TW202043182A - Method for producing halogenated butene - Google Patents
Method for producing halogenated butene Download PDFInfo
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- TW202043182A TW202043182A TW109105400A TW109105400A TW202043182A TW 202043182 A TW202043182 A TW 202043182A TW 109105400 A TW109105400 A TW 109105400A TW 109105400 A TW109105400 A TW 109105400A TW 202043182 A TW202043182 A TW 202043182A
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- Prior art keywords
- halogenated
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 29
- 125000000383 tetramethylene group Chemical class [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 title description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 97
- -1 halogenated butene compound Chemical class 0.000 claims abstract description 92
- 229910000039 hydrogen halide Inorganic materials 0.000 claims abstract description 42
- 239000012433 hydrogen halide Substances 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 21
- 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 41
- 239000007789 gas Substances 0.000 claims description 30
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 16
- 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
- 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
- 239000011968 lewis acid catalyst Substances 0.000 claims description 11
- 239000010457 zeolite Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 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
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 57
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 description 29
- 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
- 239000000758 substrate Substances 0.000 description 16
- 239000011159 matrix material Substances 0.000 description 13
- 239000012025 fluorinating agent Substances 0.000 description 12
- 239000012071 phase Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 238000003682 fluorination reaction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 229910052731 fluorine Inorganic materials 0.000 description 7
- 125000001153 fluoro group Chemical group F* 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 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
- 239000002245 particle Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 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
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- 238000012916 structural analysis Methods 0.000 description 4
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 3
- 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
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-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
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 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
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 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
- 229910004298 SiO 2 Inorganic materials 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
- 208000012839 conversion disease Diseases 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010304 firing 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
- 238000002156 mixing Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000126 substance Substances 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
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- GWBUAGAPOIBIRT-UHFFFAOYSA-G [F-].[Al+3].[Si+4].[F-].[F-].[F-].[F-].[F-].[F-] Chemical compound [F-].[Al+3].[Si+4].[F-].[F-].[F-].[F-].[F-].[F-] GWBUAGAPOIBIRT-UHFFFAOYSA-G 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 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
- 229940125782 compound 2 Drugs 0.000 description 1
- 238000007796 conventional method Methods 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
- 238000007872 degassing Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- PGZIKUPSQINGKT-UHFFFAOYSA-N dialuminum;dioxido(oxo)silane Chemical compound [Al+3].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O PGZIKUPSQINGKT-UHFFFAOYSA-N 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material 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
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 229910052742 iron 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
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 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
- 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
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 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
- 239000000243 solution Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001308 synthesis 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 potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Plasma & Fusion (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Drying Of Semiconductors (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
本揭示係有關鹵化丁烯化合物之製造方法。This disclosure relates to the production method of halogenated butene compounds.
以七氟丁烯為代表之具有7個鹵素原子之丁烯化合物係除了作為半導體用乾蝕刻氣體以外，亦被期待作為清洗氣體、有機合成用建構組元等之化合物。The butene compound with 7 halogen atoms represented by heptafluorobutene is not only used as a dry etching gas for semiconductors, but is also expected to be used as a cleaning gas, a building block for organic synthesis, and the like.
作為該具有7個鹵素原子之丁烯化合物之製造方法，例如於非專利文獻1中，使CF3 C≡CCF3 與AgF反應，獲得CF3 CF=C(CF3 )Ag後，於乙腈中與HCl反應，獲得CF3 CF=CHCF3 。 [先前技術文獻] [非專利文獻]As a method for producing the butene compound with 7 halogen atoms, for example, in Non-Patent Document 1, CF 3 C≡CCF 3 is reacted with AgF to obtain CF 3 CF=C(CF 3 )Ag and then in acetonitrile React with HCl to obtain CF 3 CF=CHCF 3 . [Prior technical literature] [Non-patent literature]
[非專利文獻1]Journal of the American Chemical Society, 91, 1969, p. 6532-6534[Non-Patent Document 1] Journal of the American Chemical Society, 91, 1969, p. 6532-6534
[發明欲解決之課題][The problem to be solved by the invention]
本發明之目的在於提供可以高轉化率且以高選擇率獲得具有7個鹵素原子之丁烯化合物之方法。 [用以解決課題之手段]The object of the present invention is to provide a method for obtaining a butene compound having 7 halogen atoms with a high conversion rate and a high selectivity. [Means to solve the problem]
本揭示包含以下構成。
項1. 一種製造方法，其係以通式(1)表示之鹵化丁烯化合物之製造方法，
依據本發明，可藉轉化率高且可以高選擇率之方法合成具有7個鹵素原子之丁烯化合物。According to the present invention, a butene compound with 7 halogen atoms can be synthesized by a method with high conversion rate and high selectivity.
本說明書中，「含有」係包含「包括(comprise)」、「實質上僅由~構成(consist essentially of)」及「由~構成(consist of)」之任一者之概念。又，本說明書中，數值範圍以「A~B」表示時，意指A以上B以下。In this specification, "contains" is a concept that includes any of "comprise", "consist essentially of", and "consist of". In addition, in this specification, when the numerical range is represented by "A to B", it means A to B or more.
本揭示中，所謂「選擇率」意指相對於自反應器出口之流出氣體中原料化合物以外之化合物合計莫耳量，該流出氣體中所含之目的化合物之合計莫耳量之比例(莫耳%)。In the present disclosure, the "selectivity" refers to the ratio of the total molar amount of the target compound contained in the effluent gas relative to the total molar amount of the compound other than the raw material compound in the outflow gas from the reactor (mole %).
本揭示中，所謂「轉化率」意指相對於供給至反應器之原料化合物之莫耳量，自反應器出口之流出氣體中所含之原料化合物以外之化合物的合計莫耳量之比例(莫耳%)。In the present disclosure, the "conversion rate" means the ratio of the total molar amount of the compound other than the raw material compound contained in the effluent gas from the reactor outlet relative to the molar amount of the raw material compound supplied to the reactor (mole ear%).
以往，依據非專利文獻1之方法，使CF3 C≡CCF3 與AgF反應，獲得CF3 CF=C(CF3 )Ag後，於乙腈中與HCl反應，獲得CF3 CF=CHCF3 ，必須要2階段之反應，合計收率不過為57%。In the past, according to the method of Non-Patent Document 1, CF 3 C≡CCF 3 was reacted with AgF to obtain CF 3 CF=C(CF 3 )Ag and then reacted with HCl in acetonitrile to obtain CF 3 CF=CHCF 3 . For a two-stage reaction, the total yield is only 57%.
由以上，依據以往方法，收率不過為57%，且係步驟數亦多之反應。依據本揭示之製造方法，與以往比較，係轉化率高且可為高選擇率之方法，可合成具有7個鹵素原子之丁烯化合物。From the above, according to the conventional method, the yield is only 57%, and it is a reaction with a large number of steps. According to the manufacturing method of the present disclosure, compared with the past, it is a method with a high conversion rate and a high selectivity, and a butene compound with 7 halogen atoms can be synthesized.
1.鹵化丁烯化合物之製造方法
本揭示之製造方法係以通式(1)表示之鹵化丁烯化合物之製造方法，
本揭示之製造方法中，以通式(2)表示之鹵化丁炔化合物與鹵化氫之反應若於無觸媒下進行，則會相當程度(例如多於9.00莫耳%之量)生成作為副產物之對於以通式(2)表示之鹵化丁炔化合物1莫耳加成有2莫耳之鹵化氫之以通式(3)表示之鹵化丁烷化合物，
另一方面，上述以通式(2)表示之鹵化丁炔化合物與鹵化氫之反應藉由於觸媒存在下進行，可抑制對於以通式(2)表示之鹵化丁炔化合物1莫耳加成2莫耳之鹵化氫，可選擇性地獲得對於以通式(2)表示之鹵化丁炔化合物1莫耳加成1莫耳之鹵化氫的以通式(1)表示之鹵化丁烯化合物。此係三鹵化甲基(CX1 X2 X3 及CX7 X8 X9 )之強力拉電子基之效應所致者。藉由其強力拉電子效應，由於三鹵化甲基使鄰接之雙鍵或三鍵的電子之電子密度降低，故不易引起對該不飽和鍵之加成反應。鹵化丁炔化合物由於具有三鍵故其反應性高，因此容易進行鹵化氫之加成反應，但鹵化丁烯化合物藉由三鹵化甲基之效應，不與鹵化氫反應而不成為鹵化丁烷化合物，而可選擇性地獲得鹵化丁烯化合物。On the other hand, the reaction between the halogenated butyne compound represented by the general formula (2) and the hydrogen halide is carried out in the presence of a catalyst, and the addition of 1 mole to the halogenated butyne compound represented by the general formula (2) can be suppressed. 2 moles of hydrogen halide can selectively obtain the halogenated butene compound represented by general formula (1) in which 1 mole of halogenated butyne compound represented by general formula (2) is added to 1 mole of hydrogen halide. This is caused by the powerful electron group pulling effect of trihalomethyl (CX 1 X 2 X 3 and CX 7 X 8 X 9 ). With its strong electron pulling effect, since the trihalide methyl group reduces the electron density of the adjacent double bond or triple bond electrons, it is difficult to cause an addition reaction to the unsaturated bond. The halogenated butyne compound has high reactivity due to the triple bond, so it is easy to carry out the addition reaction of hydrogen halide, but the halogenated butene compound does not react with the hydrogen halide and does not become a halogenated butane compound due to the effect of the trihalogenated methyl group. , And can selectively obtain halogenated butene compounds.
作為本揭示之製造方法中可使用之基質的鹵化丁炔化合物，如上述係以通式(2)表示之鹵化丁炔化合物：
通式(2)中，作為X1 、X2 、X3 、X7 、X8 及X9 表示鹵素原子可舉例為氟原子、氯原子、溴原子及碘原子。In the general formula (2), X 1 , X 2 , X 3 , X 7 , X 8 and X 9 represent a halogen atom, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
作為基質的鹵化丁炔化合物，基於可以特別高的轉化率、收率及選擇率製造鹵化丁烯化合物之觀點，較佳X1 、X2 、X3 、X7 、X8 及X9 均為氟原子。The halogenated butyne compound as a substrate is preferably produced by X 1 , X 2 , X 3 , X 7 , X 8 and X 9 from the viewpoint that the halogenated butene compound can be produced at a particularly high conversion rate, yield, and selectivity. Fluorine atom.
上述X1 、X2 、X3 、X7 、X8 及X9 可為相同亦可為相異。The aforementioned X 1 , X 2 , X 3 , X 7 , X 8 and X 9 may be the same or different.
作為滿足如上述條件之基質之鹵化丁炔化合物具體舉例為CF3 C≡CCF3 、CCl3 C≡CCCl3 、CBr3 C≡CCBr3 等。該等鹵化丁炔化合物可單獨使用，亦可組合2種以上使用。此等鹵化丁炔化合物可採用習知或市售品。且亦可依據日本特開2012-001448號公報等之常用方法合成。Specific examples of halogenated butyne compounds that satisfy the above-mentioned conditions are CF 3 C≡CCF 3 , CCl 3 C≡CCCl 3 , CBr 3 C≡CCBr 3 and the like. These halogenated butyne compounds may be used alone or in combination of two or more kinds. These halogenated butyne compounds can be conventionally or commercially available products. It can also be synthesized according to common methods such as Japanese Patent Laid-Open No. 2012-001448.
作為與鹵化丁炔化合物反應之鹵化氫，舉例為氟化氫、氯化氫、溴化氫等。又，基於反應之轉化率、收率及選擇率之觀點，較佳為氟化氫。該等鹵化氫可單獨使用，亦可組合2種以上使用。Examples of the hydrogen halide that reacts with the halogenated butyne compound include hydrogen fluoride, hydrogen chloride, hydrogen bromide, and the like. Moreover, from the viewpoint of the conversion rate, yield, and selectivity of the reaction, hydrogen fluoride is preferred. These hydrogen halides may be used alone or in combination of two or more kinds.
鹵化氫通常較佳以氣相狀態與鹵化丁炔化合物(基質)一起供給至反應器。與鹵化丁炔化合物(基質)反應之鹵化氫之供給量，相對於鹵化丁炔化合物(基質)1莫耳，較佳為30~250莫耳，更佳為35~240莫耳，又更佳為40~230莫耳。藉由設為該範圍，可更良好地進行鹵化氫之加成反應，且可更抑制鹵化氫之過度加成反應，而可更減低雜質產生，可使生成物之鹵化丁烯化合物之選擇率高，可以高收率回收。The hydrogen halide is usually preferably supplied to the reactor together with the halogenated butyne compound (substrate) in a gaseous state. The supply amount of hydrogen halide that reacts with the halogenated butyne compound (substrate) is preferably 30-250 mol, more preferably 35-240 mol, and more preferably relative to 1 mol of the halogenated butyne compound (substrate) It is 40~230 moles. By setting it in this range, the addition reaction of hydrogen halide can be performed more satisfactorily, the excessive addition reaction of hydrogen halide can be suppressed, the generation of impurities can be further reduced, and the selectivity of the halogenated butene compound of the product High, can be recycled with high yield.
本揭示之使鹵化丁炔化合物與鹵化氫反應之步驟係鹵化氫之加成反應，於觸媒存在下進行。本揭示之製造方法中使鹵化丁炔化合物與鹵化氫反應之步驟(加成反應)，較佳以氣相，特別是使用固定床反應器之氣相連續流通式進行。以氣相連續流通式進行時，可使裝置、操作等簡略化，且經濟上亦有利。The step of reacting a halogenated butyne compound with hydrogen halide in the present disclosure is an addition reaction of hydrogen halide and is carried out in the presence of a catalyst. In the manufacturing method of the present disclosure, the step of reacting the halogenated butyne compound with hydrogen halide (addition reaction) is preferably carried out in a gas phase, especially a gas phase continuous flow method using a fixed bed reactor. When the gas phase continuous flow type is used, the equipment and operation can be simplified, and it is also economically advantageous.
本揭示之使鹵化丁炔化合物與鹵化氫反應之步驟，例如作為基質，係以通式(2)表示之鹵化丁炔化合物，更佳X1 、X2 、X3 、X7 、X8 及X9 為氟原子。The step of reacting a halogenated butyne compound with hydrogen halide in the present disclosure, for example, as a substrate, is a halogenated butyne compound represented by the general formula (2), more preferably X 1 , X 2 , X 3 , X 7 , X 8 and X 9 is a fluorine atom.
亦即，係依據下述反應式之氟化氫之加成反應：
作為本揭示之製造方法中使用之觸媒較佳為氟化或非氟化活性碳觸媒、氟化或非氟化路易士酸觸媒。The catalyst used in the manufacturing method of the present disclosure is preferably a fluorinated or non-fluorinated activated carbon catalyst, and a fluorinated or non-fluorinated Lewis acid catalyst.
作為活性碳觸媒並未特別限定，可舉例為破碎碳、成形碳、顆粒碳、球狀碳等之粉末活性碳。粉末活性碳較佳使用以JIS試驗(JIS Z8801)顯示4網眼(4.75mm) ~100網眼(0.150mm)之粒度之粉末活性碳。該等活性碳可採用習知或市售品。The activated carbon catalyst is not particularly limited, and may be powdered activated carbon such as crushed carbon, formed carbon, granular carbon, and spherical carbon. The powdered activated carbon preferably uses a powdered activated carbon showing a particle size of 4 meshes (4.75 mm) to 100 meshes (0.150 mm) according to the JIS test (JIS Z8801). The activated carbon can be conventional or commercially available products.
為了使活性碳藉由氟化而顯示更強活性，亦可使用於用於反應之前，預先使活性碳氟化之氟化活性碳。亦即作為活性碳觸媒，可使用未經氟化之活性碳及氟化活性碳之任一者。In order to make the activated carbon exhibit stronger activity by fluorination, it can also be used before the fluorinated activated carbon is used in the reaction. That is, as an activated carbon catalyst, either unfluorinated activated carbon or fluorinated activated carbon can be used.
作為用以使活性碳氟化之氟化劑，除了例如HF等之無機氟化劑以外，亦可使用六氟丙烷等之氫氟碳(HFC)、氯氟甲烷等之氯氟碳(CFC)、氫氯氟碳(HCFC)等之有機氟化劑。As a fluorinating agent for fluorinating activated carbon, in addition to inorganic fluorinating agents such as HF, hydrofluorocarbon (HFC) such as hexafluoropropane, and chlorofluorocarbon (CFC) such as chlorofluoromethane can also be used , Hydrochlorofluorocarbon (HCFC) and other organic fluorinating agents.
作為使活性碳氟化之方法可舉例為例如於室溫(25℃)~400℃左右之溫度條件下於大氣壓下流通上述氟化劑而氟化之方法。As a method of fluorinating activated carbon, for example, a method of fluorinating by circulating the above-mentioned fluorinating agent under atmospheric pressure under a temperature condition of about room temperature (25°C) to 400°C.
作為路易士酸觸媒並未特別限定，舉例為氧化鉻觸媒、氧化鋁觸媒、矽鋁觸媒、沸石觸媒等。該等路易士酸觸媒可採用未經氟化之路易士酸觸媒及經氟化之路易士酸觸媒之任一者。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. The Lewis acid catalyst may be any one of the non-fluorinated road and the fluorinated road easy acid catalyst.
關於氧化鉻觸媒並未特別限定，以CrOm 表示氧化鉻時，較佳1.5＜m＜3，更佳為2＜m＜2.75，又更佳為2＜m＜2.3。且，以CrOm ・nH2 O表示氧化鉻時，亦可以n之值為3以下，特佳為1~1.5般水合。The chromium oxide catalyst is not particularly limited. When CrO m represents chromium oxide, 1.5<m<3 is preferable, 2<m<2.75 is more preferable, and 2<m<2.3 is more preferable. In addition, when CrO m ·nH 2 O represents chromium oxide, the value of n may be 3 or less, and it is particularly preferably hydrated as 1 to 1.5.
經氟化之氧化鉻觸媒可藉由使上述氧化鉻觸媒氟化而調製。該氟化例如可使用HF、氟碳等進行。此等經氟化之氧化鉻觸媒例如可依據日本特開平05-146680號公報記載之方法合成。The fluorinated chromium oxide catalyst can be prepared by fluorinating the above-mentioned chromium oxide catalyst. This fluorination can be performed using HF, fluorocarbon, etc., for example. These fluorinated chromium oxide catalysts can be synthesized, for example, according to the method described in Japanese Patent Application Laid-Open No. 05-146680.
以下，顯示氧化鉻觸媒及經氟化氧化鉻觸媒之合成方法之一。The following shows one of the synthesis methods of chromium oxide catalyst and fluorinated chromium oxide catalyst.
首先，混合鉻鹽之水溶液(硝酸鉻、氯化鉻、鉻礬、硫酸鉻等)與氨水而可獲得氫氧化鉻之沉澱。藉由此時之沉澱反應之反應速度可控制氫氧化鉻之物性。反應速度較快較佳。反應速度係受反應溶液溫度、氨水混合方法(混合速度)、攪拌狀態等而左右。First, mix the aqueous solution of chromium salt (chromium nitrate, chromium chloride, chromium alum, chromium sulfate, etc.) with ammonia water to obtain the precipitation of chromium hydroxide. The physical properties of chromium hydroxide can be controlled by the reaction rate of the precipitation reaction at this time. The reaction speed is faster and better. The reaction speed is affected by the temperature of the reaction solution, the ammonia water mixing method (mixing speed), and the stirring state.
該沉澱經過濾洗淨後，可進行乾燥。乾燥例如可於空氣中於70~200℃進行1~100小時。該階段之觸媒有時稱為氫氧化鉻狀態。其次，可使該觸媒解碎。基於顆粒之強度、觸媒活性等之觀點，較佳以使經解碎之粉末(例如粒徑為1000μm以下，特別是46~1000μm之粒徑品為95%)之粉體密度成為0.6~1.1g/ml，較佳0.6~1.0g/ml之方式調整沉澱反應速度。粉體之比表面積(利用BET法之比表面積)於例如200℃、80分鐘之脫氣條件下，較佳為100m2 /g以上，更佳為120m2 /g以上。又比表面積之上限為例如220 m2 /g左右。After the precipitate is filtered and washed, it can be dried. For example, drying can be performed in the air at 70 to 200°C for 1 to 100 hours. The catalyst at this stage is sometimes called the chromium hydroxide state. Secondly, the catalyst can be broken up. From the viewpoints of particle strength, catalyst activity, etc., it is preferable to make the powder density of the smashed powder (for example, the particle size of 1000μm or less, especially the particle size of 46~1000μm is 95%) to 0.6~1.1 g/ml, preferably 0.6~1.0g/ml to adjust the precipitation reaction rate. The specific surface area of the powder (specific surface area by the BET method) is preferably 100 m 2 /g or more, more preferably 120 m 2 /g or more under degassing conditions at 200° C. for 80 minutes, for example. The upper limit of the specific surface area is, for example, about 220 m 2 /g.
於該氫氧化鉻之粉體中根據需要混合3重量%以下之石墨，藉由打錠機可形成顆粒。顆粒之尺寸及強度可適當調整。The chromium hydroxide powder is mixed with 3% by weight or less of graphite as needed, and granules can be formed by a tablet machine. The size and strength of the particles can be adjusted appropriately.
成形之觸媒於惰性環境中，例如於氮氣流中燒成，可成為非晶質之氧化鉻。該燒成溫度較佳為360℃以上，基於抑制結晶化之觀點，較佳為380~460℃。且燒成時間可為例如1~5小時。The formed catalyst is fired in an inert environment, such as in a nitrogen stream, to become amorphous chromium oxide. The firing temperature is preferably 360°C or higher, and from the viewpoint of suppressing crystallization, it is preferably 380 to 460°C. And the firing time can be, for example, 1 to 5 hours.
經燒成之觸媒比表面積，基於觸媒活性之觀點，較佳為例如170 m2 /g以上，更佳為180m2 /g以上，又更佳為200m2 /g以上。又比表面積之上限通常較佳為240m2 /g左右，更佳為220m2 /g左右。From the viewpoint of catalyst activity, the specific surface area of the fired catalyst is preferably, for example, 170 m 2 /g or more, more preferably 180 m 2 /g or more, and still more preferably 200 m 2 /g or more. In addition, the upper limit of the specific surface area is generally preferably about 240 m 2 /g, and more preferably about 220 m 2 /g.
其次，藉由使氧化鉻氟化可獲得經氟化之氧化鉻。氟化溫度只要設為不使產生之水凝集之溫度範圍即可，只要將不因熱反應而使觸媒結晶化之溫度設為上限即可。氟化溫度可設為例如100~460℃。氟化時之壓力並未限制，但較佳以供於觸媒反應時之壓力進行。Secondly, fluorinated chromium oxide can be obtained by fluorinating chromium oxide. The fluorination temperature may be a temperature range that does not cause the generated water to condense, and the temperature at which the catalyst does not crystallize due to a thermal reaction may be set as the upper limit. The fluorination temperature can be set to, for example, 100 to 460°C. The pressure at the time of fluorination is not limited, but it is preferably carried out at the pressure provided for the catalyst reaction.
作為氧化鋁觸媒舉例為例如α-氧化鋁、活性氧化鋁等。作為活性氧化鋁舉例為ρ-氧化鋁、χ-氧化鋁、κ-氧化鋁、η-氧化鋁、擬γ-氧化鋁、γ-氧化鋁、σ-氧化鋁、θ-氧化鋁等。Examples of the alumina catalyst include α-alumina and activated alumina. Examples of activated alumina include ρ-alumina, χ-alumina, κ-alumina, η-alumina, pseudo-γ-alumina, γ-alumina, σ-alumina, and θ-alumina.
又，作為複合氧化物亦可使用矽鋁觸媒。矽鋁觸媒係包含氧化矽(SiO2 )及氧化鋁(Al2 O3 )之複合氧化物觸媒，可使用將氧化矽及氧化鋁總量設為100質量%，例如氧化矽含量為20~90質量%，特別是50~80質量%之觸媒。In addition, a silicon-aluminum catalyst can also be used as the composite oxide. The silicon-aluminum catalyst is a composite oxide catalyst containing silicon oxide (SiO 2 ) and aluminum oxide (Al 2 O 3 ). The total amount of silicon oxide and aluminum oxide can be set to 100% by mass, for example, the content of silicon oxide is 20 ~90% by mass, especially 50~80% by mass catalyst.
氧化鋁觸媒及矽鋁觸媒藉由氟化，成為顯示更強活性，故亦可在用於反應之前預先使氧化鋁觸媒氟化作為氟化氧化鋁觸媒使用，亦可使矽鋁觸媒氟化作為氟化矽鋁觸媒使用。The alumina catalyst and the silica-aluminum catalyst become more active by fluorination, so the alumina catalyst can also be used as a fluorinated alumina catalyst before being used in the reaction. The catalyst fluorination is used as a fluoride silicon aluminum catalyst.
作為用以使氧化鋁觸媒及矽鋁觸媒氟化之氟化劑，可使用例如F2 、HF等之無機氟化劑，六氟丙烷等之氟碳系有機氟化劑等。As the fluorinating agent for fluorinating the alumina catalyst and the silicon-aluminum catalyst, for example, inorganic fluorinating agents such as F 2 and HF, and fluorocarbon-based organic fluorinating agents such as hexafluoropropane can be used.
作為使氧化鋁觸媒及矽鋁觸媒氟化之方法，可舉例為例如於室溫(25℃)~400℃左右之溫度條件下於大氣壓下流通上述氟化劑而氟化之方法。As a method of fluorinating an alumina catalyst and a silicon-aluminum catalyst, for example, a method of circulating the above-mentioned fluorinating agent under atmospheric pressure under a temperature condition of room temperature (25°C) to about 400°C to fluoride.
作為沸石觸媒可廣泛採用習知種類之沸石。例如較佳為鹼金屬或鹼土類金屬之結晶性含水鋁酸矽酸鹽。沸石之結晶形並未特別限定，可舉例為A型、X型、LSX型等。沸石中之鹼金屬或鹼土類金屬並未特別限定，可舉例為鉀、鈉、鈣、鋰等。As the zeolite catalyst, conventional types of zeolite can be widely used. For example, it is preferably a crystalline hydrous aluminate silicate of an alkali metal or alkaline earth metal. The crystal form of zeolite is not particularly limited, and examples thereof include A type, X type, and LSX type. The alkali metal or alkaline earth metal in the zeolite is not particularly limited, and examples thereof include potassium, sodium, calcium, and lithium.
沸石觸媒由於藉由氟化而顯示更強活性，故亦可在用於反應之前預先使沸石觸媒氟化作成氟化沸石觸媒使用。Since the zeolite catalyst exhibits stronger activity by fluorination, it can also be used as a fluorinated zeolite catalyst by fluorinating the zeolite catalyst before use in the reaction.
作為用以使沸石觸媒氟化之氟化劑可使用例如F2 、HF等之無機氟化劑、六氟丙烷等之氟碳系之有機氟化劑。As the fluorinating agent for fluorinating the zeolite catalyst, for example, inorganic fluorinating agents such as F 2 and HF, and fluorocarbon-based organic fluorinating agents such as hexafluoropropane can be used.
作為使沸石觸媒氟化之方法，可舉例為例如於室溫(25℃)~400℃左右之溫度條件下於大氣壓下流通上述氟化劑而氟化之方法。As a method of fluorinating the zeolite catalyst, for example, a method of circulating the above-mentioned fluorinating agent under atmospheric pressure under a temperature condition of room temperature (25°C) to about 400°C to fluoride.
上述觸媒可單獨使用，亦可組合2種以上使用。該等中，基於轉化率、選擇率及收率之觀點，較佳為氟化或非氟化活性碳觸媒、氟化或非氟化氧化鉻觸媒、氟化或非氟化氧化鋁觸媒等，更佳為氟化或非氟化活性碳觸媒、氟化或非氟化氧化鉻觸媒等。The above-mentioned catalysts may be used alone or in combination of two or more kinds. Among them, based on the viewpoint of conversion rate, selectivity and yield, fluorinated or non-fluorinated activated carbon catalyst, fluorinated or non-fluorinated chromium oxide catalyst, fluorinated or non-fluorinated alumina catalyst are preferred. The catalyst is more preferably a fluorinated or non-fluorinated activated carbon catalyst, a fluorinated or non-fluorinated chromium oxide catalyst, etc.
又，使用上述氟化或非氟化路易士酸觸媒作為觸媒之情況，亦可擔持於載體上。作為此等載體舉例為例如碳、氧化鋁(Al2 O3 )、氧化鋯(ZrO2 )、氧化矽(SiO2 )、氧化鈦(TiO2 )等。作為碳，可使用活性碳、不定形碳、石墨、金剛石等。In addition, when the above-mentioned fluorinated or non-fluorinated Lewis acid catalyst is used as the catalyst, it may be supported on a carrier. Examples of such supports include carbon, aluminum oxide (Al 2 O 3 ), zirconium oxide (ZrO 2 ), silicon oxide (SiO 2 ), titanium oxide (TiO 2 ), and the like. As the carbon, activated carbon, amorphous carbon, graphite, diamond, etc. can be used.
本揭示之製造方法中，於觸媒存在下使鹵化丁炔化合物與鹵化氫反應之際，較佳為例如使觸媒以固體狀態(固相)與鹵化丁炔化合物接觸。該情況下，觸媒形狀亦可為粉末狀，但較佳於氣相連續流通式反應中採用顆粒狀之情況較佳。In the production method of the present disclosure, when reacting the halogenated butyne compound with hydrogen halide in the presence of a catalyst, it is preferable to contact the catalyst with the halogenated butyne compound in a solid state (solid phase), for example. In this case, the shape of the catalyst may also be a powder, but it is preferable to use a granular form in a gas-phase continuous flow reaction.
觸媒之利用BET法測定之比表面積(以下有時亦稱為「BET比表面積」)通常較佳為10~3,000m2 /g，更佳為10~2500m2 /g，又更佳為20~2000m2 /g，特佳為30~1500 m2 /g。觸媒之BET比表面積落於此範圍之情況，由於觸媒粒子之密度不會過小，故能以更高選擇率獲得鹵化丁烯化合物。又，鹵化丁炔化合物之轉化率亦可更為提高。Determination of specific surface area using the BET method of the catalyst (hereinafter sometimes referred to as "BET specific surface area") is generally preferably 10 ~ 3,000m 2 / g, more preferably 10 ~ 2500m 2 / g, and more preferably 20 ~2000m 2 /g, particularly preferably 30~1500 m 2 /g. When the BET specific surface area of the catalyst falls within this range, since the density of the catalyst particles will not be too small, the halogenated butene compound can be obtained with a higher selectivity. In addition, the conversion rate of the halogenated butyne compound can be further improved.
本揭示之使鹵化丁炔化合物與鹵化氫反應之步驟中，反應溫度之下限值，基於更有效率地進行鹵化氫之加成反應、更提高轉化率、以更高選擇率獲得目的化合物的鹵化丁烯化合物之觀點，通常較佳為180℃以上，更佳為200℃以上。又，使用路易士酸觸媒作為觸媒之情況，反應溫度之下限值，基於同樣理由，較佳為280℃以下，更佳為320℃以下。In the step of reacting the halogenated butyne compound with hydrogen halide in the present disclosure, the lower limit of the reaction temperature is based on the fact that the addition reaction of hydrogen halide is performed more efficiently, the conversion rate is improved, and the target compound is obtained with a higher selectivity. From the viewpoint of the halogenated butene compound, it is generally preferably at least 180°C, more preferably at least 200°C. In addition, in the case of using a Lewis acid catalyst as a catalyst, the lower limit of the reaction temperature is preferably 280°C or lower, more preferably 320°C or lower for the same reason.
本揭示之使鹵化丁炔化合物與鹵化氫反應之反應溫度之上限值，基於更有效率地進行鹵化氫之加成反應、更提高轉化率、以更高選擇率獲得目的化合物的鹵化丁烯化合物之觀點，且基於更抑制因反應生成物分解或聚合所致之選擇率降低之觀點，通常較佳為500℃以下，更佳為450℃以下，又更佳為400℃以下。The upper limit of the reaction temperature of the halogenated butyne compound and the hydrogen halide in the present disclosure is based on the more efficient addition reaction of the hydrogen halide, higher conversion rate, and higher selectivity to obtain the halogenated butene of the target compound From the viewpoint of the compound, and from the viewpoint of more suppressing the decrease in selectivity due to decomposition or polymerization of the reaction product, it is generally preferably 500°C or lower, more preferably 450°C or lower, and still more preferably 400°C or lower.
本揭示之使鹵化丁炔化合物與鹵化氫反應之反應時間，於例如採用氣相流通式之情況，原料化合物對於觸媒之接觸時間(W/F)[W：金屬觸媒之重量(g)，F：原料化合物之流量(cc/sec)]，基於反應轉化率特別高，能以更高收率及高選擇率獲得鹵化丁烯化合物之觀點，較佳為1.5~30g・sec./cc，更佳為1.8~20g・sec./cc，又更佳為2.0 ~10g・sec./cc。上述之W/F於採用氣相流通式反應之情況之反應時間雖經特定，但採用批式反應之情況，接觸時間亦可適當設定。又，所謂上述接觸時間，意指基質與觸媒接觸之時間。The reaction time of the halogenated butyne compound and the hydrogen halide in the present disclosure is, for example, the contact time of the raw material compound with the catalyst (W/F) [W: weight of the metal catalyst (g) in the case of a gas-phase flow type. , F: the flow rate of the raw material compound (cc/sec)], based on the viewpoint that the reaction conversion rate is particularly high, and the halogenated butene compound can be obtained with higher yield and high selectivity, preferably 1.5~30g·sec./cc , More preferably 1.8~20g·sec./cc, and even more preferably 2.0~10g·sec./cc. Although the reaction time of the above-mentioned W/F in the case of a gas-phase flow-through reaction is specified, in the case of a batch reaction, the contact time can also be set appropriately. In addition, the aforementioned contact time means the time during which the substrate and the catalyst are in contact.
本揭示之使鹵化丁炔化合物與鹵化氫反應之反應壓力，基於更有效率地進行鹵化氫之加成反應之觀點，較佳為-0.05MPa~2MPa，更佳為-0.01MPa~1MPa，通常又更佳為常壓~0.5MPa。又，本揭示中，關於壓力無特別表明之情況為錶壓。The reaction pressure for the reaction of the halogenated butyne compound and hydrogen halide in the present disclosure is based on the viewpoint that the addition reaction of hydrogen halide is carried out more efficiently, preferably -0.05MPa~2MPa, more preferably -0.01MPa~1MPa, usually More preferably, it is atmospheric pressure ~ 0.5MPa. In addition, in this disclosure, the case where the pressure is not specifically stated is the gauge pressure.
本揭示之使鹵化丁炔化合物與鹵化氫之反應中，作為投入鹵化丁炔化合物及觸媒並使之反應的反應器，若為可耐受上述溫度及壓力者，則形狀及構造未特別限定。作為反應器舉例為例如縱型反應器、橫型反應器、多管型反應器等。作為反應器之材質舉例為例如玻璃、不鏽鋼、鐵、鎳、鐵鎳合金等。In the reaction of the halogenated butyne compound and the hydrogen halide in the present disclosure, the shape and structure of the reactor in which the halogenated butyne compound and the catalyst are charged and reacted are not particularly limited as long as they can withstand the above-mentioned temperature and pressure. . Examples of the reactor include, for example, a vertical reactor, a horizontal reactor, and a multi-tube reactor. As the material of the reactor, for example, glass, stainless steel, iron, nickel, iron-nickel alloy, etc.
本揭示之使鹵化丁炔化合物與鹵化氫之反應(鹵化氫之加成反應)亦可藉由於反應器中連續饋入基質，自該反應器連續抽出目的化合物之流通式及批示之任一方式實施。目的化合物積存於反應器時，由於可能進而進行脫離反應，故較佳以流通式實施。本揭示之使鹵化丁炔化合物與鹵化氫反應之步驟較佳以氣相進行，特佳以使用固定床反應器之氣相連續流通式進行。以氣相連續流通式進行之情況，可簡略裝置、操作等，就經濟上有利。The reaction of the halogenated butyne compound and hydrogen halide (addition reaction of hydrogen halide) of the present disclosure can also be achieved by either the flow-through method or the instruction method of continuously extracting the target compound from the reactor because the substrate is continuously fed into the reactor Implement. When the target compound accumulates in the reactor, since it may further proceed with the separation reaction, it is preferably carried out in a flow-through mode. The step of reacting the halogenated butyne compound with hydrogen halide in the present disclosure is preferably carried out in the gas phase, and particularly preferably carried out in the gas phase continuous flow method using a fixed bed reactor. In the case of continuous flow in the gas phase, the equipment and operation can be simplified, which is economically advantageous.
關於本揭示之進行鹵化丁炔化合物與鹵化氫之反應之際的環境，基於抑制觸媒劣化之觀點，較佳於惰性氣體環境下、氟化氫氣體環境下等。該惰性氣體舉例為氮氣、氦氣、氬氣等。該等惰性氣體中，基於抑制成本之觀點，較佳為氮氣。該惰性氣體之濃度，較佳設為導入反應器之氣體成分之0~50莫耳%。Regarding the environment during the reaction of the halogenated butyne compound and the hydrogen halide in the present disclosure, from the viewpoint of suppressing degradation of the catalyst, it is preferable to be in an inert gas environment, a hydrogen fluoride gas environment, or the like. Examples of the inert gas include nitrogen, helium, and argon. Among these inert gases, nitrogen is preferred from the viewpoint of cost reduction. The concentration of the inert gas is preferably set to 0-50 mol% of the gas composition introduced into the reactor.
如此所得之本揭示之目的化合物係以通式(1)表示之鹵化丁烯化合物。
通式(1)中之X1 、X2 、X3 、X7 、X8 及X9 與上述通式(2)中之X1 、X2 、X3 、X7 、X8 及X9 對應。且通式(1)中，作為X4 所示之鹵素原子舉例為氟原子、氯原子、溴原子及碘原子。因此，欲製造之通式(1)表示之鹵化丁烯化合物具體舉例為例如CF3 CF=CHCF3 、CCl3 CCl=CHCCl3 、CBr3 CBr=CHCBr3 等。Formula X (1) in the 1, X 2, X 3, X 7, X 8 and X 9 in the general formula (2) in the X 1, X 2, X 3 , X 7, X 8 and X 9 correspond. In the general formula (1), examples of the halogen atom represented by X 4 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Therefore, specific examples of the halogenated butene compound represented by the general formula (1) to be produced are, for example, CF 3 CF=CHCF 3 , CCl 3 CCl=CHCCl 3 , CBr 3 CBr=CHCBr 3 and the like.
鹵化丁炔化合物與鹵化氫之反應(鹵化氫之加成反應)結束後，根據需要，可依據常用方法進行純化處理，獲得目的化合物之鹵化丁烯化合物。又，依據本揭示之製造方法，如上述抑制對於鹵化丁炔化合物1莫耳加成2莫耳鹵化氫，可選擇性獲得對於鹵化丁炔化合物1莫耳加成1莫耳鹵化氫之鹵化丁烯化合物。After the reaction of the halogenated butyne compound and hydrogen halide (addition reaction of hydrogen halide) is completed, purification treatment can be carried out according to common methods as needed to obtain the halogenated butene compound of the target compound. Furthermore, according to the manufacturing method of the present disclosure, as described above, the addition of 2 moles of hydrogen halide to 1 mole of halogenated butyne compound can be suppressed, and it is possible to selectively obtain butylene halide that has 1 mole of addition of 1 mole of hydrogen halide to halogenated butyne compound. Olefin compounds.
如此所得之鹵化丁烯化合物可有效利用於用以形成半導體、液晶等之最先端之微細構造之蝕刻氣體等之各種用途。The halogenated butene compound obtained in this way can be effectively used in various applications such as etching gas for forming the most advanced fine structures of semiconductors and liquid crystals.
2.鹵化丁烯組成物 如上述，雖可獲得鹵化丁烯化合物，但有時亦以含有對於鹵化丁炔化合物1莫耳加成1莫耳鹵化氫之鹵化丁烯化合物與對於鹵化丁炔化合物1莫耳加成2莫耳鹵化氫之鹵化丁烷化合物之鹵化丁烯組成物之形態。2. Halogenated butene composition As mentioned above, although halogenated butene compounds can be obtained, sometimes the halogenated butene compound containing 1 mol addition to 1 mol hydrogen halide to the halogenated butyne compound and 1 mol addition to the halogenated butyne compound 2 mol The form of halogenated butene composition of halogenated butane compound of ear hydrogen halide.
該本揭示之鹵化丁烯組成物中，鹵化丁烯化合物係以上述通式(1)表示之鹵化丁烯化合物，鹵化丁烷化合物係以上述通式(3)表示之鹵化丁烷化合物。In the halogenated butene composition of the present disclosure, 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).
通式(1)及(3)中，作為以X1 、X2 、X3 、X4 、X5 、X6 、X7 、X8 及X9 表示之鹵原子舉例為氟原子、氯原子、溴原子及碘原子，較佳為氟原子。In the general formulas (1) and (3), examples of halogen atoms represented by X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 , X 8 and X 9 are fluorine atom and chlorine atom , Bromine atom and iodine atom, preferably fluorine atom.
將該本揭示之鹵化丁烯組成物總量設為100莫耳%，以通式(1)表示之鹵化丁烯化合物之含量較佳為91.00~99.99莫耳%，更佳為92.00~ 99.98莫耳%。又以通式(3)表示之鹵化丁烷化合物之含量較佳為0.01~9.00莫耳%，更佳為0.02~8.00莫耳%。The total amount of the halogenated butene composition of the present disclosure is set to 100 mol%, and the content of the halogenated butene compound represented by the general formula (1) is preferably 91.00-99.99 mol%, more preferably 92.00~99.98 mol% ear%. The content of the halogenated butane compound represented by the general formula (3) is preferably 0.01-9.00 mol%, more preferably 0.02-8.00 mol%.
又，依據本揭示之製造方法，可作為鹵化丁烯組成物之情況下，由於如上述以通式(1)表示之鹵化丁烯化合物能以提高反應轉化率、且以高收率且高選擇率獲得，故鹵化丁烯組成物中之以通式(1)表示之鹵化丁烯化合物以外之成分可減少，故可削減用以獲得以通式(1)表示之鹵化丁烯化合物之純化勞力。In addition, according to the manufacturing method of the present disclosure, when it can be used as a halogenated butene composition, the halogenated butene compound represented by the general formula (1) can improve the reaction conversion rate, and with high yield and high selection Therefore, the components other than the halogenated butene compound represented by the general formula (1) in the halogenated butene composition can be reduced, so the purification labor for obtaining the halogenated butene compound represented by the general formula (1) can be reduced .
如此之本揭示之鹵化丁烯組成物除了可有效利用於用以形成半導體、液晶等之最先端之微細構造之蝕刻氣體以外，亦可有效利用於有機合成用建構組元等之各種用途。又，所謂有機合成用建構組元意指可成為具有反應性高的骨架之化合物的前驅物的物質。例如本揭示之鹵化丁烯組成物與CF3 Si(CH3 )3 等之含矽有機矽化合物反應時，導入CF3 基等之氟烷基並轉變為能成為洗淨劑或含氟醫藥中間物之物質。The halogenated butene composition of the present disclosure can be effectively used in addition to the etching gas used to form the most advanced microstructures of semiconductors and liquid crystals, and can also be effectively used for various purposes such as building elements for organic synthesis. In addition, the building block for organic synthesis means a substance that can be a precursor of a compound having a highly reactive skeleton. For example, when the halogenated butene composition of the present disclosure reacts with silicon-containing organosilicon compounds such as CF 3 Si(CH 3 ) 3 , fluoroalkyl groups such as CF 3 groups are introduced and converted into detergents or fluorine-containing medicines. The matter of things.
以上，說明本揭示之實施形態，但在不脫離申請專利範圍之主旨及範圍內，形態或細節可能有多種變更。 [實施例]The above describes the implementation of the present disclosure, but there may be various changes in the form or details without departing from the spirit and scope of the patent application. [Example]
以下顯示實施例，而明確出本揭示之特徵。本揭示並非限定於該等實施例。Examples are shown below to clarify the characteristics of the present disclosure. The present disclosure is not limited to these embodiments.
實施例1~6及比較例1~2之鹵化丁烯化合物之製造方法中，原料化合物係以通式(2)表示之鹵化丁炔化合物中，X1
、X2
、X3
、X7
、X8
及X9
為氟原子，鹵化氫為氟化氫，依據下述反應式：
實施例1~4：使用活性碳觸媒之氟化氫加成反應 於反應管的SUS配管(外徑：1/2吋)添加10g作為觸媒之活性碳觸媒(大阪氣體化學(股)製：比表面積1200m2 /g)。於氮氣環境下，於200℃乾燥2小時後，以使壓力為常壓，CF3 C≡CCF3 (基質)及氟化氫與活性碳觸媒之接觸時間(W/F)成為2g・sec/cc之方式，於反應管中流通CF3 C≡CCF3 (基質)及氟化氫氣體。Examples 1~4: Hydrogen fluoride addition reaction using activated carbon catalyst. The SUS pipe (outer diameter: 1/2 inch) of the reaction tube was added with 10g of activated carbon catalyst (Osaka Gas Chemical Co., Ltd.) as a catalyst. The specific surface area is 1200m 2 /g). After drying for 2 hours at 200°C in a nitrogen atmosphere, the contact time (W/F) between CF 3 C≡CCF 3 (substrate) and hydrogen fluoride and activated carbon catalyst becomes 2g·sec/cc under normal pressure. In this way, CF 3 C≡CCF 3 (matrix) and hydrogen fluoride gas are circulated in the reaction tube.
反應係以氣相連續流通式進行。The reaction system is carried out in a continuous flow through gas phase.
反應管於200℃、250℃、300℃或400℃加熱，開始氟化氫加成反應。The reaction tube is heated at 200°C, 250°C, 300°C or 400°C to start the hydrogen fluoride addition reaction.
以與CF3 C≡CCF3 (基質)接觸之氟化氫氣體之莫耳比(HF/CF3 C≡CCF3 比)為150，接觸時間(W/F)為 2g・sec/cc之方式，調整基質與氟化氫氣體之流量，反應開始1小時後收集通過除害塔之餾出分。Adjust the molar ratio (HF/CF 3 C≡CCF 3 ratio) of the hydrogen fluoride gas in contact with CF 3 C≡CCF 3 (substrate) to 150 and the contact time (W/F) to 2g·sec/cc. The flow rate of substrate and hydrogen fluoride gas, collect the distillate that passed through the detoxification tower 1 hour after the reaction started.
隨後，使用氣相層析儀(島津製作所(股)製，商品名「GC-2014」)藉由氣體層析/質量分析法(GC/MS)進行質量分析，使用NMR (JEOL公司製，商品名「400YH」)進行NMR光譜之構造解析。Subsequently, mass analysis was carried out by gas chromatography/mass analysis (GC/MS) using a gas chromatograph (manufactured by Shimadzu Corporation, trade name "GC-2014"), and NMR (manufactured by JEOL Co., product Name "400YH") for structural analysis of NMR spectrum.
由質量分析及構造解析之結果，確認生成作為目的化合物之CF3 CF=CHCF3 。實施例1中，自CF3 C≡CCF3 (基質)之轉化率為99.75莫耳%，CF3 CF=CHCF3 (目的化合物)之選擇率為99.85莫耳%，CF3 CF2 CH2 CF3 之選擇率為0.11莫耳%，CF3 CFHCFHCF3 之選擇率為0.01莫耳%。實施例2中，自CF3 C≡CCF3 (基質)之轉化率為100.00莫耳%，CF3 CF=CHCF3 (目的化合物)之選擇率為99.36莫耳%，CF3 CF2 CH2 CF3 之選擇率為0.34莫耳%，CF3 CFHCFHCF3 之選擇率為0.26莫耳%。實施例3中，自CF3 C≡CCF3 (基質)之轉化率為100.00莫耳%，CF3 CF=CHCF3 (目的化合物)之選擇率為98.45莫耳%，CF3 CF2 CH2 CF3 之選擇率為0.98莫耳%，CF3 CFHCFHCF3 之選擇率為0.10莫耳%。實施例4中，自CF3 C≡CCF3 (基質)之轉化率為100.00莫耳%，CF3 CF=CHCF3 (目的化合物)之選擇率為99.15莫耳%，CF3 CF2 CH2 CF3 之選擇率為0.80莫耳%，CF3 CFHCFHCF3 之選擇率為0.02莫耳%。From the results of mass analysis and structural analysis, it was confirmed that CF 3 CF=CHCF 3 was produced as the target compound. In Example 1, the conversion rate from CF 3 C≡CCF 3 (matrix) was 99.75 mol%, the selectivity of CF 3 CF=CHCF 3 (target compound) was 99.85 mol%, and CF 3 CF 2 CH 2 CF The selectivity for 3 is 0.11 mol%, and the selectivity for CF 3 CFHCFHCF 3 is 0.01 mol%. In Example 2, the conversion rate from CF 3 C≡CCF 3 (matrix) was 100.00 mol%, the selectivity of CF 3 CF=CHCF 3 (target compound) was 99.36 mol%, and CF 3 CF 2 CH 2 CF The selectivity for 3 is 0.34 mol%, and the selectivity for CF 3 CFHCFHCF 3 is 0.26 mol%. In Example 3, the conversion rate from CF 3 C≡CCF 3 (matrix) is 100.00 mol%, the selectivity of CF 3 CF=CHCF 3 (target compound) is 98.45 mol%, CF 3 CF 2 CH 2 CF The selectivity for 3 is 0.98 mol%, and the selectivity for CF 3 CFHCFHCF 3 is 0.10 mol%. In Example 4, the conversion rate from CF 3 C≡CCF 3 (matrix) was 100.00 mol%, the selectivity of CF 3 CF=CHCF 3 (target compound) was 99.15 mol%, and CF 3 CF 2 CH 2 CF The selectivity for 3 is 0.80 mol%, and the selectivity for CF 3 CFHCFHCF 3 is 0.02 mol%.
實施例5~6：使用氧化鉻觸媒之氟化氫加成反應 除了使用氧化鉻觸媒(Cr2 O3 )作為觸媒，以反應溫度為350℃，CF3 C≡CCF3 (基質)及氟化氫氣體之與氧化鉻觸媒之接觸時間(W/F)成為4g・sec/cc或5g・sec/cc之方式，調整CF3 C≡CCF3 (基質)及氟化氫氣體之合計流量，將與CF3 C≡CCF3 (基質)接觸之氟化氫氣體之莫耳比(HF/CF3 C≡CCF3 比)設為50或200以外，與實施例1~4同樣進行反應。Examples 5~6: Addition reaction of hydrogen fluoride using chromium oxide catalyst In addition to using chromium oxide catalyst (Cr 2 O 3 ) as the catalyst, the reaction temperature is 350 ℃, CF 3 C≡CCF 3 (substrate) and hydrogen fluoride The contact time (W/F) between the gas and the chromium oxide catalyst becomes 4g·sec/cc or 5g·sec/cc. Adjust the total flow rate of CF 3 C≡CCF 3 (substrate) and hydrogen fluoride gas. The molar ratio (HF/CF 3 C≡CCF 3 ratio) of the hydrogen fluoride gas contacted by 3 C≡CCF 3 (substrate) was set to other than 50 or 200, and the reaction was carried out in the same manner as in Examples 1 to 4.
由質量分析及構造解析之結果，確認生成作為目的化合物之CF3 CF=CHCF3 。實施例5中，自CF3 C≡CCF3 (基質)之轉化率為97.59莫耳%，CF3 CF=CHCF3 (目的化合物)之選擇率為99.98莫耳%，CF3 CF2 CH2 CF3 之選擇率為0.01莫耳%，CF3 CFHCFHCF3 之選擇率為0.00莫耳%。實施例6中，自CF3 C≡CCF3 (基質)之轉化率為80.90莫耳%，CF3 CF=CHCF3 (目的化合物)之選擇率為99.96莫耳%，CF3 CF2 CH2 CF3 之選擇率為0.03莫耳%，CF3 CFHCFHCF3 之選擇率為0.00莫耳%。From the results of mass analysis and structural analysis, it was confirmed that CF 3 CF=CHCF 3 was produced as the target compound. In Example 5, the conversion rate from CF 3 C≡CCF 3 (matrix) was 97.59 mol%, the selectivity of CF 3 CF=CHCF 3 (target compound) was 99.98 mol%, and CF 3 CF 2 CH 2 CF The selectivity for 3 is 0.01 mol%, and the selectivity for CF 3 CFHCFHCF 3 is 0.00 mol%. In Example 6, the conversion rate from CF 3 C≡CCF 3 (matrix) was 80.90 mol%, the selectivity of CF 3 CF=CHCF 3 (target compound) was 99.96 mol%, and CF 3 CF 2 CH 2 CF The selectivity for 3 is 0.03 mol%, and the selectivity for CF 3 CFHCFHCF 3 is 0.00 mol%.
比較例1~2：未使用觸媒之氟化氫加成反應 除了未使用觸媒，以反應溫度為200℃或350℃，CF3 C≡CCF3 (基質)及氟化氫氣體之與觸媒之接觸時間(W/F)設為20g・sec/cc，與CF3 C≡CCF3 (基質)接觸之氟化氫氣體之莫耳比(HF/CF3 C≡CCF3 比)設為200以外，與實施例1~4同樣進行反應。又，比較例1~2中，所謂W/F設為20g・sec/cc意指與使用觸媒之實施例1~6中將W/F設為20g・sec/cc之情況相同的流量流通CF3 C≡CCF3 (基質)。Comparative example 1~2: Hydrogen fluoride addition reaction without using a catalyst, except that no catalyst is used, the reaction temperature is 200℃ or 350℃, the contact time of CF 3 C≡CCF 3 (substrate) and hydrogen fluoride gas with the catalyst (W/F) is set to 20g·sec/cc, and the molar ratio of hydrogen fluoride gas in contact with CF 3 C≡CCF 3 (substrate) (HF/CF 3 C≡CCF 3 ratio) is set to other than 200. 1~4 react in the same way. In addition, in Comparative Examples 1 and 2, the so-called W/F set to 20g·sec/cc means the same flow rate as the case where W/F is set to 20g·sec/cc in Examples 1 to 6 using a catalyst. CF 3 C≡CCF 3 (matrix).
由質量分析及構造解析之結果，確認生成作為目的化合物之CF3 CF=CHCF3 。比較例1中，儘管CF3 C≡CCF3 (基質)之流量與實施例1~6比較顯著較多，但自CF3 C≡CCF3 (基質)之轉化率為1.92莫耳%，CF3 CF=CHCF3 (目的化合物)之選擇率為90.83莫耳%，CF3 CF2 CH2 CF3 之選擇率為8.27莫耳%，CF3 CFHCFHCF3 之選擇率為0.82莫耳%。比較例2中，儘管CF3 C≡CCF3 (基質)之流量與實施例1~6比較顯著較多，但自CF3 C≡CCF3 (基質)之轉化率為2.17莫耳%，CF3 CF=CHCF3 (目的化合物)之選擇率為85.52莫耳%，CF3 CF2 CH2 CF3 之選擇率為7.83莫耳%，CF3 CFHCFHCF3 之選擇率為0.62莫耳%。因此，自CF3 C≡CCF3 (基質)之轉化率顯著較低，且產生相當程度之雜質的CF3 CF2 CH2 CF3 ，目的化合物的CF3 CF=CHCF3 之選擇率亦低。From the results of mass analysis and structural analysis, it was confirmed that CF 3 CF=CHCF 3 was produced as the target compound. In Comparative Example 1, although CF 3 C≡CCF 3 (matrix) of the flow rate of Comparative Examples 1 to 6 are more significant, but since CF 3 C≡CCF 3 (matrix) of conversion was 1.92 mole%, CF 3 The selectivity of CF=CHCF 3 (target compound) is 90.83 mol%, the selectivity of CF 3 CF 2 CH 2 CF 3 is 8.27 mol%, and the selectivity of CF 3 CFHCFHCF 3 is 0.82 mol%. In Comparative Example 2, although CF 3 C≡CCF 3 (matrix) of the flow rate of Comparative Examples 1 to 6 are more significant, but since (matrix) of conversion was 2.17 mole% CF 3 C≡CCF 3, CF 3 The selectivity of CF=CHCF 3 (target compound) is 85.52 mol%, the selectivity of CF 3 CF 2 CH 2 CF 3 is 7.83 mol%, and the selectivity of CF 3 CFHCFHCF 3 is 0.62 mol%. Therefore, the conversion rate from CF 3 C≡CCF 3 (matrix) is significantly lower, and CF 3 CF 2 CH 2 CF 3 is produced to a considerable degree of impurities, and the selectivity of CF 3 CF=CHCF 3 of the target compound is also low.
結果示於表1。The results are shown in Table 1.
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