CN113474319A - Process for producing halogenated butene compound - Google Patents
Process for producing halogenated butene compound Download PDFInfo
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- CN113474319A CN113474319A CN202080015744.4A CN202080015744A CN113474319A CN 113474319 A CN113474319 A CN 113474319A CN 202080015744 A CN202080015744 A CN 202080015744A CN 113474319 A CN113474319 A CN 113474319A
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- halogenated
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- compound
- fluorinated
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- -1 halogenated butene compound Chemical class 0.000 title claims abstract description 95
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 95
- 229910000039 hydrogen halide Inorganic materials 0.000 claims abstract description 42
- 239000012433 hydrogen halide Substances 0.000 claims abstract description 42
- 125000005843 halogen group Chemical group 0.000 claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 40
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 32
- 239000007789 gas Substances 0.000 claims description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 27
- 238000004519 manufacturing process Methods 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 14
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 13
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 13
- 239000011968 lewis acid catalyst Substances 0.000 claims description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 12
- 229910021536 Zeolite Inorganic materials 0.000 claims description 11
- 239000010457 zeolite Substances 0.000 claims description 11
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 238000005530 etching Methods 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 69
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 description 30
- 150000001875 compounds Chemical class 0.000 description 25
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 19
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 19
- 238000007259 addition reaction Methods 0.000 description 17
- 239000012025 fluorinating agent Substances 0.000 description 12
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical class CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 11
- 239000012071 phase Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 9
- 238000003682 fluorination reaction Methods 0.000 description 9
- 125000001153 fluoro group Chemical group F* 0.000 description 8
- 229910052731 fluorine Inorganic materials 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- UOUJSJZBMCDAEU-UHFFFAOYSA-N chromium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Cr+3].[Cr+3] UOUJSJZBMCDAEU-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- KDKYADYSIPSCCQ-UHFFFAOYSA-N but-1-yne Chemical class CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 description 4
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 238000004949 mass spectrometry Methods 0.000 description 4
- 238000012916 structural analysis Methods 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 3
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- NUPBXTZOBYEVIR-UHFFFAOYSA-N 1,1,2,3,3,4,4-heptafluorobut-1-ene Chemical compound FC(F)C(F)(F)C(F)=C(F)F NUPBXTZOBYEVIR-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- XWCDCDSDNJVCLO-UHFFFAOYSA-N Chlorofluoromethane Chemical compound FCCl XWCDCDSDNJVCLO-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910007161 Si(CH3)3 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 230000000704 physical effect Effects 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
- 239000002243 precursor Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001256 stainless steel alloy Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000004953 trihalomethyl group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
- C07C17/087—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B61/00—Other general methods
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C19/00—Acyclic saturated compounds containing halogen atoms
- C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C21/00—Acyclic unsaturated compounds containing halogen atoms
- C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
- C07C21/18—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds containing fluorine
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/3065—Plasma etching; Reactive-ion etching
Abstract
The invention provides a CX1X2X3CX4＝CHCX7X8X9[ in the formula, X1、X2、X3、X4、X7、X8And X9The same or different, represent a halogen atom.]A process for producing the halogenated butene compound, which comprisesComprising reacting CX in the presence of a catalyst1X2X3C≡CCX7X8X9[ in the formula, X1、X2、X3、X7、X8And X9As described above.]The process for producing a butene compound having 7 halogen atoms with high conversion and high selectivity comprises the step of reacting a halogenated butyne compound with a hydrogen halide.
Description
Technical Field
The present invention relates to a method for producing a halogenated butene compound.
Background
Butene compounds having 7 halogen atoms, represented by heptafluorobutene, are promising compounds for dry etching gases and cleaning gases for semiconductors, organic synthesis blocks, and the like.
As a method for producing the butene compound having 7 halogen atoms, for example, in non-patent document 1, CF is used3C≡CCF3Reaction with AgF to give CF3CF＝C(CF3) After Ag, reaction with HCl in acetonitrile to CF3CF＝CHCF3。
Documents of the prior art
Non-patent document
Non-patent document 1: journal of the American Chemical Society,91,1969, p.6532-6534
Disclosure of Invention
Technical problem to be solved by the invention
The purpose of the present invention is to provide a method for obtaining butene compounds having 7 halogen atoms with high conversion and high selectivity.
Technical solution for solving technical problem
The present invention includes the following aspects.
Item 1. A process for producing a halogenated butene compound represented by the general formula (1), which comprises a step of reacting a halogenated butyne compound of the general formula (2) with a hydrogen halide in the presence of a catalyst,
general formula (1):
CX1X2X3CX4＝CHCX7X8X9 (1)
[ in the formula, X1、X2、X3、X4、X7、X8And X9The same or different, represent a halogen atom.]
General formula (2):
CX1X2X3C≡CCX7X8X9 (2)
[ in the formula, X1、X2、X3、X7、X8And X9As described above.]。
Item 2 the production method according to item 1, wherein the halogenated butene compound represented by the general formula (1) is CF3CF＝CHCF3And the halogenated butyne compound represented by the above general formula (2) is CF3C≡CCF3。
Item 3. the production process according to item 1 or 2, wherein the catalyst contains at least 1 selected from a fluorinated or non-fluorinated activated carbon catalyst and a fluorinated or non-fluorinated Lewis acid catalyst.
The process according to any one of items 1 to 3, wherein the catalyst is a fluorinated or non-fluorinated Lewis acid catalyst, and the Lewis acid catalyst is at least 1 selected from the group consisting of a chromium oxide catalyst, an alumina catalyst, a silica alumina catalyst and a zeolite catalyst.
The process according to any one of the above 1 to 4, wherein 30 to 250 moles of the hydrogen halide are reacted with 1 mole of the halogenated butyne compound represented by the general formula (2).
Item 6. A composition containing a halogenated butene compound represented by the general formula (1) and a halogenated butane compound represented by the general formula (3),
the content of the halogenated butene compound represented by the general formula (1) is 91.00 to 99.99 mol% based on 100 mol% of the total composition,
general formula (1):
CX1X2X3CX4＝CHCX7X8X9 (1)
[ in the formula, X1、X2、X3、X4、X7、X8And X9The same or different, represent a halogen atom.]
General formula (3):
CX1X2X3CX4X5CHX6CX7X8X9 (3)
[ in the formula, X1、X2、X3、X4、X7、X8And X9As described above. X5And X6One of them represents a hydrogen atom and the other represents a halogen atom.]。
Item 7. the composition of item 6 for use as a cleaning gas, an etching gas, or a block for organic synthesis.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, it is possible to synthesize a butene compound having 7 halogen atoms by a method of obtaining a product with high conversion and high selectivity.
Detailed Description
In the present specification, "containing" is a concept including any one of "including (contains)", "consisting essentially of only … … (consistency approach of)", and "consisting of only … … (consistency of)". In the present specification, the numerical range represented by "a to B" means a range from a to B.
In the present invention, the "selectivity" refers to the ratio (mol%) of the total molar amount of the target compound contained in the effluent gas from the reactor outlet to the total molar amount of the compounds other than the raw material compound in the effluent gas.
In the present invention, "conversion" means a ratio (mol%) of a total molar amount of compounds other than the raw material compound contained in the effluent gas from the reactor outlet to a molar amount of the raw material compound supplied to the reactor.
At present, according to the method of non-patent document 1, CF is prepared3C≡CCF3Reaction with AgF to give CF3CF＝C(CF3) After Ag, reaction with HCl in acetonitrile to CF3CF＝CHCF3However, 2 steps of reaction were required, and the total yield was only 57%.
Thus, according to the conventional method, the yield was only 57% and the number of steps was large. According to the production method of the present invention, a butene compound having 7 halogen atoms can be synthesized by a method of obtaining a product with a high conversion rate and a high selectivity as compared with conventional methods.
1. Process for producing halogenated butene compound
The process for producing a halogenated butene compound of the present invention is a process for producing a halogenated butene compound represented by the general formula (1), comprising a step of reacting a halogenated butyne compound of the general formula (2) with a hydrogen halide in the presence of a catalyst,
general formula (1):
CX1X2X3CX4＝CHCX7X8X9 (1)
[ in the formula, X1、X2、X3、X4、X7、X8And X9The same or different, represent a halogen atom.]
General formula (2):
CX1X2X3C≡CCX7X8X9 (2)
[ in the formula, X1、X2、X3、X7、X8And X9As described above.]。
In the production method of the present invention, if the reaction of the halogenated butyne compound represented by the general formula (2) with the hydrogen halide is carried out in the absence of a catalyst, a halogenated butane compound represented by the general formula (3) in which 2 moles of hydrogen halide is added to 1 mole of the halogenated butyne compound represented by the general formula (2) is produced as a by-product to a considerable extent (for example, in an amount of more than 9.00 mol%).
General formula (3):
CX1X2X3CX4X5CHX6CX7X8X9 (3)
[ in the formula, X1、X2、X3、X4、X7、X8And X9As described above. X5And X6One of them represents a hydrogen atom and the other represents a halogen atom.]。
On the other hand, when the reaction of the halogenated butyne compound represented by the above general formula (2) with a hydrogen halide is carried out in the presence of a catalyst, the addition of 2 moles of the hydrogen halide to 1 mole of the halogenated butyne compound represented by the general formula (2) can be suppressed, and the halogenated butene compound represented by the general formula (1) in which 1 mole of the hydrogen halide is added to 1 mole of the halogenated butyne compound represented by the general formula (2) can be selectively obtained. This is due to the trihalogenated methyl (CX)1X2X3And CX7X8X9) Has strong electron-withdrawing effect. Due to this strong electron-withdrawing effect, the trihalomethyl group decreases the electron density of electrons of the adjacent double bond and triple bond, and therefore, an addition reaction to the unsaturated bond is less likely to occur. The halogenated butyne compound has a triple bond and high reactivity, and therefore, an addition reaction of hydrogen halide is easily caused, while the halogenated butene compound does not react with hydrogen halide due to the effect of a trihalogenated methyl group, and a halogenated butane compound is not formed, and thus, the halogenated butene compound can be selectively obtained.
The halogenated butyne compound which is a substrate usable in the production method of the present invention is a halogenated butyne compound represented by the general formula (2) as described above,
general formula (2):
CX1X2X3C≡CCX7X8X9 (2)
[ in the formula, X1、X2、X3、X7、X8And X9The same or different, represent a halogen atom.]。
In the general formula (2), as X1、X2、X3、X7、X8And X9Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The halogenated butyne compound as the substrate is preferably X, particularly from the viewpoint of being able to produce a halogenated butene compound with high conversion, yield and selectivity1、X2、X3、X7、X8And X9Are all fluorine atoms.
X as described above1、X2、X3、X7、X8And X9May be the same or different.
As the halogenated butyne compound serving as the substrate satisfying the above conditions, there can be specifically mentioned CF3C≡CCF3、CCl3C≡CCCl3、CBr3C≡CCBr3And the like. These halogenated butyne compounds can be used alone, or 2 or more kinds can be used in combination. The halogenated butyne compound can be any known or commercially available compound. Further, the synthesis can be performed according to a general method such as Japanese patent application laid-open No. 2012 and 001448.
Examples of the hydrogen halide to be reacted with the halogenated butyne compound include hydrogen fluoride, hydrogen chloride, and hydrogen bromide. Further, hydrogen fluoride is preferable from the viewpoint of the conversion rate, yield and selectivity of the reaction. These hydrogen halides can be used alone, or 2 or more kinds can be used in combination.
The hydrogen halide is generally preferably supplied to the reactor in the gas phase together with the halogenated butyne compound (substrate). The amount of the hydrogen halide to be supplied for the reaction with the halogenated butyne compound (substrate) is preferably 30 to 250 moles, more preferably 35 to 240 moles, and still more preferably 40 to 230 moles per 1 mole of the halogenated butyne compound (substrate). By setting the amount to this range, the addition reaction of the hydrogen halide can be more favorably advanced, and the excessive addition reaction of the hydrogen halide can be further suppressed, whereby the production of impurities can be further reduced, the selectivity of the halogenated butene compound as a product is high, and the product can be recovered with a high yield.
In the present invention, the step of reacting the halogenated butyne compound with the hydrogen halide is an addition reaction of the hydrogen halide, and is carried out in the presence of a catalyst. In the production method of the present invention, the step of reacting the halogenated butyne compound with the hydrogen halide (addition reaction) is preferably carried out in a gas phase, particularly in a gas phase continuous flow system using a fixed bed reactor. When the reaction is carried out in a gas-phase continuous flow system, the apparatus, operation, and the like can be simplified, and it is economically advantageous.
In the step of reacting a halogenated butyne compound with a hydrogen halide in the present invention, for example, X is more preferably selected from the halogenated butyne compounds represented by the general formula (2) as the substrate1、X2、X3、X7、X8And X9Is a fluorine atom.
That is, the addition reaction of hydrogen fluoride is preferably performed according to the following reaction formula.
CF3C≡CCF3+HF→CF3CF＝CHCF3
The catalyst used in the production method of the present invention is preferably a fluorinated or non-fluorinated activated carbon catalyst, a fluorinated or non-fluorinated lewis acid catalyst, or the like.
The activated carbon catalyst is not particularly limited, and examples thereof include powdered activated carbons such as crushed carbons, molded carbons, granular carbons, and spherical carbons. As the powdery activated carbon, powdery activated carbon having a particle size of 4 mesh (4.75mm) to 100 mesh (0.150mm) in JIS test (JIS Z8801) is preferably used. The activated carbon can be any of those known or commercially available.
Since activated carbon exhibits a stronger activity by fluorination, fluorinated activated carbon obtained by fluorinating activated carbon in advance before use in the reaction can also be used. That is, as the activated carbon catalyst, either of activated carbon that is not fluorinated and fluorinated activated carbon can be used.
Examples of the fluorinating agent used for fluorinating the activated carbon include inorganic fluorinating agents such as HF, and organic fluorinating agents such as Hydrofluorocarbons (HFC) such as hexafluoropropylene, chlorofluorocarbons (CFC) such as chlorofluoromethane, and Hydrochlorofluorocarbons (HCFC).
Examples of the method for fluorinating activated carbon include a method in which the above fluorinating agent is circulated under atmospheric pressure at a temperature of about room temperature (25 ℃) to 400 ℃ to fluorinate the activated carbon.
The lewis acid catalyst is not particularly limited, and examples thereof include a chromium oxide catalyst, an alumina catalyst, a silica alumina catalyst, and a zeolite catalyst. These lewis acid catalysts can employ either of a non-fluorinated lewis acid catalyst and a fluorinated lewis acid catalyst.
The chromium oxide catalyst is not particularly limited, and when the chromium oxide is expressed as CrOm, it is preferably 1.5<m<3, more preferably 2<m<2.75, more preferably 2<m<2.3. In addition, chromium oxide is denoted as CrOm·nH2In the case of O, the hydration may be carried out so that the value of n is 3 or less, particularly 1 to 1.5.
Fluorinated chromium oxide catalysts can be prepared by fluorination of the chromium oxide catalysts described above. The fluorination can be performed using, for example, HF, a fluorocarbon, or the like. Such a fluorinated chromium oxide catalyst can be synthesized, for example, by the method described in japanese patent application laid-open No. h 05-146680.
Hereinafter, an example of a method for synthesizing a chromium oxide catalyst and a fluorinated chromium oxide catalyst will be described.
First, a precipitate of chromium hydroxide is obtained by mixing an aqueous solution of a chromium salt (chromium nitrate, chromium chloride, chromium alum, chromium sulfate, etc.) with aqueous ammonia. The physical properties of the chromium hydroxide are controlled by the reaction rate of the precipitation reaction at this time. Preferably, the reaction rate is high. The reaction rate is affected by the temperature of the reaction solution, the method of mixing ammonia water (mixing speed), the state of stirring, and the like.
The precipitate can be filtered and washed, and then dried. The drying can be carried out, for example, in air at 70 to 200 ℃ for 1 to 100 hours. The catalyst at this stage is sometimes referred to as chromium hydroxide. Subsequently, the catalyst can be disintegrated. From the viewpoint of the strength of the pellet, the activity of the catalyst, and the like, the precipitation reaction rate is preferably adjusted so that the powder density of the disintegrated powder (for example, 95% for a particle size of 1000 μm or less, particularly 46 to 1000 μm) is 0.6 to 1.1g/ml, preferably 0.6 to 1.0 g/ml. The specific surface area (specific surface area measured by BET method) of the powder is preferably 100m under the degassing condition of 200 ℃ for 80 minutes2A value of at least 120 m/g, more preferably2More than g. In addition, of specific surface areaUpper limit of, for example, 220m2And about/g.
The chromium hydroxide powder is mixed with 3 wt% or less of graphite as necessary, and formed into pellets by a tablet press. The size and strength of the pellets can be appropriately adjusted.
The molded catalyst can be fired in an inert atmosphere, for example, a nitrogen gas flow to form amorphous chromium oxide. The firing temperature is preferably 360 ℃ or higher, and from the viewpoint of suppressing crystallization, 380 to 460 ℃ is preferred. The firing time may be set to 1 to 5 hours, for example.
From the viewpoint of catalyst activity, the specific surface area of the catalyst after firing is preferably 170m, for example2A value of at least one of,/g, more preferably 180m2A total of 200m or more, preferably2More than g. Further, the upper limit of the specific surface area is preferably 240m in general2(ii) about/g, more preferably 220m2And about/g.
Fluorinated chromium oxide is then obtained by fluorination of the chromium oxide. The temperature of fluorination may be within a temperature range in which the generated water is not condensed, and the upper limit of the temperature at which the catalyst is not crystallized by the heat of reaction may be set. The temperature of the fluorination can be set to, for example, 100 to 460 ℃. The pressure at the time of fluorination is not limited, and it is preferably carried out at a pressure which is supplied to the catalytic reaction.
Examples of the alumina catalyst include α -alumina and activated alumina. The activated alumina includes rho-alumina, chi-alumina, kappa-alumina, eta-alumina, pseudo-gamma-alumina, sigma-alumina, and theta-alumina.
In addition, a silica alumina catalyst can be used as the composite oxide. The silica alumina catalyst is a catalyst comprising Silica (SiO)2) And alumina (Al)2O3) The composite oxide catalyst of (3) can be used in which the content of silica is, for example, 20 to 90 mass%, particularly 50 to 80 mass%, based on 100 mass% of the total amount of silica and alumina.
The alumina catalyst and the silica alumina catalyst exhibit stronger activity by fluorination, and therefore, the alumina catalyst may be fluorinated in advance before use in the reaction and used as a fluorinated alumina catalyst, and the silica alumina catalyst may be fluorinated and used as a fluorinated silica alumina catalyst.
As the fluorinating agent for fluorinating the alumina catalyst and the silica alumina catalyst, for example, F can be used2Inorganic fluorinating agents such as HF, and fluorocarbon organic fluorinating agents such as hexafluoropropylene.
Examples of the method for fluorinating the alumina catalyst and the silica alumina catalyst include a method in which the above fluorinating agent is circulated under atmospheric pressure at a temperature of about room temperature (25 ℃) to 400 ℃ to fluorinate the catalyst.
As the zeolite catalyst, a known zeolite can be widely used. For example, crystalline aqueous aluminosilicates of alkali metals or alkaline earth metals are preferred. The crystal form of the zeolite is not particularly limited, and examples thereof include a-type, X-type, LSX-type, and the like. The alkali metal or alkaline earth metal in the zeolite is not particularly limited, and examples thereof include potassium, sodium, calcium, and lithium.
The zeolite catalyst exhibits a stronger activity by fluorination, and therefore, the zeolite catalyst can be fluorinated in advance before use in the reaction as a fluorinated zeolite catalyst.
As the fluorinating agent for fluorinating the zeolite catalyst, for example, F can be used2Inorganic fluorinating agents such as HF, and fluorocarbon organic fluorinating agents such as hexafluoropropylene.
The method of fluorinating the zeolite catalyst includes, for example, a method of fluorinating by flowing the fluorinating agent under atmospheric pressure at a temperature of about room temperature (25 ℃) to 400 ℃.
The above catalysts can be used alone, and 2 or more kinds can be used in combination. Among these, from the viewpoint of conversion, selectivity and yield, a fluorinated or nonfluorinated activated carbon catalyst, a fluorinated or nonfluorinated chromium oxide catalyst, a fluorinated or nonfluorinated alumina catalyst and the like are preferable, and a fluorinated or nonfluorinated activated carbon catalyst, a fluorinated or nonfluorinated chromium oxide catalyst and the like are more preferable.
When the above-mentioned fluorinated or nonfluorinated lewis acid catalyst is used as the catalyst, it may be supported on a carrier. Examples of such a carrier include carbon and alumina (Al)2O3) Zirconium oxide (ZrO)2) Silicon dioxide (SiO)2) Titanium oxide (TiO)2) And the like. As carbon, activated carbon, amorphous carbon, graphite, diamond, or the like can be used.
In the production method of the present invention, when the halogenated butyne compound is reacted with the hydrogen halide in the presence of the catalyst, for example, the catalyst is preferably contacted with the halogenated butyne compound in a solid state (solid phase). In this case, the catalyst may be in the form of powder, but in the case of a gas-phase continuous flow reaction, it is preferable to use a granular form.
The specific surface area of the catalyst measured by the BET method (hereinafter, sometimes referred to as "BET specific surface area") is preferably 10 to 3,000m2A more preferable range is 10 to 2500m2(ii)/g, more preferably 20 to 2000m2A specific preferred range is 30 to 1500m2(ii) in terms of/g. When the BET specific surface area of the catalyst is in this range, the density of the catalyst particles is not excessively small, and therefore, the halogenated butene compound can be obtained with a higher selectivity. In addition, the conversion of the halogenated butyne compound can be further improved.
In the step of reacting the halogenated butyne compound with the hydrogen halide in the present invention, the lower limit of the reaction temperature is preferably 180 ℃ or higher, and more preferably 200 ℃ or higher, from the viewpoint of more efficiently performing the addition reaction of the hydrogen halide, further improving the conversion rate, and obtaining the desired halogenated butene compound with a higher selectivity. When a lewis acid catalyst is used as the catalyst, the lower limit of the reaction temperature is preferably 280 ℃ or more, and more preferably 320 ℃ or more for the same reason.
From the viewpoint of more efficiently carrying out the addition reaction of the hydrogen halide, further improving the conversion rate, obtaining the halogenated butene compound as the target compound with a higher selectivity, and further suppressing the decrease in selectivity due to the decomposition or polymerization of the reaction product, the upper limit of the reaction temperature for reacting the halogenated butyne compound with the hydrogen halide in the present invention is usually preferably 500 ℃ or less, more preferably 450 ℃ or less, and still more preferably 400 ℃ or less.
In the present invention, the reaction time for reacting the halogenated butyne compound with the hydrogen halide is, for example, a contact time (W/F) of the raw material compound with respect to the catalyst in the case of a gas-phase flow method [ W: weight (g) of metal catalyst, F: the flow rate (cc/sec) ] of the raw material compound is preferably 1.5 to 30g sec./cc, more preferably 1.8 to 20g sec./cc, and still more preferably 2.0 to 10g sec./cc. The W/F is determined particularly by the reaction time in the case of a gas-phase flow-through reaction, and the contact time can be appropriately set even in the case of a batch reaction. Further, the contact time refers to a time during which the substrate and the catalyst are in contact.
In the present invention, the reaction pressure for reacting the halogenated butyne compound with the hydrogen halide is preferably from-0.05 MPa to 2MPa, more preferably from-0.01 MPa to 1MPa, and still more preferably from normal pressure to 0.5MPa, from the viewpoint of more efficiently carrying out the addition reaction of the hydrogen halide. In the present invention, the pressure is a gauge pressure unless otherwise specified.
In the reaction of the halogenated butyne compound with the hydrogen halide in the present invention, the reactor into which the halogenated butyne compound and the catalyst are charged and reacted is not particularly limited as long as it can withstand the above-mentioned temperature and pressure. Examples of the reactor include a vertical reactor, a horizontal reactor, and a multitubular reactor. Examples of the material of the reactor include glass, stainless steel, iron, nickel, and iron-nickel alloy.
The reaction of the halogenated butyne compound with the hydrogen halide (addition reaction of the hydrogen halide) in the present invention can be carried out by any of flow-through and batch-wise modes in which the substrate is continuously charged into the reactor and the target compound is continuously withdrawn from the reactor. The target compound is left in the reactor and the elimination reaction proceeds further, and therefore, the reaction is preferably carried out by a flow-through method. In the step of reacting the halogenated butyne compound with the hydrogen halide in the present invention, it is preferable to carry out the reaction in a gas phase, and particularly, it is carried out in a gas phase continuous flow system using a fixed bed reactor. When the reaction is carried out in a gas-phase continuous flow system, the apparatus, operation, and the like can be simplified, which is economically advantageous.
The atmosphere in the reaction of the halogenated butyne compound with the hydrogen halide in the present invention is preferably an inert gas atmosphere, a hydrogen fluoride gas atmosphere, or the like, from the viewpoint of suppressing deterioration of the catalyst. Examples of the inert gas include nitrogen, helium, and argon. Among these inert gases, nitrogen gas is preferable from the viewpoint of cost reduction. The concentration of the inert gas is preferably 0 to 50 mol% of the gas component introduced into the reactor.
The object compound of the present invention thus obtained is a halogenated butene compound represented by the general formula (1).
General formula (1):
CX1X2X3CX4＝CHCX7X8X9 (1)
[ in the formula, X1、X2、X3、X4、X7、X8And X9The same or different, represent a halogen atom.]
X in the general formula (1)1、X2、X3、X7、X8And X9Corresponding to X in the above general formula (2)1、X2、X3、X7、X8And X9. In the general formula (1), X is4Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Thus, the halogenated butene compound represented by the general formula (1) to be produced may specifically be, for example, CF3CF＝CHCF3、CCl3CCl＝CHCCl3、CBr3CBr＝CHCBr3And the like.
After the reaction of the halogenated butyne compound with the hydrogen halide (addition reaction of the hydrogen halide) is completed, purification treatment can be carried out according to a conventional method as necessary to obtain a halogenated butene compound as a target compound. Further, according to the production method of the present invention, as described above, the reaction of adding 2 moles of hydrogen halide to 1 mole of the butyne halide compound is suppressed, and the butene halide compound to which 1 mole of hydrogen halide is added to 1 mole of the butyne halide compound can be selectively obtained.
The halogenated butene compound obtained in this way can be effectively used in various applications such as etching gases for forming the foremost fine structure of semiconductors, liquid crystals, and the like.
2. Halogenated butene compositions
In the above-described manner, a halogenated butene compound can be obtained, and a halogenated butene composition containing a halogenated butene compound obtained by adding 1 mol of hydrogen halide to 1 mol of a halogenated butyne compound and a halogenated butane compound obtained by adding 2 mol of hydrogen halide to 1 mol of the halogenated butyne compound can also be obtained.
In the halogenated butene composition of the present invention, the halogenated butene compound is a halogenated butene compound represented by the above general formula (1), and the halogenated butane compound is a halogenated butane compound represented by the above general formula (3).
In the general formulae (1) and (3), as X1、X2、X3、X4、X5、X6、X7、X8And X9Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.
The content of the halogenated butene compound represented by the general formula (1) is preferably 91.00 to 99.99 mol%, and more preferably 92.00 to 99.98 mol%, based on 100 mol% of the total amount of the halogenated butene composition of the present invention. The content of the halogenated butane compound represented by the general formula (3) is preferably 0.01 to 9.00 mol%, more preferably 0.02 to 8.00 mol%.
Further, according to the production method of the present invention, even when the halogenated butene compound is obtained as the halogenated butene composition, as described above, the conversion rate of the reaction can be increased, and the halogenated butene compound represented by the general formula (1) can be obtained with high yield and high selectivity, and therefore, components other than the halogenated butene compound represented by the general formula (1) in the halogenated butene composition can be reduced, and therefore, the labor for purification to obtain the halogenated butene compound represented by the general formula (1) can be reduced.
Such a halogenated butene composition of the present invention can be effectively used for various applications such as a block for organic synthesis, in addition to an etching gas for forming the foremost fine structure of semiconductors, liquid crystals, and the like. The organic synthesis block is a substance that can be a precursor of a compound having a highly reactive skeleton. For example, halogenated butene compositions of the present invention with CF3Si(CH3)3By reaction of organosilicon compounds containing fluorine, CF can be introduced3Fluoroalkyl groups such as a fluoro group are converted into a substance which can be used as a cleaning agent or a fluorine-containing pharmaceutical intermediate.
While the embodiments of the present invention have been described, various modifications can be made in the form and details without departing from the spirit and scope of the appended claims.
Examples
The following examples are provided to clarify the features of the present invention. The present invention is not limited to these examples.
In the processes for producing halogenated butene compounds of examples 1 to 6 and comparative examples 1 to 2, the starting compound is a halogenated butyne compound represented by the general formula (2) wherein X is1、X2、X3、X7、X8And X9A compound containing fluorine atoms and hydrogen halide as hydrogen fluoride, and obtaining a halogenated butene compound by a hydrogen fluoride addition reaction according to the following reaction formula:
CF3C≡CCF3+HF→CF3CF＝CHCF3
examples 1 to 4: hydrogen fluoride addition reaction using activated carbon catalyst
An activated carbon catalyst (available from Osaka gas chemical Co., Ltd.; specific surface area 1200 m) was added to an SUS pipe (outer diameter: 1/2 inches) as a reaction tube as a catalyst2G)10 g. After drying at 200 ℃ for 2 hours under a nitrogen atmosphere, the pressure was set toAt normal pressure, with CF3C≡CCF3The contact time (W/F) between the substrate and hydrogen fluoride and the activated carbon catalyst was 2g sec/cc, and CF was passed through the reaction tube3C≡CCF3(substrate) and hydrogen fluoride gas.
The reaction is carried out in a gas phase continuous flow mode.
The reaction tube is heated at 200 ℃, 250 ℃, 300 ℃ or 400 ℃ to start the hydrogen fluoride addition reaction.
Will react with CF3C≡CCF3Molar ratio of hydrogen fluoride gas (HF/CF) contacted (substrate)3C≡CCF3Ratio) was 150, and the flow rates of the substrate and the hydrogen fluoride gas were adjusted so that the contact time (W/F) was 2g sec/cc, and the distillate passed through the haz column was collected 1 hour after the start of the reaction.
Thereafter, mass spectrometry was performed by gas chromatography/mass spectrometry (GC/MS) using a gas chromatograph (product name "GC-2014" manufactured by shimadzu corporation), and structural analysis was performed by NMR (product name "400 YH" manufactured by JEOL corporation).
From the results of mass spectrometry and structural analysis, it was confirmed that CF was produced as the objective compound3CF＝CHCF3. In example 1, from CF3C≡CCF3Conversion (substrate) 99.75 mol%, CF3CF＝CHCF3The selectivity of (the objective Compound) was 99.85 mol%, CF3CF2CH2CF3The selectivity of (A) was 0.11 mol%, CF3CFHCFHCF3The selectivity of (3) was 0.01 mol%. In example 2, from CF3C≡CCF3Conversion of (substrate) 100.00 mol%, CF3CF＝CHCF3The selectivity of (the objective Compound) was 99.36 mol%, CF3CF2CH2CF3The selectivity of (A) was 0.34 mol%, CF3CFHCFHCF3The selectivity of (3) was 0.26 mol%. In example 3, from CF3C≡CCF3Conversion of (substrate) 100.00 mol%, CF3CF＝CHCF3The selectivity of (the objective Compound) was 98.45 mol%, CF3CF2CH2CF3The selectivity of (A) was 0.98 mol%, CF3CFHCFHCF3The selectivity of (3) was 0.10 mol%. In example 4, from CF3C≡CCF3Conversion of (substrate) 100.00 mol%, CF3CF＝CHCF3The selectivity of (the objective Compound) was 99.15 mol%, CF3CF2CH2CF3The selectivity of (A) was 0.80 mol%, CF3CFHCFHCF3The selectivity of (3) was 0.02 mol%.
Examples 5 to 6: hydrogen fluoride addition reaction using chromium oxide catalyst
Chromium oxide catalyst (Cr) as the catalyst2O3) At a reaction temperature of 350 ℃ and CF3C≡CCF3The contact time (W/F) between the (substrate) and the hydrogen fluoride gas and the chromium oxide catalyst was adjusted to 4g sec/cc or 5g sec/cc to adjust CF3C≡CCF3(substrate) and hydrogen fluoride gas in a total flow rate such that CF and3C≡CCF3molar ratio of hydrogen fluoride gas (HF/CF) contacted (substrate)3C≡CCF3Ratio) was 50 or 200, and the reaction was carried out in the same manner as in examples 1 to 4.
From the results of mass spectrometry and structural analysis, it was confirmed that CF was produced as the objective compound3CF＝CHCF3. In example 5, from CF3C≡CCF3The conversion (substrate) was 97.59 mol%, CF3CF＝CHCF3The selectivity of (the objective Compound) was 99.98 mol%, CF3CF2CH2CF3The selectivity of (A) was 0.01 mol%, CF3CFHCFHCF3The selectivity of (3) was 0.00 mol%. In example 6, from CF3C≡CCF3Conversion (substrate) 80.90 mol%, CF3CF＝CHCF3The selectivity of (the objective Compound) was 99.96 mol%, CF3CF2CH2CF3The selectivity of (A) was 0.03 mol%, CF3CFHCFHCF3The selectivity of (3) was 0.00 mol%.
Comparative examples 1 to 2: hydrogen fluoride addition reaction without catalyst
Without using a catalyst, the reaction temperature is 200 ℃ or 350 ℃, CF3C≡CCF3The contact time (W/F) between the (substrate) and the hydrogen fluoride gas and the catalyst was 20g sec/cc, and CF was3C≡CCF3Molar ratio of (substrate) to hydrogen fluoride gas contacted (HF/CF)3C≡CCF3Ratio) was 200, and reactions were carried out in the same manner as in examples 1 to 4. In comparative examples 1 to 2, the term "W/F" means that CF was flowed at the same flow rate as that at which W/F was 20g sec/cc in examples 1 to 6 using a catalyst3C≡CCF3(substrate) means.
From the results of mass spectrometry and structural analysis, it was confirmed that CF was produced as the objective compound3CF＝CHCF3. In comparative example 1, although CF was used3C≡CCF3The flow rate of (substrate) was significantly greater than that of examples 1 to 6, from CF3C≡CCF3The conversion (substrate) was also 1.92 mol%, CF3CF＝CHCF3The selectivity of (the objective Compound) was 90.83 mol%, CF3CF2CH2CF3The selectivity of (A) was 8.27 mol%, CF3CFHCFHCF3The selectivity of (3) was 0.82 mol%. In comparative example 2, although CF was used3C≡CCF3The flow rate of (substrate) was significantly greater than that of examples 1 to 6, from CF3C≡CCF3The conversion (substrate) was also 2.17 mol%, CF3CF＝CHCF3The selectivity of (the objective Compound) was 85.52 mol%, CF3CF2CH2CF3The selectivity of (A) was 7.83 mol%, CF3CFHCFHCF3The selectivity of (3) was 0.62 mol%. Thus, from CF3C≡CCF3The conversion rate of (substrate) is remarkably decreased, and CF as an impurity is considerably generated3CF2CH2CF3CF as the object Compound3CF＝CHCF3The selectivity of (2) is also low.
The results are shown in Table 1.
[ Table 1]
Claims (7)
1. A process for producing a halogenated butene compound represented by the general formula (1), which comprises:
comprising a step of reacting a halogenated butyne compound represented by the general formula (2) with a hydrogen halide in the presence of a catalyst,
general formula (1):
CX1X2X3CX4＝CHCX7X8X9 (1)
in the formula (1), X1、X2、X3、X4、X7、X8And X9Identical or different, represent a halogen atom,
general formula (2):
CX1X2X3C≡CCX7X8X9 (2)
in the formula (2), X1、X2、X3、X7、X8And X9As described above.
2. The manufacturing method according to claim 1, wherein:
the halogenated butene compound represented by the general formula (1) is CF3CF＝CHCF3And the halogenated butyne compound represented by the general formula (2) is CF3C≡CCF3。
3. The manufacturing method according to claim 1 or 2, characterized in that:
the catalyst comprises at least 1 selected from a fluorinated or non-fluorinated activated carbon catalyst, and a fluorinated or non-fluorinated lewis acid catalyst.
4. The production method according to any one of claims 1 to 3, characterized in that:
the catalyst is a fluorinated or non-fluorinated lewis acid catalyst, and the lewis acid catalyst is at least 1 selected from a chromium oxide catalyst, an alumina catalyst, a silica alumina catalyst, and a zeolite catalyst.
5. The production method according to any one of claims 1 to 4, characterized in that:
30 to 250 moles of hydrogen halide are reacted with respect to 1 mole of the halogenated butyne compound represented by the general formula (2).
6. A composition characterized by:
comprising a halogenated butene compound represented by the general formula (1) and a halogenated butane compound represented by the general formula (3),
the content of the halogenated butene compound represented by the general formula (1) is 91.00 to 99.99 mol% based on 100 mol% of the total composition,
general formula (1):
CX1X2X3CX4＝CHCX7X8X9 (1)
in the formula (1), X1、X2、X3、X4、X7、X8And X9Identical or different, represent a halogen atom,
general formula (3):
CX1X2X3CX4X5CHX6CX7X8X9 (3)
in the formula (3), X1、X2、X3、X4、X7、X8And X9Same as above, X5And X6One of them represents a hydrogen atom and the other represents a halogen atom.
7. The composition of claim 6, wherein:
it is used as a cleaning gas, an etching gas or a block for organic synthesis.
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| CN106966856A (en) * | 2017-03-08 | 2017-07-21 | 浙江衢化氟化学有限公司 | A kind of preparation method of the butylene of 1,1,1,4,4,4 hexafluoro 2 |
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2019
- 2019-02-21 JP JP2019029424A patent/JP6827246B2/en active Active
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2020
- 2020-02-14 WO PCT/JP2020/005856 patent/WO2020170980A1/en active Application Filing
- 2020-02-14 KR KR1020217029187A patent/KR20210129107A/en not_active Application Discontinuation
- 2020-02-14 CN CN202080015744.4A patent/CN113474319A/en active Pending
- 2020-02-20 TW TW109105400A patent/TWI829871B/en active
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| CN1098332A (en) * | 1993-06-18 | 1995-02-08 | 昭和电工株式会社 | Fluorination catalyst and fluorination process |
| CN1911512A (en) * | 2005-07-07 | 2007-02-14 | 独立行政法人产业技术综合研究所 | Fluorination catalysts, method for their preparation, and method for producing fluorinated compounds using the catalysts |
| CN102105422A (en) * | 2008-08-06 | 2011-06-22 | 大金工业株式会社 | Process for preparing 2,3,3,3-tetrafluoropropene and 1,3,3,3-tetrafluoropropene |
| CN106966856A (en) * | 2017-03-08 | 2017-07-21 | 浙江衢化氟化学有限公司 | A kind of preparation method of the butylene of 1,1,1,4,4,4 hexafluoro 2 |
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Also Published As
| Publication number | Publication date |
|---|---|
| TW202043182A (en) | 2020-12-01 |
| JP6827246B2 (en) | 2021-02-10 |
| TWI829871B (en) | 2024-01-21 |
| KR20210129107A (en) | 2021-10-27 |
| WO2020170980A1 (en) | 2020-08-27 |
| JP2020132585A (en) | 2020-08-31 |
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