CN103360202B - The preparation method of a kind of phenyl-hexafluoride and a chlorine penta fluoro benzene - Google Patents
The preparation method of a kind of phenyl-hexafluoride and a chlorine penta fluoro benzene Download PDFInfo
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- KYPGQUIDUJCUTI-UHFFFAOYSA-N [Cl].FC=1C(=C(C(=C(C1)F)F)F)F Chemical compound [Cl].FC=1C(=C(C(=C(C1)F)F)F)F KYPGQUIDUJCUTI-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 30
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- CKAPSXZOOQJIBF-UHFFFAOYSA-N hexachlorobenzene Chemical compound ClC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl CKAPSXZOOQJIBF-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 235000003270 potassium fluoride Nutrition 0.000 claims abstract description 11
- 239000011698 potassium fluoride Substances 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 8
- 238000009833 condensation Methods 0.000 claims abstract description 7
- 230000005494 condensation Effects 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 239000000376 reactant Substances 0.000 claims abstract description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 3
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 13
- 238000009835 boiling Methods 0.000 claims description 12
- 125000001153 fluoro group Chemical group F* 0.000 claims description 9
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims description 7
- 230000031709 bromination Effects 0.000 claims description 5
- 238000005893 bromination reaction Methods 0.000 claims description 5
- WIHIUTUAHOZVLE-UHFFFAOYSA-N 1,3-diethoxypropan-2-ol Chemical compound CCOCC(O)COCC WIHIUTUAHOZVLE-UHFFFAOYSA-N 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 238000001514 detection method Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- 239000003444 phase transfer catalyst Substances 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000012360 testing method Methods 0.000 claims description 2
- 238000012805 post-processing Methods 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 6
- ZQBFAOFFOQMSGJ-UHFFFAOYSA-N hexafluorobenzene Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1F ZQBFAOFFOQMSGJ-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000004939 coking Methods 0.000 description 4
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- PMOIAJVKYNVHQE-UHFFFAOYSA-N phosphanium;bromide Chemical compound [PH4+].[Br-] PMOIAJVKYNVHQE-UHFFFAOYSA-N 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- KGCDGLXSBHJAHZ-UHFFFAOYSA-N 1-chloro-2,3,4,5,6-pentafluorobenzene Chemical compound FC1=C(F)C(F)=C(Cl)C(F)=C1F KGCDGLXSBHJAHZ-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005796 dehydrofluorination reaction Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 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 2
- -1 perfluoro aromatic compound Chemical class 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- AJKNNUJQFALRIK-UHFFFAOYSA-N 1,2,3-trifluorobenzene Chemical compound FC1=CC=CC(F)=C1F AJKNNUJQFALRIK-UHFFFAOYSA-N 0.000 description 1
- OZRCFSKDIYWITR-UHFFFAOYSA-N 1,2-dichloro-3,4,5,6-tetrafluorobenzene Chemical compound FC1=C(F)C(F)=C(Cl)C(Cl)=C1F OZRCFSKDIYWITR-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910018287 SbF 5 Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- HXELGNKCCDGMMN-UHFFFAOYSA-N [F].[Cl] Chemical compound [F].[Cl] HXELGNKCCDGMMN-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QICQRRAHXUYAHB-UHFFFAOYSA-N benzene;formonitrile Chemical compound N#C.C1=CC=CC=C1 QICQRRAHXUYAHB-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexediene Natural products C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 1
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- IHZAEIHJPNTART-UHFFFAOYSA-N tribromofluoromethane Chemical compound FC(Br)(Br)Br IHZAEIHJPNTART-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention is the preparation method of a kind of phenyl-hexafluoride and a chlorine penta fluoro benzene.The preparation method of phenyl-hexafluoride of the present invention and a chlorine penta fluoro benzene comprises the following steps: (1) raw material Perchlorobenzene, active potassium fluoride and catalyzer are put into reactor; (2) nitrogen replacement carried out to reactor and add solvent; (3) reactor is heated, after reaction terminates, stop heating; (4) after lowering the temperature, open the air valve of reactor, the reaction product in reactor and solvent are steamed in the lump and condensation recovery; By step (4) in condensation reclaim reaction product and solvent remove sour part by acid separator; (6) the phenyl-hexafluoride in reaction product and a chlorine penta fluoro benzene are separated by the method for rectifying by the reaction product after step (5) middle deacidification and solvent; (7), after the reactant in question response device and solvent recuperation, cooling, opens reactor, takes out the residues such as the Repone K in still.The present invention has that technological operation is easy, reaction temperature and, safety is controlled, postprocessing working procedures simple, loss less, feature that productive rate is high.
Description
Technical field
The present invention relates to the preparation method of a kind of phenyl-hexafluoride and a chlorine penta fluoro benzene.
Background technology
Phenyl-hexafluoride, also claims perfluor benzene, CAS:392-56-3, English name Perfluorobenzene, another name hexafluorobenzene, water white liquid, molecular formula C
6f
6, molecular weight 186.05, fusing point 3.7-4.1 ° C, boiling point 81-82 ° C, density 1.612g/cm
3, specific refractory power 1.376-1.378.
One chlorine penta fluoro benzene, also claims five fluorochlorobenzenes, CAS:344-07-0, English name chloropentafluorobenzene, water white liquid, molecular formula C
6f
5cl, molecular weight 202.50, fusing point 18.1 DEG C, boiling point 122-123 DEG C, density 1.64g/cm
3, specific refractory power 1.424.
Phenyl-hexafluoride and a chlorine penta fluoro benzene can as the important intermediate of synthesis perfluoro aromatic compound, synthesize multiple medicine, agricultural chemicals, liquid crystal material and special copolymer etc., find in the research of exploitation liquid crystal material in recent years, the liquid crystalline cpd using perfluor benzene and a chlorine penta fluoro benzene to derive has good performance, therefore has boundless development prospect.
Show according to current data, the study on the synthesis of phenyl-hexafluoride and a chlorine penta fluoro benzene is not yet carried out at home, do not retrieve the data about this aspect, the research report of phenyl-hexafluoride and a chlorine penta fluoro benzene is also few abroad, according to current grasped data, the synthetic route of phenyl-hexafluoride and a chlorine penta fluoro benzene mainly contains following several:
Method one: the dehydrofluorination method taking benzene as raw material
1956, Godsell, Stacey and Tatlow obtained phenyl-hexafluoride by nine fluorine hexanaphthenes dehydrofluorination in alkali lye.But nine fluorine hexanaphthenes need under 150 ° of C conditions by benzene vapour and CoF
3prepared by reaction, transformation efficiency is lower, limits its application.
Method two: the high-temperature cracking method taking fluorotribromomethane as raw material
Nineteen fifty-five, Desirant reports more directly and effective means: CFBr
3, in the platinotron of 630 ~ 640 DEG C, Pintsch process prepares phenyl-hexafluoride.
6CFBr
3——C
6F
6+9Br
2
Although this method is simple, the complicacy of radical polymerization causes product also more complicated, and selectivity is not high, and yield is low, and raw materials cost is high, is unfavorable for suitability for industrialized production.
Method three: take Perchlorobenzene as raw material direct fluorination
The people such as Mcbee, Lindgren and Ligett, successively use BrF
3, SbF
5, zinc powder process Perchlorobenzene, can obtain a small amount of phenyl-hexafluoride, other by products have tetrahydrobenzene and the cyclohexadiene compound of perfluor, fluorine chlorine.Be use Perchlorobenzene as raw material equally, Vorozhtsov, Platonov and Yakobson attempt using anhydrous K F to replace chlorine atom and prepare phenyl-hexafluoride.Reaction is carried out in autoclave, and temperature 450 ~ 500 DEG C, finally isolates C
6f
6fluorochlorobenzene (the C of (productive rate 2l%) and incomplete fluoro
6f
5c1:20%; C
6f
4c1
2: 14%; C
6f
3c1
3: 12%).
This method operational path is short, and raw materials cost is low, but it is low also to there is yield, and reactor coking is serious, limits industrialized application.
In sum, the synthetic method of existing phenyl-hexafluoride and a chlorine penta fluoro benzene also exists that transformation efficiency is lower, yield is low, reactor coking serious, is unfavorable for the weak point of suitability for industrialized production.
Summary of the invention
The object of the invention is to lower for the transformation efficiency existing for the synthetic method of existing phenyl-hexafluoride and a chlorine penta fluoro benzene, yield is low, reactor coking is serious, be unfavorable for the weak point of suitability for industrialized production, provide that a kind of technological operation is easy, reaction temperature and, safety is controlled, postprocessing working procedures simple, loss less, the preparation method of the high phenyl-hexafluoride of productive rate and a chlorine penta fluoro benzene.
Technical scheme of the present invention realizes in the following way: the preparation method of a kind of phenyl-hexafluoride and a chlorine penta fluoro benzene, with Perchlorobenzene and Potassium monofluoride for raw material, under phase-transfer catalyst effect, adopt single reaction vessel, prepare phenyl-hexafluoride and a chlorine penta fluoro benzene in a solvent, the preparation method of a kind of phenyl-hexafluoride of the present invention and a chlorine penta fluoro benzene comprises the following steps:
(1) raw material Perchlorobenzene, active potassium fluoride and catalyzer are put into reactor;
(2) pressure testing leakage detection and nitrogen replacement are carried out to the reactor that Perchlorobenzene, active potassium fluoride and catalyzer are housed, then add solvent in the reactor;
(3) the reactor that Perchlorobenzene, active potassium fluoride, catalyzer and solvent are housed is heated, make the slow increasing temperature and pressure of this reactor to temperature of reaction and reaction pressure, react after 24 ~ 48 hours, stop heating, cooling;
Until step (3) in reactor greenhouse cooling to 300 DEG C below time, open the air valve of reactor, the reaction product in reactor and solvent to be steamed in the lump and condensation is reclaimed;
By step (4) in condensation reclaim reaction product and solvent remove sour part by acid separator;
(6) the phenyl-hexafluoride in reaction product and a chlorine penta fluoro benzene are separated by the method for rectifying by the reaction product after step (5) middle deacidification and solvent, the fluorochlorobenzene (C of complete fluoro
6f
4c1
2; C
6f
3c1
3; C
6f
2c1
4, C
6fC1
5deng) rejoin after super-dry in reactor continue to use with solvent;
(7) after the reactant in question response device and solvent recuperation, be cooled to less than 60 DEG C, open reactor, take out the residues such as the Repone K in still, the preparation work of phenyl-hexafluoride and a chlorine penta fluoro benzene completes.
In the preparation method of above-mentioned a kind of phenyl-hexafluoride and a chlorine penta fluoro benzene, step (1) in, described Perchlorobenzene and the mass ratio of active potassium fluoride are 1:1.2 ~ 2.5.
In the preparation method of above-mentioned a kind of phenyl-hexafluoride and a chlorine penta fluoro benzene, step (1) in, described Perchlorobenzene and the mass ratio of active potassium fluoride are 1:1.7 ~ 2.0.
In the preparation method of above-mentioned a kind of phenyl-hexafluoride and a chlorine penta fluoro benzene, step (1) in, described Perchlorobenzene and the mass ratio of catalyzer are 1:0.005 ~ 0.03.
In the preparation method of above-mentioned a kind of phenyl-hexafluoride and a chlorine penta fluoro benzene, step (1) in, described Perchlorobenzene and the mass ratio of catalyzer are 1:0.01 ~ 0.015.
In the preparation method of above-mentioned a kind of phenyl-hexafluoride and a chlorine penta fluoro benzene, step (1) in, described catalyzer adopts the four (one in diethylin) phosphonium bromide, bromination Shi six alkyl San Ding Ji Phosphonium, bromination hexadecane base San Yi Ji Phosphonium, hexadecyl San Ding Ji Phosphonium.
In the preparation method of above-mentioned a kind of phenyl-hexafluoride and a chlorine penta fluoro benzene, step (1) in, described catalyzer adopts four (diethylin) phosphonium bromides.
In the preparation method of above-mentioned a kind of phenyl-hexafluoride and a chlorine penta fluoro benzene, step (2) in, the mass ratio of Perchlorobenzene and solvent is 1:1.
In the preparation method of above-mentioned a kind of phenyl-hexafluoride and a chlorine penta fluoro benzene, step (2) in, described solvent adopts the cyanobenzene solvent of drying process, and wherein, the moisture in cyanobenzene solvent is less than 30ppm; Carrying out drying treatment to cyanobenzene solvent adopts calcium chloride or molecular sieve to carry out drying treatment.
In the preparation method of above-mentioned a kind of phenyl-hexafluoride and a chlorine penta fluoro benzene, step (3) in, described temperature of reaction is 500 ~ 650 DEG C, and described reaction pressure is 6.0 ~ 10Mpa.
In the preparation method of above-mentioned a kind of phenyl-hexafluoride and a chlorine penta fluoro benzene, step (3) in, described temperature of reaction is 580 ~ 630 DEG C, and described reaction pressure is 8.0 ~ 9.0Mpa.
In the preparation method of above-mentioned a kind of phenyl-hexafluoride and a chlorine penta fluoro benzene, step (5) in, described acid separator adopts solid sodium bicarbonate acid separator.
In the preparation method of a kind of phenyl-hexafluoride of the present invention and a chlorine penta fluoro benzene, with Perchlorobenzene and Potassium monofluoride, for raw material high-temperature catalytic, to fluoridize the reaction equation preparing phenyl-hexafluoride and a chlorine penta fluoro benzene as follows:
Fluorochlorobenzene (the C of other incomplete fluoro is also had in reaction product
6f
4c1
2; C
6f
3c1
3; C
6f
2c1
4, C
6fC1
5deng), by these completely the fluorochlorobenzene of fluoro re-start high-temperature catalytic after being separated and fluoridize and can be further converted to phenyl-hexafluoride and a chlorine penta fluoro benzene, the overall yield of phenyl-hexafluoride and a chlorine penta fluoro benzene can be improved.
The present invention compares with the synthetic method of existing phenyl-hexafluoride with a chlorine penta fluoro benzene, has following characteristics:
1, avoid the coking of reaction product, the yield that improve, the productive rate of one way can reach more than 60%, is applicable to suitability for industrialized production.
2, synthesis route is short, one-step synthesis phenyl-hexafluoride and a chlorine penta fluoro benzene, and product proportion can regulate easily, and can obtain dichloro-tetrafluoro benzene as required, the fluorochlorobenzene of the incomplete fluoro such as trichlorine trifluoro-benzene.
3, technological operation is easy, reaction temperature and, safety is controlled, and postprocessing working procedures is simple, and loss is few, and productive rate is high.
4, raw material used is general chemical product, and the prices of raw and semifnished materials are low, and the productive rate of building-up reactions is high, and production cost is lower.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of the preparation method of a kind of phenyl-hexafluoride of the present invention and a chlorine penta fluoro benzene.
In fig. 1,1 represents reactor; 2 represent crude product condenser; 3 represent acid separator; 4 represent rectifying tower; 5 represent solvent drier; 6 represent solvent feed tank.
Embodiment
Below by embodiment the present invention made and further illustrating, but the present invention is not limited only to these embodiments.
Embodiment 1:
Add raw material Perchlorobenzene 130g, active potassium fluoride 260g in the reactor, with catalyzer four (diethylin) phosphonium bromide 1.3g, after methylene dichloride dehydration, add dry benzene formonitrile HCN 130g, after having fed in raw material, reactor is slowly warmed up to 580 DEG C, and constant temperature is after 30 hours, reaction pressure is 8.0 ~ 8.2Mpa, stops heating, when being cooled to 300 DEG C, open air valve, reactant and solvent are steamed in the lump and condensation recovery.Record the yield data of reaction product in table one:
Table one:
| Embodiment | C 6F 6，％ | C 6F 5C1，％ | Other fluorochlorobenzene, % | Other high boiling material, % |
| 1 | 31.6 | 30.3 | 33.3 | 4.8 |
Other fluorochlorobenzene refers to: C
6f
4c1
2, C
6f
3c1
3, C
6f
2c1
4, C
6fC1
5deng.
Other high boiling material refers to the product except fluorochlorobenzene, mainly comprises: C
8f
9c1, C
12f
14, C
13f
10c
12deng.
Embodiment 2,3,4,5:
By the operation steps of example one, keep other reaction conditions constant, controlling temperature of reaction is respectively 500 DEG C, 550 DEG C, 600 DEG C, 650 DEG C, and the yield data of assaying reaction product is in table two:
Table two:
| Embodiment | Temperature of reaction | C 6F 6，％ | C 6F 5C1，％ | Other fluorochlorobenzene, % | Other high boiling material, % |
| 2 | 500℃ | 14.6 | 18.4 | 63.8 | 3.2 |
| 3 | 550℃ | 28.9 | 29.8 | 37.0 | 4.3 |
| 4 | 600℃ | 33.2 | 30.1 | 31.1 | 5.6 |
| 5 | 650℃ | 34.6 | 29.7 | 25.4 | 10.3 |
Embodiment 6,7,8:
By the operation steps of example one, keep other reaction conditions constant, the mass ratio controlling Perchlorobenzene and catalyzer is respectively 1:005,1:0.015,1:0.03, and the yield data of assaying reaction product is in table three:
Table three:
| Embodiment | Ratio | C 6F 6，％ | C 6F 5C1，％ | Other fluorochlorobenzene, % | Other high boiling material, % |
| 6 | 1:005 | 19.8 | 21.2 | 55.7 | 3.3 |
| 7 | 1:0.015 | 33.1 | 29.3 | 32.71 | 4.9 |
| 8 | 1:0.03 | 34.8 | 28.1 | 32.0 | 5.1 |
Embodiment 9,10,11:
By the operation steps of example one, keep other reaction conditions constant, the mass ratio controlling Perchlorobenzene and Potassium monofluoride is respectively 1:1.2,1:7,1:2.5, and the yield data of assaying reaction product is in table four:
Table four:
| Embodiment | Ratio | C 6F 6，％ | C 6F 5C1，％ | Other fluorochlorobenzene, % | Other high boiling material, % |
| 9 | 1:1.2 | 21.2 | 24.9 | 50.0 | 3.9 |
| 10 | 1:1.7 | 30.5 | 29.8 | 35.3 | 4.4 |
| 11 | 1:2.5 | 32.6 | 27.9 | 34.6 | 4.9 |
Embodiment 12,13:
By the operation steps of example one, keep other reaction conditions constant, controlling the reaction times is respectively 24 hours, 48 hours, and the yield data of assaying reaction product is in table five:
Table five:
| Embodiment | Reaction times | C 6F 6，％ | C 6F 5C1，％ | Other fluorochlorobenzene, % | Other high boiling material, % |
| 12 | 24 hours | 25.6 | 27.8 | 42.3 | 4.3 |
| 13 | 48 hours | 32.0 | 29.4 | 33.7 | 4.9 |
Embodiment 14,15,16:
By the operation steps of example one, keep other reaction conditions constant, catalyzer is changed into bromination Shi six alkyl San Ding Ji Phosphonium, bromination hexadecane base San Yi Ji Phosphonium, hexadecyl San Ding Ji Phosphonium, the yield data of assaying reaction product is in table six:
Table six:
Embodiment 17:
By the operation steps of example one, keep other reaction conditions constant, using containing other fluorochlorobenzene and high boiling material be the cyanobenzene of 31.2% as solvent, the yield data of assaying reaction product is in table seven:
Table seven:
| Embodiment | C 6F 6，％ | C 6F 5C1，％ | Other fluorochlorobenzene, % | Other high boiling material, % |
| 17 | 37.8 | 36.6 | 19.3 | 6.3 |
Claims (1)
1. the preparation method of a phenyl-hexafluoride and a chlorine penta fluoro benzene, it is characterized in that with Perchlorobenzene and Potassium monofluoride for raw material, under phase-transfer catalyst effect, adopt single reaction vessel, prepare phenyl-hexafluoride and a chlorine penta fluoro benzene in a solvent, the preparation method of this phenyl-hexafluoride and a chlorine penta fluoro benzene comprises the following steps:
(1) raw material Perchlorobenzene, active potassium fluoride and catalyzer are put into reactor;
(2) pressure testing leakage detection and nitrogen replacement are carried out to the reactor that Perchlorobenzene, active potassium fluoride and catalyzer are housed, then add solvent in the reactor;
(3) the reactor that Perchlorobenzene, active potassium fluoride, catalyzer and solvent are housed is heated, wherein solvent is the fluorochlorobenzene of completely fluoro and high boiling material is the cyanobenzene of 31.2%, this reactor is made slowly to be warmed up to 580 DEG C, boosting to is 8.0 ~ 8.2Mpa, react 30 hours, stop heating, cooling;
Until step (3) in reactor greenhouse cooling to 300 DEG C below time, open the air valve of reactor, the reaction product in reactor and solvent to be steamed in the lump and condensation is reclaimed;
By step (4) in condensation reclaim reaction product and solvent remove sour part by acid separator;
(6) the reaction product after step (5) middle deacidification and solvent the phenyl-hexafluoride in reaction product and a chlorine penta fluoro benzene are separated by the method for rectifying, the fluorochlorobenzene of complete fluoro and solvent rejoin in reactor and continue to use after super-dry;
(7) after the reactant in question response device and solvent recuperation, be cooled to less than 60 DEG C, open reactor, take out the Repone K residue in still, the preparation work of phenyl-hexafluoride and a chlorine penta fluoro benzene completes; Described solvent adopts the fluorochlorobenzene of not fluoro completely and high boiling material to be the cyanobenzene of 31.2%, and wherein, the moisture in cyanobenzene solvent is less than 30ppm; The fluorochlorobenzene of described incomplete fluoro is C
6f
4c1
2, C
6f
3c1
3, C
6f
2c1
4, C
6fC1
5, described acid separator adopts solid sodium bicarbonate acid separator, wherein Perchlorobenzene 130g, active potassium fluoride 260g, catalyzer four (diethylin) bromination squama 1.3g.
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| CN1238748A (en) * | 1996-11-22 | 1999-12-15 | 阿尔伯麦尔公司 | Halogen exchange reactions and uses thereof |
| CN101168493A (en) * | 2006-10-26 | 2008-04-30 | 中国石油化工股份有限公司 | Preparation method for fluorochlorobenzene |
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| CN1238748A (en) * | 1996-11-22 | 1999-12-15 | 阿尔伯麦尔公司 | Halogen exchange reactions and uses thereof |
| US6241917B1 (en) * | 1996-11-22 | 2001-06-05 | Albemarle Corporation | Halogen exchange reactions in preparing catalysts and their precursors |
| CN101168493A (en) * | 2006-10-26 | 2008-04-30 | 中国石油化工股份有限公司 | Preparation method for fluorochlorobenzene |
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| 六氟苯制备研究进展;冉德强等;《有机氟工业》;20121231(第4期);第36-38页 * |
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