CN103664503B - The synthesis of 1,2,3,4-tetrachloro-hexafluoro butane - Google Patents
The synthesis of 1,2,3,4-tetrachloro-hexafluoro butane Download PDFInfo
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- CN103664503B CN103664503B CN201310700165.5A CN201310700165A CN103664503B CN 103664503 B CN103664503 B CN 103664503B CN 201310700165 A CN201310700165 A CN 201310700165A CN 103664503 B CN103664503 B CN 103664503B
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- IRHYACQPDDXBCB-UHFFFAOYSA-N 1,2,3,4-tetrachloro-1,1,2,3,4,4-hexafluorobutane Chemical compound FC(F)(Cl)C(F)(Cl)C(F)(Cl)C(F)(F)Cl IRHYACQPDDXBCB-UHFFFAOYSA-N 0.000 title abstract description 47
- 230000015572 biosynthetic process Effects 0.000 title abstract description 12
- 238000003786 synthesis reaction Methods 0.000 title abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 79
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000011737 fluorine Substances 0.000 claims abstract description 45
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims description 45
- 239000007789 gas Substances 0.000 claims description 42
- 239000000463 material Substances 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 13
- 238000010189 synthetic method Methods 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- DDMOUSALMHHKOS-UHFFFAOYSA-N 1,2-dichloro-1,1,2,2-tetrafluoroethane Chemical compound FC(F)(Cl)C(F)(F)Cl DDMOUSALMHHKOS-UHFFFAOYSA-N 0.000 claims description 8
- 238000005796 dehydrofluorination reaction Methods 0.000 claims description 7
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 claims description 7
- 229910000105 potassium hydride Inorganic materials 0.000 claims description 7
- 229940087091 dichlorotetrafluoroethane Drugs 0.000 claims description 6
- 238000010790 dilution Methods 0.000 claims description 6
- 239000012895 dilution Substances 0.000 claims description 6
- 239000001307 helium Substances 0.000 claims description 6
- 229910052734 helium Inorganic materials 0.000 claims description 6
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 230000002459 sustained effect Effects 0.000 claims description 6
- 238000000746 purification Methods 0.000 abstract description 18
- LWDGFGTYBDRKHU-UHFFFAOYSA-N 1,2-dichloro-1-fluoroethene Chemical compound FC(Cl)=CCl LWDGFGTYBDRKHU-UHFFFAOYSA-N 0.000 abstract description 16
- 239000002994 raw material Substances 0.000 abstract description 13
- 239000006227 byproduct Substances 0.000 abstract description 6
- 238000007086 side reaction Methods 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 2
- 230000008676 import Effects 0.000 description 14
- 239000000126 substance Substances 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- -1 butyl halide Chemical class 0.000 description 7
- 239000007791 liquid phase Substances 0.000 description 7
- UPVJEODAZWTJKZ-UHFFFAOYSA-N 1,2-dichloro-1,2-difluoroethene Chemical compound FC(Cl)=C(F)Cl UPVJEODAZWTJKZ-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- IDSKMUOSMAUASS-UHFFFAOYSA-N 1,2-dichloro-1,2-difluoroethane Chemical compound FC(Cl)C(F)Cl IDSKMUOSMAUASS-UHFFFAOYSA-N 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 4
- 229930013930 alkaloid Natural products 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 230000000977 initiatory effect Effects 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- KIZFHUJKFSNWKO-UHFFFAOYSA-M calcium monohydroxide Chemical compound [Ca]O KIZFHUJKFSNWKO-UHFFFAOYSA-M 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 229910052754 neon Inorganic materials 0.000 description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 3
- UJMWVICAENGCRF-UHFFFAOYSA-N oxygen difluoride Chemical compound FOF UJMWVICAENGCRF-UHFFFAOYSA-N 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 description 3
- LGPPATCNSOSOQH-UHFFFAOYSA-N 1,1,2,3,4,4-hexafluorobuta-1,3-diene Chemical compound FC(F)=C(F)C(F)=C(F)F LGPPATCNSOSOQH-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 229910018487 Ni—Cr Inorganic materials 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 2
- VNTLIPZTSJSULJ-UHFFFAOYSA-N chromium molybdenum Chemical compound [Cr].[Mo] VNTLIPZTSJSULJ-UHFFFAOYSA-N 0.000 description 2
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 229910000856 hastalloy Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- QYSGYZVSCZSLHT-UHFFFAOYSA-N octafluoropropane Chemical compound FC(F)(F)C(F)(F)C(F)(F)F QYSGYZVSCZSLHT-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229960004065 perflutren Drugs 0.000 description 2
- VBKNTGMWIPUCRF-UHFFFAOYSA-M potassium;fluoride;hydrofluoride Chemical compound F.[F-].[K+] VBKNTGMWIPUCRF-UHFFFAOYSA-M 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- IXZVKECRTHXEEW-UHFFFAOYSA-N 1,2,3,4-tetrachlorobutane Chemical compound ClCC(Cl)C(Cl)CCl IXZVKECRTHXEEW-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000003190 augmentative effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to synthesis and the purification process of 1,2,3,4-tetrachloro-hexafluoro butane, press the mol ratio of 0.2-0.5:1 at-20 DEG C ~-100 DEG C by the fluoro-1,2-dichloroethene solution of 1,2-bis-and fluorine gas, react lower than under the condition of 0.1Mpa, containing 1,2,3,4-tetrachloro-hexafluoro butane in gained solution; Gained solution is distilled successively, rectifying and drying, obtain highly purified 1,2,3,4-tetrachloro-hexafluoro butane.1,2,3,4-tetrachloro-hexafluoro butane preparation were established of the present invention is short, only needs single step reaction and three step purifying; Preparation 1mol1,2,3,4-tetrachloro-hexafluoro butane only need consume the theoretical fluorine gas amount of 1mol, reduces raw materials cost; Temperature of reaction is low, decrease side reaction and occur, and by product has higher economic worth; Reaction easily controls, simple to operate; Feed stock conversion is close to 100%.The inventive method has higher economy, can be used for the industrialization scale operation of 1,2,3,4-tetrachloro-hexafluoro butane.
Description
Technical field
The present invention relates to chemical field, specifically, relate to a kind of synthesis and purification process of 1,2,3,4-tetrachloro-hexafluoro butane.
Background technology
1,2,3,4-tetrachloro-hexafluoro butane is the main synthesis material of hexafluoro-1,3-butadiene, and hexafluoro-1, the etching gas that 3-divinyl uses as semiconductor machining receives much concern, and it can etch 100nm, even narrower width, and has very high accuracy; Hexafluoro-1,3-butadiene makes the latent energy value of Global warming be 290 simultaneously, and lifetime was lower than 2 days in an atmosphere.Therefore, the synthetic method developing 1,2,3,4-tetrachloro-hexafluoro butane has good economic worth and environment protection significance.
At present, the method for synthesizing 1,2,3,4-tetrachloro-hexafluoro butane comprises:
1, be raw material through three-step reaction synthesis 1,2,3,4-tetrachloro-hexafluoro butane with the fluoro-1,2-dichloroethene of 1,2-bis-.But require higher to temperature of reaction in building-up process, and need photochemical reaction be carried out, to reaction controlling not easily and higher to equipment requirements.
2, take trifluorochloroethylene as raw material, prepare 1,2,3,4-tetrachloro-hexafluoro butane at mercury as under catalyzer.Its disadvantage is to employ the larger heavy metal Hg of toxicity in reaction.
3, with iodo-1, the 2-dichlorotrifluoroethane of 1-for raw material, in organic solvent and methylene dichloride medium, react preparation 1,2,3,4-tetrachloro-hexafluoro butane with zinc powder.But raw material methylene dichloride toxicity is comparatively large, needs to drip organic solvent continuously, complicated operation in reaction, and simultaneous reactions is violent, be difficult to control, and side reaction is more.
4, be that raw material is through chlorination with fluoridize preparation 1,2,3,4-tetrachloro-hexafluoro butane with 1,3-butadiene.Need in this method building-up process to consume a large amount of chlorine and fluorine gas, preparation 1mol1,2,3,4-tetrachloro-hexafluoro butane need consume the theoretical amount of chlorine of 2mol and the theoretical fluorine gas amount of 3mol, and therefore cost is higher, and produces gas HF and HCl in reaction process, serious to equipment corrosion, also increase the difficulty of separation and purification simultaneously; Two kinds of optically active isomer nature differences of intermediate 1,2,3,4-tetra-chlorobutane in this method building-up process are comparatively large, add its treatment step; A series of butyl halide can be produced because chlorination is different with the degree of fluoridizing in this method building-up process, reduce the selectivity of 1,2,3,4-tetrachloro-hexafluoro butane, also make separating difficulty strengthen.
Summary of the invention
The object of this invention is to provide a kind of synthesis and purification process of 1,2,3,4-tetrachloro-hexafluoro butane.
In order to realize the object of the invention, of the present invention a kind of 1,2,3, the synthetic method of 4-tetrachloro-hexafluoro butane, makes 1,2-bis-fluoro-1,2-Ethylene Dichloride solution and fluorine gas press the mol ratio of 0.2-0.5:1 at-20 DEG C ~-100 DEG C, react lower than under the condition of 0.1Mpa, containing 1,2 in gained solution, 3,4-tetrachloro-hexafluoro butane; Wherein, in described 1,2-bis-fluoro-1,2-dichloroethene solution, the starting point concentration of 1,2-bis-fluoro-1,2-dichloroethene is 2%-60v/v%, and the solvent of use includes but not limited at least one in perfluoro alkane, fluorochloroparaffins, fluorochloro ether, PFPE etc.Wherein, perfluoro alkane, fluorochloroparaffins, fluorochloro ether institute carbon atom quantity≤15, the molecular weight of PFPE is 800 ~ 20000 dalton.Such as, octafluoropropane, 1,2-dichloro tetrafluoro ethane, perfluoro-methyl-1,2-dichloro-tetrafluoro ethyl ether, poly-perfluor isopropyl ether wet goods.
Wherein, fluorine oxide, perfluoroalkyl superoxide (ROF), the perfluoroalkyl superoxide (R that concentration is 1 ~ 10v/v% is also contained in described 1,2-bis-fluoro-1,2-dichloroethene solution
foOR
/ f), perfluoroacyl peroxides ((R
fcOOOOCR
/ f) etc. at least one auxiliary material.Wherein, the molecular weight of fluorine oxide, perfluoroalkyl superoxide, perfluoroacyl peroxides is 100 ~ 1000 dalton.Such as, CF
3oF, CF
3oOCF
3, CF
2clCOOOOCCF
2cl etc.
In aforementioned synthetic methods, fluorine gas inert gas dilution to concentration is that after 20 ~ 85v/v%, fluoro-1,2-dichloroethene solution reacts with 1,2-bis-.Described rare gas element includes but not limited to nitrogen, helium, argon gas etc.
In aforementioned synthetic methods, the importing flow of fluorine gas is 10-500L/h.
In aforementioned synthetic methods, described reaction carries out in the reaction vessel be made up of Hastelloy, nickel chromium stainless steel, molybdenum Chromium Stainless Steel, corrosion-resistant, low temperature resistant material such as lining tetrafluoro resin material or tetrafluoro resin material etc.Described 1,2-bis-fluoro-1,2-dichloroethene solution accounts for the 5%-100% of reaction vessel volume.
The present invention also provides 1, and 2,3, the purification process of 4-tetrachloro-hexafluoro butane, contains 1,2 by what prepare according to above-mentioned synthetic method, the solution of 3,4-tetrachloro-hexafluoro butane imports in retort, isolates fluorine-containing low-boiling-point substance, then will containing 1,2,3, the solution of 4-tetrachloro-hexafluoro butane imports in rectifying tower, and isolated 1,2,3,4-tetrachloro-hexafluoro butane contacts with siccative with alkaloids successively.
In aforementioned purification process, the temperature of retort controls at 10 DEG C-60 DEG C.
In aforementioned purification process, in rectifying tower, implement negative pressure (gauge pressure) rectifying.In rectifying tower, be separated the content of 1,2,3, the 4-tetrachloro-hexafluoro butane obtained higher than 95% from containing in the solution of 1,2,3,4-tetrachloro-hexafluoro butane, be recycled in retort lower than the solution of 95%.
In aforementioned purification process, described alkaloids includes but not limited to NaOH, KOH, CaOH, CaO, MgO etc., and described siccative includes but not limited to soda-lime, CaCl
2, CaSO
4, P
2o
5, Na
2sO
4, MgSO
4, CaSO
4deng.
The present invention uses the fluoro-1,2-dichloroethene of 1,2-bis-as starting raw material, make its containing in fluorous solvent with fluorine gas, there is telomerization at low temperatures, thus preparation 1,2,3,4-tetrachloro-hexafluoro butane.Reaction formula is as follows:
Main reaction 2CFCl=CFCl+F
2→ CF
2clCFClCFClCF
2cl ... 1.
Side reaction CFCl=CFCl+F
2→ CF
2clCF
2cl ... 2.
CFCl=CFCl+F
2→2CF
3Cl……③
3CFCl=CFCl+F
2→CF
2Cl（CFCl）
4CF
2Cl……④
Use the fluoro-1,2-dichloroethene of 1,2-bis-as starting raw material in the present invention, the fluoro-1,2-dichloroethene of 1,2-bis-is a kind of important chemical intermediate, and its content, higher than 99.00%, wherein containing a small amount of HF and trifluorochloroethylene, does not affect reaction of the present invention.There are cis and trans two kinds of steric isomers in the fluoro-1,2-dichloroethene of 1,2-bis-, its physical properties slightly difference, but do not affect reaction of the present invention.
The raw material fluorine gas that the present invention uses, obtained by electrolysis potassium bifluoride, wherein containing a small amount of hydrogen fluoride gas and potassium bifluoride molecule, after dehydrofluorination and the process of defluorinate potassium hydride KH, then use after being diluted to 20%-85% concentration (volume percent) through inert nitrogen gas, helium, neon, argon pressurization.
The reactor used in the present invention is voltage-resistant reactor, generally to configure fluorine gas gauger, refrigerating unit, whipping appts and conduit and distribution device in gas-fluid for importing gas in liquid phase, and then add the contact of atmospheric and liquid, filler need be added, with the exchange of substance dynamics in augmenting response in reactor.
In reaction of the present invention, the gas fluorine gas of highly corrosive need be imported in reactor, simultaneous reactions temperature controls at-20 DEG C ~-100 DEG C, therefore, fluorine gas gauger, reactor, whipping appts, for import the conduit of gas and distribution device in gas-fluid, filler in liquid phase must be low temperature resistant and fluorine gas is had to the material of erosion resistance.The material such as Hastelloy, nickel chromium stainless steel, molybdenum Chromium Stainless Steel, lining tetrafluoro resin material, tetrafluoro resin material can be selected.
The reaction solvent used in the present invention, must possess following condition: 1. do not react with fluorine gas, is inert liq relative to fluorine gas; 2. be in a liquid state in the scope of-20 DEG C ~-100 DEG C; 3. there is not any chemical reaction with equipment material, the fluoro-1,2-dichloroethene of raw material 1,2-bis-and reaction product.Perfluoro alkane, fluorochloroparaffins, fluorochloro ether, perfluor, PFPE etc. can be selected, as octafluoropropane, 1,2-dichloro tetrafluoro ethane, perfluoro-methyl-1,2-dichloro-tetrafluoro ethyl ether, poly-perfluor isopropyl ether wet goods.
As reaction solution of the present invention, the starting point concentration of the fluoro-1,2-dichloroethene of raw material 1,2-bis-in above-mentioned solvent controls in 2% ~ 60%(volume percent).Loaded in above-mentioned reaction vessel, accounted for 5% ~ 100% of reactor volume.
In the fluoro-1,2-dichloroethene solution of reaction solution 1,2-bis-of the present invention, import appropriate auxiliary material, auxiliary material can be fluorine oxide (ROF), perfluoroalkyl superoxide (R
foOR
/ f), perfluoroacyl peroxides ((R
fcOOOOCR
/ f) etc. one or more, its role is to the initiation reaction as initiator.As reaction of the present invention, generally fluorine gas can initiation reaction, and end group is fluorine, on reaction product structure without impact, but under special circumstances, as too low in temperature etc., and fluorine gas can not initiation reaction, then need to add above-mentioned auxiliary material to reach the object of initiation reaction; After introducing auxiliary material, the end group of byproduct of reaction is other group, and reaction product structure, without impact, therefore, imports auxiliary material and consumption can be considered as one sees fit in the fluoro-1,2-dichloroethene solution of reaction solution 1,2-bis-.
The temperature of reaction that the present invention reacts is controlled in the scope of-20 DEG C ~-100 DEG C, reduces above-mentioned reaction object 2., 3. and 4. to reach.
By reaction system pressure-controlling of the present invention lower than 0.1Mpa(gauge pressure) scope.
In the present invention, the fluorine gas of the dilution imported in reaction vessel liquid-phase system as mentioned above, has neither part nor lot in the part of reaction through carrying out washing treatment emptying.
The target product of synthetic method of the present invention is 1,2,3,4-tetrachloro-hexafluoro butane, therefore, need isolate target product 1,2,3,4-tetrachloro-hexafluoro butane from reaction solution described above.
In the purification process of 1,2,3,4-tetrachloro-hexafluoro butane of the present invention, use at least one retort and at least one rectifying tower, separation and purification is carried out to the above-mentioned reaction solution containing 1,2,3,4-tetrachloro-hexafluoro butane.That is, with rare gas element as nitrogen, helium, neon, argon gas, make pressurization in reaction unit, reaction solution slowly imported in retort, isolates fluorine-containing low-boiling-point substance, as 1,2-dichloro tetrafluoro ethane etc. is discharged by retort top.Isolated fluorine-containing low-boiling-point substance has higher economic worth, can be used as byproduct and collects.The configurable heating unit of retort used, and temperature controls at 15 DEG C ~ 80 DEG C.
To in retort, use rare gas element as nitrogen, helium, neon, argon pressurization, rectifying tower is imported isolating the reaction solution after fluorine-containing low-boiling-point substance through retort, 1 is at least partially isolated from this reaction solution, the content of 2,3,4-tetrachloro-hexafluoro butane is higher than 95%, by lower than 95% containing 1, the liquids recovery of 2,3,4-tetrachloro-hexafluoro butane is in retort.The rectifying tower of at least 10 blocks of theoretical trays selected by this rectifying tower, and working pressure implements negative pressure (gauge pressure) operation.
The part isolating the fluorine-containing liquid after 1,2,3,4-tetrachloro-hexafluoro butane is at least partially back in fluorine gas and 1,2-bis-fluoro-1,2-dichloroethene solution reaction device to be recycled.Because isolating in the fluorine-containing liquid after 1,2,3,4-tetrachloro-hexafluoro butane at least partially containing the CF with higher economic worth
2cl(CFCl)
4cF
2cl, so collect the fluorine-containing liquid of above-mentioned another part as byproduct.
Isolated 1,2,3,4-tetrachloro-hexafluoro butane is contacted with siccative with alkaloids successively.Alkaloids is as NaOH, KOH, CaOH, CaO, MgO etc., and siccative is as soda-lime, CaCl
2, CaSO
4, P
2o
5, Na
2sO
4, MgSO
4, CaSO
4deng.
1,2,3,4-tetrachloro-hexafluoro butane after purified imports in 95%(mass percent), preferably in 98%(mass percent).1,2,3,4-tetrachloro-hexafluoro butane selectivity is more than 70%.
1,2,3,4-tetrachloro-hexafluoro butane preparation were established provided by the invention is short, only needs single step reaction and three step purifying; Preparation 1mol1,2,3,4-tetrachloro-hexafluoro butane only need consume the theoretical fluorine gas amount of 1mol, reduces raw materials cost; 1,2-bis-fluoro-1,2-dichloroethene transformation efficiency is high, and 1,2,3,4-tetrachloro-hexafluoro butane selectivity is high, and temperature of reaction is low, decrease side reaction and occur, and by product has higher economic worth, can be used as byproduct and recycles, solvent reusable edible; Reaction easily controls, simple to operate; Feed stock conversion is close to 100%, and the selectivity of 1,2,3,4-tetrachloro-hexafluoro butane is more than 70%.The inventive method has higher economy, industrialization can stably prepare highly purified 1,2,3,4-tetrachloro-hexafluoro butane on a large scale.
Accompanying drawing explanation
Fig. 1 is the setting drawing used in 1,2,3,4-tetrachloro-hexafluoro butane preparation technology of the present invention; Wherein, 1: the reactor of fluorine gas and the fluoro-1,2-dichloroethene of 1,2-bis-; 2: retort; 3: rectifying tower; 4: condenser; 5: alkaline matter contact tower; 6: drying tower.
Embodiment
Following examples for illustration of the present invention, but are not used for limiting the scope of the invention.If do not specialize, the conventional means that technique means used in embodiment is well known to those skilled in the art, is raw materials usedly commercial goods.
The synthesis of embodiment 11,2,3,4-tetrachloro-hexafluoro butane and purifying
Volume be 10L be in the homemade reactor of material with 316L, splendid attire is with 1, 2-dichloro tetrafluoro ethane is solvent and 1, 2-bis-fluoro-1, 2-Ethylene Dichloride content is 50%(volume percent) solution 5L, by the fluorine gas of electrolytic preparation after dehydrofluorination and the process of defluorinate potassium hydride KH, be forced into 0.15Mpa, by fluorine gas with nitrogen dilution to 40%(volume percent), 1 is imported by the flow of 200L/h, 2-bis-fluoro-1, 1 of 2-Ethylene Dichloride, sustained reaction 9 hours in 2-dichloro tetrafluoro ethane solution, maintaining reaction unit internal pressure in reaction process is 0.05Mpa, maintain the liquidus temperature of reaction system at-75 ± 1 DEG C.Get liquid phase reaction liquid after reaction terminating, analyze by gas-chromatography.Analytical results is as follows: the selectivity 81.355% of transformation efficiency 98.263%, 1,2,3, the 4-tetrachloro-hexafluoro butane of the fluoro-1,2-dichloroethene of 1,2-bis-.
1,2,3, the 4-tetrachloro-hexafluoro butane that purity is 99.57% will be obtained after carrying out purification process containing 1,2,3,4-tetrachloro-hexafluoro butane reaction solution.The method of purification process is: contain 1,2,3 by what prepare according to above-mentioned synthetic method, the solution of 4-tetrachloro-hexafluoro butane imports in the retort of 50 DEG C, isolate fluorine-containing low-boiling-point substance, then will containing 1,2,3, the solution of 4-tetrachloro-hexafluoro butane imports in rectifying tower implements negative pressure (gauge pressure) rectifying, isolated 1,2,3,4-tetrachloro-hexafluoro butane contacts with soda-lime with NaOH successively.The yield of 1,2,3,4-tetrachloro-hexafluoro butane is 79.292%.
The synthesis of embodiment 21,2,3,4-tetrachloro-hexafluoro butane and purifying
Volume be 10L be in the homemade reactor of material with 316L, splendid attire is with 1, 2-dichloro tetrafluoro ethane is solvent and 1, 2-bis-fluoro-1, 2-Ethylene Dichloride content is 50%(volume percent) solution 5L, by the fluorine gas of electrolytic preparation after dehydrofluorination and the process of defluorinate potassium hydride KH, be forced into 0.07Mpa, fluorine gas helium is diluted to 60%(volume percent), 1 is imported by the flow of 200L/h, 2-bis-fluoro-1, 1 of 2-Ethylene Dichloride, sustained reaction 7 hours in 2-dichloro tetrafluoro ethane solution, maintaining reaction unit internal pressure in reaction process is 0.02Mpa, maintain the liquidus temperature of reaction system at-75 ± 1 DEG C.Get liquid phase reaction liquid after reaction terminating, analyze by gas-chromatography.Analytical results is as follows: the selectivity 72.34% of transformation efficiency 99.058%, 1,2,3, the 4-tetrachloro-hexafluoro butane of the fluoro-1,2-dichloroethene of 1,2-bis-.
1,2,3, the 4-tetrachloro-hexafluoro butane that purity is 99.913% will be obtained after carrying out purification process containing 1,2,3,4-tetrachloro-hexafluoro butane reaction solution.The method of purification process is: contain 1,2,3 by what prepare according to above-mentioned synthetic method, the solution of 4-tetrachloro-hexafluoro butane imports in the retort of 10 DEG C, isolate fluorine-containing low-boiling-point substance, then will containing 1,2,3, the solution of 4-tetrachloro-hexafluoro butane imports in rectifying tower implements negative pressure (gauge pressure) rectifying, isolated 1,2,3,4-tetrachloro-hexafluoro butane successively with CaOH and MgSO
4contact.The yield of 1,2,3,4-tetrachloro-hexafluoro butane is 70.116%.
The synthesis of embodiment 31,2,3,4-tetrachloro-hexafluoro butane and purifying
Volume be 10L be in the homemade reactor of material with 316L, splendid attire is with 1, 2-dichloro tetrafluoro ethane is solvent and 1, 2-bis-fluoro-1, 2-Ethylene Dichloride content is 50%(volume percent) solution 5L, by the fluorine gas of electrolytic preparation after dehydrofluorination and the process of defluorinate potassium hydride KH, be forced into 0.15Mpa, by fluorine gas by argon-dilution to 40%(volume percent), 1 is imported by the flow of 200L/h, 2-bis-fluoro-1, 1 of 2-Ethylene Dichloride, sustained reaction 9 hours in 2-dichloro tetrafluoro ethane solution, maintaining reaction unit internal pressure in reaction process is 0.05Mpa, maintain the liquidus temperature of reaction system at-45 ± 1 DEG C.Get liquid phase reaction liquid after reaction terminating, analyze by gas-chromatography.Analytical results is as follows: the selectivity 58.387% of transformation efficiency 100%, 1,2,3, the 4-tetrachloro-hexafluoro butane of the fluoro-1,2-dichloroethene of 1,2-bis-.
After carrying out purification process containing 1,2,3,4-tetrachloro-hexafluoro butane reaction solution, obtain 1,2,3, the 4-tetrachloro-hexafluoro butane that purity is 98.836%.The method of purification process is: contain 1,2,3 by what prepare according to above-mentioned synthetic method, the solution of 4-tetrachloro-hexafluoro butane imports in the retort of 60 DEG C, isolate fluorine-containing low-boiling-point substance, then will containing 1,2,3, the solution of 4-tetrachloro-hexafluoro butane imports in rectifying tower implements negative pressure (gauge pressure) rectifying, isolated 1,2,3,4-tetrachloro-hexafluoro butane successively with MgO and P
2o
5contact.The yield of 1,2,3,4-tetrachloro-hexafluoro butane is 52.5%.
The synthesis of embodiment 41,2,3,4-tetrachloro-hexafluoro butane and purifying
Volume be 10L be in the homemade reactor of material with 316L, splendid attire is with perfluoro-methyl-1, 2-dichloro-tetrafluoro ethyl ether is solvent and 1, 2-bis-fluoro-1, 2-Ethylene Dichloride content is 50%(volume percent) solution 5L, by the fluorine gas of electrolytic preparation after dehydrofluorination and the process of defluorinate potassium hydride KH, be forced into 0.15Mpa, by fluorine gas with nitrogen dilution to 40%(volume percent), 1 is imported by the flow of 200L/h, 2-bis-fluoro-1, 1 of 2-Ethylene Dichloride, sustained reaction 9 hours in 2-dichloro tetrafluoro ethane solution, maintaining reaction unit internal pressure in reaction process is 0.05Mpa, maintain the liquidus temperature of reaction system at-75 ± 1 DEG C.Get liquid phase reaction liquid after reaction terminating, analyze by gas-chromatography.Analytical results is as follows; The selectivity 80% of transformation efficiency 98.832%, 1,2,3, the 4-tetrachloro-hexafluoro butane of the fluoro-1,2-dichloroethene of 1,2-bis-.
1,2,3, the 4-tetrachloro-hexafluoro butane that purity is 98.246% will be obtained after carrying out purification process containing 1,2,3,4-tetrachloro-hexafluoro butane reaction solution.The method of purification process is: contain 1,2,3 by what prepare according to above-mentioned synthetic method, the solution of 4-tetrachloro-hexafluoro butane imports in the retort of 60 DEG C, isolate fluorine-containing low-boiling-point substance, then will containing 1,2,3, the solution of 4-tetrachloro-hexafluoro butane imports in rectifying tower implements negative pressure (gauge pressure) rectifying, isolated 1,2,3,4-tetrachloro-hexafluoro butane successively with KOH and CaSO
4contact.The yield of 1,2,3,4-tetrachloro-hexafluoro butane is 77.334%.
Device that the synthesis of 1,2,3,4-tetrachloro-hexafluoro butane and purifying use is carried out as shown in Figure 1 in embodiment 1-4.
Although above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, all belong to the scope of protection of present invention.
Claims (1)
1.1, 2, 3, the synthetic method of 4-tetrachloro-hexafluoro butane, it is characterized in that, volume be 10L be in the homemade reactor of material with 316L, splendid attire is with 1, 2-dichloro tetrafluoro ethane is solvent and 1, 2-bis-fluoro-1, the volumn concentration of 2-Ethylene Dichloride is the solution 5L of 50%, by the fluorine gas of electrolytic preparation after dehydrofluorination and the process of defluorinate potassium hydride KH, be forced into 0.15Mpa, be 40% by fluorine gas nitrogen dilution to volume percent, 1 is imported by the flow of 200L/h, 2-bis-fluoro-1, 1 of 2-Ethylene Dichloride, sustained reaction 9 hours in 2-dichloro tetrafluoro ethane solution, maintaining reaction unit internal pressure in reaction process is 0.05Mpa, maintain the liquidus temperature of reaction system at-75 ± 1 DEG C,
Or volume be 10L be in the homemade reactor of material with 316L, splendid attire is with 1, 2-dichloro tetrafluoro ethane is solvent and 1, 2-bis-fluoro-1, the volumn concentration of 2-Ethylene Dichloride is the solution 5L of 50%, by the fluorine gas of electrolytic preparation after dehydrofluorination and the process of defluorinate potassium hydride KH, be forced into 0.07Mpa, fluorine gas helium being diluted to volume percent is 60%, 1 is imported by the flow of 200L/h, 2-bis-fluoro-1, 1 of 2-Ethylene Dichloride, sustained reaction 7 hours in 2-dichloro tetrafluoro ethane solution, maintaining reaction unit internal pressure in reaction process is 0.02Mpa, maintain the liquidus temperature of reaction system at-75 ± 1 DEG C.
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