and 2# cold hydrazines temperature is -20 DEG C.In three-necked flask
It is 30%KOH and 0.9g DTACs to add 69g concentration, and by 60g raw materials 1,2- bis- bromo- 1,1,2- trifluoro
Ethane loads constant pressure funnel (NaOH：CF2BrCHFBr=1.5:1 mol ratio).When oil bath pan is warming up to 70 DEG C, while stirring
Raw material CF is added dropwise into three-necked flask2BrCHFBr, is added dropwise to complete follow-up continuation of insurance temperature 3h.Reaction result is shown in Table 1.
Embodiment 4
250ml three-necked flasks are placed in oil bath pan, 1# cold hydrazines are filled on three-necked flask is used for flow back unreacted raw material, 1#
Cold hydrazine temperature is -2 DEG C, and 2# cold hydrazines are refilled after 1# cold hydrazines is used for the collection of product, and 2# cold hydrazines temperature is -20 DEG C.In three-necked flask
It is 30%KOH and 0.9g TBABs to add 69g concentration, and by 60g raw materials 1,2- bis- bromo- 1,1,2- HFC-143a loads
Constant pressure funnel (NaOH：CF2BrCHFBr=1.5:1 mol ratio).When oil bath pan is warming up to 70 DEG C, burnt while stirring to three mouthfuls
Raw material CF is added dropwise in bottle2BrCHFBr, is added dropwise to complete follow-up continuation of insurance temperature 3h.Reaction result is shown in Table 1.
Embodiment 5
250ml three-necked flasks are placed in oil bath pan, 1# cold hydrazines are filled on three-necked flask is used for flow back unreacted raw material, 1#
Cold hydrazine temperature is -2 DEG C, and 2# cold hydrazines are refilled after 1# cold hydrazines is used for the collection of product, and 2# cold hydrazines temperature is -20 DEG C.In three-necked flask
It is 30%KOH and 0.9g 4 bromides to add 69g concentration, and by 60g raw materials 1,2- bis- bromo- 1,1,2- HFC-143a loads
Constant pressure funnel (NaOH：CF2BrCHFBr=1.5:1 mol ratio).When oil bath pan is warming up to 70 DEG C, burnt while stirring to three mouthfuls
Raw material CF is added dropwise in bottle2BrCHFBr, is added dropwise to complete follow-up continuation of insurance temperature 3h.Reaction result is shown in Table 1.
Embodiment 6
250ml three-necked flasks are placed in oil bath pan, 1# cold hydrazines are filled on three-necked flask is used for flow back unreacted raw material, 1#
Cold hydrazine temperature is -2 DEG C, and 2# cold hydrazines are refilled after 1# cold hydrazines is used for the collection of product, and 2# cold hydrazines temperature is -20 DEG C.In three-necked flask
It is 30%KOH and 0.9g cetyl trimethylammonium bromides to add 69g concentration, and by 60g raw materials 1,2- bis- bromo- 1,1,2- trifluoro
Ethane loads constant pressure funnel (NaOH：CF2BrCHFBr=1.5:1 mol ratio).When oil bath pan is warming up to 70 DEG C, while stirring
Raw material CF is added dropwise into three-necked flask2BrCHFBr, is added dropwise to complete follow-up continuation of insurance temperature 3h.Reaction result is shown in Table 1.
Embodiment 7
250ml three-necked flasks are placed in oil bath pan, 1# cold hydrazines are filled on three-necked flask is used for flow back unreacted raw material, 1#
Cold hydrazine temperature is -2 DEG C, and 2# cold hydrazines are refilled after 1# cold hydrazines is used for the collection of product, and 2# cold hydrazines temperature is -20 DEG C.In three-necked flask
It is 30%KOH and 1.2g DTACs to add 69g concentration, and by 60g raw materials 1,2- bis- bromo- 1,1,2- trifluoro
Ethane loads constant pressure funnel (NaOH：CF2BrCHFBr=1.5:1 mol ratio).When oil bath pan is warming up to 70 DEG C, while stirring
Raw material CF is added dropwise into three-necked flask2BrCHFBr, is added dropwise to complete follow-up continuation of insurance temperature 3h.Reaction result is shown in Table 1.
Embodiment 8
250ml three-necked flasks are placed in oil bath pan, 1# cold hydrazines are filled on three-necked flask is used for flow back unreacted raw material, 1#
Cold hydrazine temperature is -2 DEG C, and 2# cold hydrazines are refilled after 1# cold hydrazines is used for the collection of product, and 2# cold hydrazines temperature is -20 DEG C.In three-necked flask
It is 30%KOH and 0.6g DTACs to add 69g concentration, and by 60g raw materials 1,2- bis- bromo- 1,1,2- trifluoro
Ethane loads constant pressure funnel (NaOH：CF2BrCHFBr=1.5:1 mol ratio).When oil bath pan is warming up to 70 DEG C, while stirring
Raw material CF is added dropwise into three-necked flask2BrCHFBr, is added dropwise to complete follow-up continuation of insurance temperature 3h.Reaction result is shown in Table 1.
Embodiment 9
250ml three-necked flasks are placed in oil bath pan, 1# cold hydrazines are filled on three-necked flask is used for flow back unreacted raw material, 1#
Cold hydrazine temperature is -2 DEG C, and 2# cold hydrazines are refilled after 1# cold hydrazines is used for the collection of product, and 2# cold hydrazines temperature is -20 DEG C.In three-necked flask
It is 30%KOH and 0.3g DTACs to add 69g concentration, and by 60g raw materials 1,2- bis- bromo- 1,1,2- trifluoro
Ethane loads constant pressure funnel (NaOH：CF2BrCHFBr=1.5:1 mol ratio).When oil bath pan is warming up to 70 DEG C, while stirring
Raw material CF is added dropwise into three-necked flask2BrCHFBr, is added dropwise to complete follow-up continuation of insurance temperature 3h.Reaction result is shown in Table 1.
Comparative example 1
250ml three-necked flasks are placed in oil bath pan, 1# cold hydrazines are filled on three-necked flask is used for flow back unreacted raw material, 1#
Cold hydrazine temperature is -2 DEG C, and 2# cold hydrazines are refilled after 1# cold hydrazines is used for the collection of product, and 2# cold hydrazines temperature is -20 DEG C.In three-necked flask
It is 20%NaOH to add 69g concentration, and by 60g raw materials 1,2- bis- bromo- 1,1,2- HFC-143a loads constant pressure funnel (NaOH：
CF2BrCHFBr=1.5:1 mol ratio).When oil bath pan is warming up to 70 DEG C, raw material is added dropwise into three-necked flask while stirring
CF2BrCHFBr, is added dropwise to complete follow-up continuation of insurance temperature 5h.Reaction result is shown in Table 1.
Comparative example 2
250ml three-necked flasks are placed in oil bath pan, 1# cold hydrazines are filled on three-necked flask is used for flow back unreacted raw material, 1#
Cold hydrazine temperature is -2 DEG C, and 2# cold hydrazines are refilled after 1# cold hydrazines is used for the collection of product, and 2# cold hydrazines temperature is -20 DEG C.In three-necked flask
It is 20%NaOH to add 69g concentration, and by 60g raw materials 1,2- bis- bromo- 1,1,2- HFC-143a loads constant pressure funnel (NaOH：
CF2BrCHFBr=1.5:1 mol ratio).When oil bath pan is warming up to 120 DEG C, raw material is added dropwise into three-necked flask while stirring
CF2BrCHFBr, is added dropwise to complete follow-up continuation of insurance temperature 5h.Reaction result is shown in Table 1.
Comparative example 3
250ml three-necked flasks are placed in oil bath pan, 1# cold hydrazines are filled on three-necked flask is used for flow back unreacted raw material, 1#
Cold hydrazine temperature is -2 DEG C, and 2# cold hydrazines are refilled after 1# cold hydrazines is used for the collection of product, and 2# cold hydrazines temperature is -20 DEG C.In three-necked flask
It is 20%NaOH to add 33g concentration, and by 60g raw materials 1,2- bis- bromo- 1,1,2- HFC-143a loads constant pressure funnel (NaOH：
CF2BrCHFBr=0.7:1 mol ratio).When oil bath pan is warming up to 70 DEG C, raw material is added dropwise into three-necked flask while stirring
CF2BrCHFBr, is added dropwise to complete follow-up continuation of insurance temperature 5h.Reaction result is shown in Table 1.
Comparative example 4
250ml three-necked flasks are placed in oil bath pan, 1# cold hydrazines are filled on three-necked flask is used for flow back unreacted raw material, 1#
Cold hydrazine temperature is -2 DEG C, and 2# cold hydrazines are refilled after 1# cold hydrazines is used for the collection of product, and 2# cold hydrazines temperature is -20 DEG C.In three-necked flask
It is 20%NaOH to add 115g concentration, and by 60g raw materials 1,2- bis- bromo- 1,1,2- HFC-143a loads constant pressure funnel (NaOH：
CF2BrCHFBr=2.5:1 mol ratio).When oil bath pan is warming up to 70 DEG C, raw material is added dropwise into three-necked flask while stirring
CF2BrCHFBr, is added dropwise to complete follow-up continuation of insurance temperature 5h.Reaction result is shown in Table 1.
Comparative example 5
250ml three-necked flasks are placed in oil bath pan, 1# cold hydrazines are filled on three-necked flask is used for flow back unreacted raw material, 1#
Cold hydrazine temperature is -2 DEG C, and 2# cold hydrazines are refilled after 1# cold hydrazines is used for the collection of product, and 2# cold hydrazines temperature is -20 DEG C.In three-necked flask
It is 20%NaOH to add 161g concentration, and by 60g raw materials 1,2- bis- bromo- 1,1,2- HFC-143a loads constant pressure funnel (NaOH：
CF2BrCHFBr=3.5:1 mol ratio).When oil bath pan is warming up to 70 DEG C, raw material is added dropwise into three-necked flask while stirring
CF2BrCHFBr, is added dropwise to complete follow-up continuation of insurance temperature 5h.Reaction result is shown in Table 1.
The reaction result carried out under the different condition of table 1.
As can be known from Table 1, added in reaction system after phase transfer catalyst, because phase transfer catalyst is promoted instead
Effective contact of material is answered, improves mass transfer effect, accelerate reaction rate, not only under identical soaking time, the conversion ratio of reaction is equal
Have obvious rise, even and if shorten soaking time, the conversion ratio of reaction is also apparently higher than the reactant for being not added with catalyst
System.
Embodiment 10
Present embodiment describes the recycled technique that the present invention realizes phase transfer catalyst and alkali lye：First set reaction is protected
Temperature is down to room temperature after terminating, and filters out Bromide, and carry out a point liquid to organic phase and aqueous phase；A certain amount of alkali is added in aqueous phase
It is 30% to concentration of lye, filters the Bromide solid now separated out, due to filtering and dividing in liquid operating process, phase transfer is urged
Agent has a certain amount of loss, applies mechanically be both needed to add a certain amount of catalyst every time, other specific operations are implemented with contrast
Example 1 is identical, and reaction temperature is 70 DEG C, and alkali lye is 30%KOH solution, and soaking time 3h, reaction result is as shown in table 2.
Reaction result under the conditions of the phase transfer catalyst of table 2. and alkali lye recycled
Claims (9)
1. a kind of method for preparing bromotrifluoroethylene, it is characterised in that in aqueous slkali, under phase transfer catalyst effect, 1,2-
Two bromo- 1, dehydrobromination reaction generation bromotrifluoroethylene occurs for 1,2- HFC-143a, wherein：
The aqueous slkali be alkali the aqueous solution or alkali alcosol, the alkali be selected from KOH and/or NaOH, the alcohol be selected from methanol,
One kind, two or three of combination of the above in ethanol, normal propyl alcohol, isopropanol, n-butanol and cyclohexanol；
The phase transfer catalyst be selected from 4 bromide, tetraethylammonium bromide, TBAB, tetrabutylammonium chloride,
4-butyl ammonium hydrogen sulfate, DTAC, DTAB, tetradecyltrimethylammonium chlorination
One kind, two or three of combination of the above in ammonium, TTAB and cetyl trimethylammonium bromide.
2. according to the method for preparing bromotrifluoroethylene described in claim 1, it is characterised in that the quality percentage of the aqueous slkali
Concentration is 5.0~40.0%.
3. according to the method for preparing bromotrifluoroethylene described in claim 2, it is characterised in that the quality percentage of the aqueous slkali
Concentration is 15.0~30.0%.
4. according to the method for preparing bromotrifluoroethylene described in claim 1, it is characterised in that the alcohol is selected from ethanol, normal propyl alcohol
With in isopropanol it is a kind of, two or three.
5. according to the method for preparing bromotrifluoroethylene described in claim 1, it is characterised in that the phase transfer catalyst is selected from
One kind in 4 bromide, tetraethylammonium bromide, DTAB and cetyl trimethylammonium bromide,
Two or three of combination of the above.
6. according to the method for preparing bromotrifluoroethylene described in claim 1, it is characterised in that the phase transfer catalyst adds
Dosage is 1,2- bis- bromo- 1, the 0.1~5.0% of 1,2- HFC-143a quality, and the addition of the alkali is 1,2- bis- bromo- 1,1,2-
0.5~4.0 times of HFC-143a mole.
7. according to the method for preparing bromotrifluoroethylene described in claim 6, it is characterised in that the phase transfer catalyst adds
Dosage is 1,2- bis- bromo- 1, the 0.5~2.0% of 1,2- HFC-143a amount, and the addition of the alkali is 1,2- bis- bromo- 1,1,2- tri-
1.5~2.0 times of fluoroethane mole.
8. according to the method for preparing bromotrifluoroethylene described in claim 1, it is characterised in that the phase transfer catalyst and alkali
The aqueous solution or alkali alcosol recycled.
9. according to the method for preparing bromotrifluoroethylene described in claim 1, it is characterised in that 1, the 2- bis- bromo- 1,1,2- tri-
Fluoroethane is prepared by trifluoro-ethylene or CTFE.
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| CN101563308A (en) * | 2006-12-19 | 2009-10-21 | 英尼奥斯弗罗控股有限公司 | Process for the preparation of c3-7 fluoroalkenes by base-mediated dehydrohalogenatation of hydrohalogenated c3 -7 fluoroalkanes |
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| CN101563308A (en) * | 2006-12-19 | 2009-10-21 | 英尼奥斯弗罗控股有限公司 | Process for the preparation of c3-7 fluoroalkenes by base-mediated dehydrohalogenatation of hydrohalogenated c3 -7 fluoroalkanes |
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