CN107586251A - One kind 1,1, Isosorbide-5-Nitrae, the preparation method of the butylene of 4,4 hexafluoro 2 - Google Patents
One kind 1,1, Isosorbide-5-Nitrae, the preparation method of the butylene of 4,4 hexafluoro 2 Download PDFInfo
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- CN107586251A CN107586251A CN201710620087.6A CN201710620087A CN107586251A CN 107586251 A CN107586251 A CN 107586251A CN 201710620087 A CN201710620087 A CN 201710620087A CN 107586251 A CN107586251 A CN 107586251A
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- nitrae
- isosorbide
- hexafluoro
- butylene
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 title abstract 8
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 title abstract 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000460 chlorine Substances 0.000 claims abstract description 10
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 10
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 claims abstract description 9
- CYXIKYKBLDZZNW-UHFFFAOYSA-N 2-Chloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)CCl CYXIKYKBLDZZNW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000006298 dechlorination reaction Methods 0.000 claims abstract description 5
- 239000000047 product Substances 0.000 claims abstract description 5
- 238000005286 illumination Methods 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 7
- HWJPHQNEWARZLH-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5-decafluoro-6,6-bis(trifluoromethyl)cyclohexane Chemical compound FC(F)(F)C1(C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C1(F)F HWJPHQNEWARZLH-UHFFFAOYSA-N 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 230000000630 rising effect Effects 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 239000006200 vaporizer Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical class FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 claims description 3
- 239000013067 intermediate product Substances 0.000 abstract description 2
- UAZUEJTXWAXSMA-UHFFFAOYSA-N 1,1-dichlorobut-1-ene Chemical class CCC=C(Cl)Cl UAZUEJTXWAXSMA-UHFFFAOYSA-N 0.000 abstract 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 abstract 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- FRCHKSNAZZFGCA-UHFFFAOYSA-N 1,1-dichloro-1-fluoroethane Chemical compound CC(F)(Cl)Cl FRCHKSNAZZFGCA-UHFFFAOYSA-N 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000004088 foaming agent Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 description 2
- 230000002572 peristaltic effect Effects 0.000 description 2
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- WZLFPVPRZGTCKP-UHFFFAOYSA-N 1,1,1,3,3-pentafluorobutane Chemical compound CC(F)(F)CC(F)(F)F WZLFPVPRZGTCKP-UHFFFAOYSA-N 0.000 description 1
- SXKNYNUXUHCUHX-UHFFFAOYSA-N 1,1,2,3,3,4-hexafluorobut-1-ene Chemical compound FCC(F)(F)C(F)=C(F)F SXKNYNUXUHCUHX-UHFFFAOYSA-N 0.000 description 1
- YZXSQDNPKVBDOG-UHFFFAOYSA-N 2,2-difluoropropane Chemical compound CC(C)(F)F YZXSQDNPKVBDOG-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- MJBPUQUGJNAPAZ-UHFFFAOYSA-N Butine Natural products O1C2=CC(O)=CC=C2C(=O)CC1C1=CC=C(O)C(O)=C1 MJBPUQUGJNAPAZ-UHFFFAOYSA-N 0.000 description 1
- XRPKRSLLVXAECN-UHFFFAOYSA-N CCCC.[F] Chemical compound CCCC.[F] XRPKRSLLVXAECN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- GNDMWRNTJIARLO-UHFFFAOYSA-N ClC(C)Cl.[F] Chemical class ClC(C)Cl.[F] GNDMWRNTJIARLO-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000007256 debromination reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- -1 fluorine hydrogen alkene Chemical class 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000005828 hydrofluoroalkanes Chemical class 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- QVTVDJWJGGEOGX-UHFFFAOYSA-N urea;cyanide Chemical compound N#[C-].NC(N)=O QVTVDJWJGGEOGX-UHFFFAOYSA-N 0.000 description 1
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to one kind 1,1, Isosorbide-5-Nitrae, 4, the preparation method of the butylene of 4 hexafluoro 2, one kind 1,1, Isosorbide-5-Nitrae, the preparation method of the butylene of 4,4 hexafluoro 2, comprises the following steps, and (1) is with 1,1,1 trifluoro-chloroethane and/or 1, the dichloroethanes of 1,1 trifluoro 2,2 is raw material, using chlorine as catalyst, reaction generation 1,1 under light illumination, Isosorbide-5-Nitrae, 4, the chlorobutane of 4 hexafluoro 2,2,3,3 four；(2) obtain step (1) 1,1, Isosorbide-5-Nitrae, the zinc powder dechlorination obtained 1,1 of the chlorobutane of 4,4 hexafluoro 2,2,3,3 four, Isosorbide-5-Nitrae, the dichloro-butenes of 4,4 hexafluoro 2,3；(3) obtain step (2) 1,1, Isosorbide-5-Nitrae, the dichloro-butenes of 4,4 hexafluoro 2,3 react to obtain in the presence of a hydrogenation catalyst 1,1 with hydrogen, Isosorbide-5-Nitrae, the butylene of 4,4 hexafluoro 2.Catalyst raw material of the present invention is easy to get and intermediate product can obtain final products, high income by mulitpath.
Description
Technical field
It is used to produce the preparation method of Fluorine containing olefine the present invention relates to a kind of, more particularly, to one kind 1,1, Isosorbide-5-Nitrae, 4,4- six
The preparation method of fluoro- 2- butylene.
Background technology
Once by widely used Arcton 11 (CFC-11) as foaming agent, because it can destroy atmospheric ozone layer,
Substituted by performance and its fluorine dichloroethanes (HCFC-141b) relatively now.But HCFC-141b ODP is not
It is zero, atmospheric ozone layer can be still damaged, therefore Montreal Protocol is included in and eliminated in the works, some are flourishing
Country eliminates HCFC-141b in advance.The substitute for substituting HCFC-141b in the world now mainly has 1,1,1,3,3- five fluorine
Butane (HFC-365mfc), 1,1,1,3,3- pentafluoropropane (HFC-245fa) etc., these compounds are to ozone layer without destruction
Property, but because they can promote " greenhouse effects ", i.e., they can promote global warming, therefore by sifting, and
It is applied can also be restricted in the future.Therefore, research and development had not only met low-ozone consumption but also had had low global warming up trend
Compound is the active demand of Vehicles Collected from Market, and fluorine hydrogen alkene 1,1, and Isosorbide-5-Nitrae, 4,4- hexafluoro -2- butylene (HFO-1336mzz) are exactly
Current requirement can be met.
For 1,1, Isosorbide-5-Nitrae, the preparation of 4,4- hexafluoro -2- butylene, most proposed earlier than nineteen fifty-two by Haszeldine R.N.,
With 2,3- dibromos hexafluorobutene for raw material, first carry out debromination with zinc powder and obtain 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- butine, then pass through
Catalytic hydrogenation obtains 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- butylene.
With the growing interest to global warming issue, the hydrofluoroalkane product of the latent value of low temperature chamber effect is developed into grinding
The focus studied carefully.1,1, Isosorbide-5-Nitrae, the ODP of 4,4- hexafluoro -2- butylene is that 0, GWP is about 9, and atmospheric lifetime is short, it is considered to be Yi Zhongxin
The environment-friendly substitute of type.
In E.I.Du Pont Company patent CN103524297A, with 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2,3- dichloro-2-butenes and hydrogen exist
200~450 DEG C pass through special catalyst reaction preparation 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- butylene.Sinochem Lantian Co., Ltd.
Then it is that Isosorbide-5-Nitrae, 4,4- hexafluoro -2,3- dichloro-2-butenes and zinc powder are in organic acid and solvent with 1,1 in patent CN103373896B
In the presence of, in 100~200 DEG C of reaction preparations 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- butylene.
In E.I.Du Pont Company patent CN102015592B, then with 2,2- bis- chloro- 1,1,1- HFC-143a is molten in acid amides with copper powder
In the presence of agent and 2,2- bipyridyl, in 20~150 DEG C of reaction preparations 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- butylene.
Then with carbon tetrachloride and 3 in the patent CN102884030A of Honeywell, 3,3- trifluoro propenes are that raw material prepares 1,1,
Isosorbide-5-Nitrae, 4,4- hexafluoro -2- butylene；Then described in patent CN102892736B and prepare 1,1 with carbon tetrachloride and ethylene reaction,
Isosorbide-5-Nitrae, 4,4- hexafluoro -2- butylene；In patent CN103193586B using hexachlorobutadiene be raw material by fluorination, dechlorination, reduction
Preparation 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- butylene.
With 1,1 in Ju Hua groups patent CN103172489B, Isosorbide-5-Nitrae, 4,4- hexafluoro butanes are that raw material is prepared through chlorination, alkaline hydrolysis
1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- butylene.
The content of the invention
The purpose of the present invention is：Overcome deficiency of the prior art, there is provided one kind is used to produce polyurethane or poly- isocyanide urea
The foaming agent containing difluoropropane of acid esters foams, the foaming agent not only alternative HCFC-141b, and be not the existing world
The material of the destruction atmospheric ozone layer used is limited, at the same it is moderate.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：
One kind 1,1, Isosorbide-5-Nitrae, the preparation method of 4,4- hexafluoro -2- butylene, comprises the following steps,
(1) it is raw material with 1,1,1- trifluoro-chloroethane and/or 1,1,1- tri- fluoro- 2,2- dichloroethanes, using chlorine as catalysis
Agent, under light illumination reaction generation 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoros -2,2,3,3- tetra- chlorobutanes；
(2) obtain step (1) 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoros -2,2,3,3- tetra- chlorobutanes are made 1,1 with zinc powder dechlorination,
Isosorbide-5-Nitrae, 4,4- hexafluoro -2,3- dichloro-butenes；
(3) obtain step (2) 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2,3- dichloro-butenes in the presence of a hydrogenation catalyst with hydrogen
Solid/liquid/gas reactions obtain 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- butylene.
Preferably, in step (1), obtained product is reacted except 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoros -2,2,3,3- tetra- neoprenes
Outside alkane, also contain 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2,3- dichloroetane and 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoros -2,2, the chlorobutanes of 3- tri-.
Preferably, in step (3), hydrogenation catalyst is added into hydrogenation reactor, it is even under the hydrogen stream of 20 Grams Per Hours
Speed heating, after 8 hours are warming up to 280 DEG C, with the flow of 470 Grams Per Hours by 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2,3- dichloro-butenes lead to
Enter vaporizer, being mixed into hydrogenation reactor with hydrogen after preheated device, superheater reacts；Reaction product is through cooling down, washing, essence
Obtain 1,1 after evaporating, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- butylene.
Preferably, in step (2), also including the use of 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoros -2,2, the chlorobutanes of 3- tri- take off with zinc powder
Chlorine reaction obtained 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- chlorobutylenes.
Preferably, in step (2), 68 grams of zinc powders, 300 grams of methanol are added in 2 liters of flasks, temperature rising reflux are stirred, 4
Hour in thereto be added dropwise 270 gram 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoros -2,2, the chlorobutanes of 3- tri-, after completion of dropwise addition continuation return stirring one
Hour；Distillation, collect 70 DEG C of foreshot, wash 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- chlorobutylenes.
Preferably, in step (2), 70 grams of zinc powders, 300 grams of methanol are added in 2 liters of flasks, stir temperature rising reflux,
It was added dropwise 305 gram 1 thereto in 4 hours, 1, Isosorbide-5-Nitrae, 4,4- hexafluoros -2,2,3,3- tetra- chlorobutanes, continue to flow back after completion of dropwise addition
Stirring one hour；Distillation, collect 70 DEG C of foreshot, wash 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2,3- dichloro-butenes.
Preferably, in step (1), the mol ratio of raw material and chlorine is 1 ﹕ 0.1-1.5.
Preferably, in step (2), the mol ratio of raw material and zinc powder is 1 ﹕ 1-1.6.
It is using the beneficial effect of technical scheme：
The hydrogenation catalyst used comprising copper, nickel, chromium, palladium and ruthenium of the present invention is known in the art, this kind of catalyst
It can be prepared by the precipitation method or infusion process, so that catalyst raw material is easy to get；In addition, the intermediate product of the present invention can pass through
Mulitpath obtains final products, high income.
Embodiment
With reference to embodiment, the invention will be further described.
Embodiment 1
1,1,1- trifluoro-chloroethane is sent into vaporizer with the speed of 237 Grams Per Hours by peristaltic pump to vaporize, after vaporization
1,1,1- trifluoro-chloroethane mixed with chlorine after by preheater preheating enter chlorinator in, reacted under illumination condition, instead
26~30 seconds residence times are answered, chlorine intake is 45 Grams Per Hours, and controlling reaction temperature is maintained at 80 DEG C.Reaction product passes through
Condenser cooling absorbs, then through alkali cleaning, washing, rectifying isolated 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoros -2,2,3,3- tetra- chlorobutanes, turns
Rate 33%.
Embodiment 2
1,1,1- tri- fluoro- 2,2- dichloroethanes is sent to by vaporizer vapour with the speed of 306 Grams Per Hours by peristaltic pump
Change, 1 after vaporization, 1,1- tri- fluoro- 2,2- dichloroethanes is entered in chlorinator after being mixed with chlorine by preheater preheating, in light
Reacted according under the conditions of, reaction time 18~21 seconds, chlorine intake is 20 Grams Per Hours, and controlling reaction temperature is maintained at 100
℃.Reaction product is cooled down by condenser to be absorbed, then through alkali cleaning, washing, rectifying isolated 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoros -2,2,
3,3- tetra- chlorobutanes, conversion ratio 46%.
Embodiment 3
68 grams of zinc powders, 300 grams of methanol are added in 2 liters of flasks, temperature rising reflux is stirred, was added dropwise thereto in 4 hours
270 gram 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoros -2,2, the chlorobutanes of 3- tri-, continuation return stirring one hour after completion of dropwise addition.Distillation, collect 70
DEG C foreshot, wash 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- chlorobutylenes, yield 92%.
Embodiment 4
70 grams of zinc powders, 300 grams of methanol are added in 2 liters of flasks, temperature rising reflux is stirred, was added dropwise thereto in 4 hours
305 gram 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoros -2,2,3,3- tetra- chlorobutanes, continuation return stirring one hour after completion of dropwise addition.Distillation, collect
70 DEG C of foreshot, wash 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2,3- dichloro-butenes, yield 95%.
Embodiment five
To diameter 5cm, long 200cm hydrogenation reactor in add hydrogenation catalyst, it is even under the hydrogen stream of 20 Grams Per Hours
Speed heating, after 8 hours are warming up to 280 DEG C, with the flow of 470 Grams Per Hours by 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2,3- dichloro-butenes lead to
Enter vaporizer, being mixed into hydrogenation reactor with hydrogen after preheated device, superheater reacts.Reaction product is through cooling down, washing, essence
Obtain 1,1 after evaporating, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- butylene.
Although the foregoing describing the embodiment of the present invention, those skilled in the art should be appreciated that this
Be merely illustrative of, various changes or modifications can be made to present embodiment, without departing from the present invention principle and essence,
Protection scope of the present invention is only limited by the claims that follow.
Claims (8)
1. one kind 1,1, Isosorbide-5-Nitrae, the preparation method of 4,4- hexafluoro -2- butylene, it is characterised in that comprise the following steps,
(1) with 1,1,1- trifluoro-chloroethane and/or 1,1,1- tri- fluoro- 2,2- dichloroethanes is raw material, using chlorine as catalyst,
Reaction generation 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoros -2,2,3,3- tetra- chlorobutanes under illumination；
(2) obtain step (1) 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoros -2,2, the zinc powder dechlorination obtained 1,1 of 3,3- tetra- chlorobutanes, Isosorbide-5-Nitrae,
4,4- hexafluoro -2,3- dichloro-butenes；
(3) obtain step (2) 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2,3- dichloro-butenes are anti-with hydrogen in the presence of a hydrogenation catalyst
It should obtain 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- butylene.
2. according to claim 1 a kind of 1,1, Isosorbide-5-Nitrae, the preparation method of 4,4- hexafluoro -2- butylene, it is characterised in that：
In step (1), obtained product is reacted except 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoros -2,2, outside 3,3- tetra- chlorobutanes, also contains 1,1,1,
4,4,4- hexafluoro -2,3- dichloroetane and 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoros -2,2, the chlorobutanes of 3- tri-.
3. according to one kind 1,1 described in claim 1, Isosorbide-5-Nitrae, the preparation method of 4,4- hexafluoro -2- butylene, it is characterised in that：Step
Suddenly in (3), hydrogenation catalyst is added into hydrogenation reactor, is at the uniform velocity heated up under the hydrogen stream of 20 Grams Per Hours, is heated up within 8 hours
To after 280 DEG C, with the flow of 470 Grams Per Hours by 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2,3- dichloro-butenes are passed through vaporizer, preheated
Hydrogenation reactor reaction is mixed into after device, superheater with hydrogen；Reaction product through cooling down, wash, 1,1,1 being obtained after rectifying,
4,4,4- hexafluoro -2- butylene.
4. according to claim 2 a kind of 1,1, Isosorbide-5-Nitrae, the preparation method of 4,4- hexafluoro -2- butylene, it is characterised in that：
In step (2), also including the use of 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoros -2,2, the chlorobutanes of 3- tri- and zinc powder dechlorination reaction be made 1,1, Isosorbide-5-Nitrae,
4,4- hexafluoro -2- chlorobutylenes.
5. according to claim 4 a kind of 1,1, Isosorbide-5-Nitrae, the preparation method of 4,4- hexafluoro -2- butylene, it is characterised in that：Step
Suddenly in (2), 68 grams of zinc powders, 300 grams of methanol are added in 2 liters of flasks, temperature rising reflux is stirred, was added dropwise thereto in 4 hours
270 gram 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoros -2,2, the chlorobutanes of 3- tri-, continuation return stirring one hour after completion of dropwise addition；Distillation, collect 70
DEG C foreshot, wash 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- chlorobutylenes.
6. according to claim 2 a kind of 1,1, Isosorbide-5-Nitrae, the preparation method of 4,4- hexafluoro -2- butylene, it is characterised in that：
In step (2), 70 grams of zinc powders, 300 grams of methanol are added in 2 liters of flasks, temperature rising reflux is stirred, was dripped thereto in 4 hours
Add 305 gram 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoros -2,2,3,3- tetra- chlorobutanes continue return stirring one hour after completion of dropwise addition；Distillation, receive
70 DEG C of foreshot of collection, wash 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2,3- dichloro-butenes.
7. according to claim 1 a kind of 1,1, Isosorbide-5-Nitrae, the preparation method of 4,4- hexafluoro -2- butylene, it is characterised in that：
In step (1), the mol ratio of raw material and chlorine is 1 ﹕ 0.1-1.5.
8. according to claim 1 a kind of 1,1, Isosorbide-5-Nitrae, the preparation method of 4,4- hexafluoro -2- butylene, it is characterised in that：
In step (2), the mol ratio of raw material and zinc powder is 1 ﹕ 1-1.6.
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| CN112745192A (en) * | 2020-12-31 | 2021-05-04 | 山东华夏神舟新材料有限公司 | Continuous preparation method of cis-hexafluoro-2-butene |
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