WO2020137825A1 - シクロブテンの製造方法 - Google Patents
シクロブテンの製造方法 Download PDFInfo
- Publication number
- WO2020137825A1 WO2020137825A1 PCT/JP2019/049900 JP2019049900W WO2020137825A1 WO 2020137825 A1 WO2020137825 A1 WO 2020137825A1 JP 2019049900 W JP2019049900 W JP 2019049900W WO 2020137825 A1 WO2020137825 A1 WO 2020137825A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- halogen atom
- reaction
- mol
- general formula
- cyclobutene
- Prior art date
Links
- CFBGXYDUODCMNS-UHFFFAOYSA-N cyclobutene Chemical compound C1CC=C1 CFBGXYDUODCMNS-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 125000005843 halogen group Chemical group 0.000 claims abstract description 72
- 239000007789 gas Substances 0.000 claims abstract description 35
- 238000003379 elimination reaction Methods 0.000 claims abstract description 29
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 25
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims description 25
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 19
- 238000005530 etching Methods 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000006704 dehydrohalogenation reaction Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 description 52
- 239000003054 catalyst Substances 0.000 description 50
- 238000006243 chemical reaction Methods 0.000 description 43
- 239000002994 raw material Substances 0.000 description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 24
- 229910052731 fluorine Inorganic materials 0.000 description 22
- 125000001153 fluoro group Chemical group F* 0.000 description 21
- 229910000423 chromium oxide Inorganic materials 0.000 description 16
- 238000005796 dehydrofluorination reaction Methods 0.000 description 15
- 239000012071 phase Substances 0.000 description 15
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 13
- 238000003795 desorption Methods 0.000 description 12
- 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 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 238000003682 fluorination reaction Methods 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- 238000004949 mass spectrometry Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000012916 structural analysis Methods 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910021563 chromium fluoride Inorganic materials 0.000 description 4
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- FTBATIJJKIIOTP-UHFFFAOYSA-K trifluorochromium Chemical compound F[Cr](F)F FTBATIJJKIIOTP-UHFFFAOYSA-K 0.000 description 4
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 3
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- -1 crushed coal Chemical compound 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 2
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- DXSOBOFFMLHPRJ-UHFFFAOYSA-L [Ni](F)(F)=O Chemical compound [Ni](F)(F)=O DXSOBOFFMLHPRJ-UHFFFAOYSA-L 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000001047 cyclobutenyl group Chemical group C1(=CCC1)* 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite 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
- 239000002440 industrial waste Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- MDKPDHUQPDWHHD-UHFFFAOYSA-M iron(3+);oxygen(2-);fluoride Chemical compound [O-2].[F-].[Fe+3] MDKPDHUQPDWHHD-UHFFFAOYSA-M 0.000 description 1
- SHXXPRJOPFJRHA-UHFFFAOYSA-K iron(iii) fluoride Chemical compound F[Fe](F)F SHXXPRJOPFJRHA-UHFFFAOYSA-K 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
- C07C17/357—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction by dehydrogenation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C23/00—Compounds containing at least one halogen atom bound to a ring other than a six-membered aromatic ring
- C07C23/02—Monocyclic halogenated hydrocarbons
- C07C23/06—Monocyclic halogenated hydrocarbons with a four-membered ring
-
- 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
Definitions
- the present disclosure relates to a method for producing cyclobutene.
- Cyclobutene containing a halogen atom is a compound useful as a dry etching gas for semiconductors, various refrigerants, foaming agents, heat transfer media, and the like.
- 1H-pentafluorocyclobutene is known to be a method for producing 1H-pentafluorocyclobutene from 1H,2H-hexafluorocyclobutane by dehydrofluorination reaction (for example, Non-Patent Documents 1 and 2).
- This technology synthesizes 1H-pentafluorocyclobutene in an open reaction system using glassware.
- the present disclosure aims to produce cyclobutene containing a halogen atom with high selectivity.
- the present disclosure includes the following configurations.
- X 1 , X 2 , X 3 , X 4 and Y are the same as above.
- X 5 and X 6 are the same or different and each represents a hydrogen atom, a halogen atom or a perfluoroalkyl group. .) Including a step of removing cyclobutane represented by A manufacturing method, wherein the step of performing the elimination reaction is performed in a gas phase.
- Item 2 The production method according to Item 1, wherein X 5 is a hydrogen atom, X 6 is a halogen atom, and the elimination reaction is a dehydrohalogenation reaction.
- Item 4 The content of 1H-perfluorocyclobutene (1H-cC 4 F 5 H) is 99 mol% or more, the content of 3H-perfluorocyclobutene (3H-cC 4 F 5 H) is 1 mol% or less, Item 4.
- Item 5. The composition according to Item 3 or 4, which is used as a cleaning gas, an etching gas, a deposit gas, or a building block for organic synthesis.
- cyclobutene containing a halogen atom can be produced with high selectivity.
- the inventors of the present invention performed a step of eliminating a raw material compound in a gas phase to obtain cyclobutene containing a halogen atom represented by the general formula (1) with high selectivity. It was found that it can be manufactured.
- the present disclosure includes the following embodiments.
- X 1 , X 2 , X 3 , X 4 and Y are the same as above.
- X 5 and X 6 are the same or different and each represents a hydrogen atom, a halogen atom or a perfluoroalkyl group. .
- the step of performing the elimination reaction is performed in the gas phase.
- cyclobutene containing a halogen atom can be produced with high selectivity.
- the “selectivity” refers to the target compound (halogen atom is included in the effluent gas with respect to the total molar amount of compounds other than the raw material compound (cyclobutene containing a halogen atom) in the effluent gas from the reactor outlet. (Including cyclobutene) means the ratio (mol %) of the total molar amount.
- the “conversion rate” means a compound other than the raw material compound (halogen atom is included in the outflow gas from the reactor outlet, with respect to the molar amount of the raw material compound (cyclobutane containing a halogen atom) supplied to the reactor. (Including cyclobutene, etc.) means the ratio (mol%) of the total molar amount.
- the method for producing cyclobutene according to the present disclosure has a merit that it is not a batch reaction but a gas phase reaction of a distribution system, and therefore a solvent is not required and industrial waste does not occur.
- Raw material compound In the present disclosure, the raw material compound is represented by the general formula (2):
- X 1 , X 2 , X 3 , X 4 , X 5 and X 6 are the same or different and represent a hydrogen atom, a halogen atom or a perfluoroalkyl group.
- Y represents a halogen atom.
- X 1 , X 2 , X 3 , X 4 , X 5 and X 6 are the same or different and each represents a hydrogen atom, a halogen atom or a perfluoroalkyl group.
- Y represents a halogen atom
- Examples of the halogen atom of X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and Y include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
- the perfluoroalkyl group of X 1 , X 2 , X 3 , X 4 , X 5 and X 6 is an alkyl group in which all hydrogen atoms are replaced by fluorine atoms.
- the perfluoroalkyl group is, for example, a perfluoroalkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 4 carbon atoms, particularly preferably 1 to 3 carbon atoms. It is preferably a fluoroalkyl group.
- the perfluoroalkyl group is preferably a linear or branched perfluoroalkyl group.
- the perfluoroalkyl group is preferably a trifluoromethyl group (CF 3 -) and a pentafluoroethyl group (C 2 F 5 -).
- cyclobutane containing a halogen atom represented by the general formula (2) which is a raw material compound
- X 1 , X 2 , X 3 and X 4 are the same or different and each independently represent a hydrogen atom, a halogen atom or a perfluoroalkyl group
- X 5 is a hydrogen atom
- X 6 is a fluorine atom
- Y is more preferably a fluorine atom.
- cyclobutane represented by the general formula (2) which is a raw material compound, include:
- the cyclobutane represented by the general formula (2) can be used alone or in combination of two or more kinds. As such cyclobutane, a commercially available product can be adopted.
- X 1 , X 2 , X 3 , X 4 and X 6 are, in that cyclobutene containing a halogen atom can be produced with high selectivity. More preferably, it is a fluorine atom, X 5 is a hydrogen atom, and Y is a fluorine atom.
- the elimination reaction is performed in a gas phase.
- the step of the desorption reaction in the present disclosure is preferably carried out in a gas phase, particularly preferably in a gas phase continuous flow system using a fixed bed reactor.
- the apparatus, operation, etc. can be simplified, and it is economically advantageous.
- X 5 is a hydrogen atom
- X 6 is a halogen atom
- the elimination reaction is a dehydrohalogenation reaction.
- X 5 is a hydrogen atom
- X 6 is a fluorine atom
- the elimination reaction is a dehydrofluorination reaction.
- X 1 , X 2 , X 3 , X 4 and X 6 are fluorine atoms and X 5 is a hydrogen atom.
- Y is preferably a fluorine atom.
- the elimination reaction is preferably a dehydrofluorination reaction.
- Catalyst In the step of the elimination reaction in the present disclosure, it is preferable to perform the elimination reaction in the gas phase in the presence of a catalyst.
- the catalyst used in this step is preferably activated carbon.
- the catalyst used in this step is preferably a metal catalyst.
- a metal catalyst chromium oxide, chromium fluoride oxide, chromium fluoride, aluminum oxide, aluminum fluoride oxide, aluminum fluoride, iron oxide, iron oxide fluoride, iron fluoride, nickel oxide, nickel fluoride oxide, fluoride It is preferably at least one selected from the group consisting of nickel, magnesium oxide, magnesium fluoride oxide and magnesium fluoride.
- activated carbon, chromium oxide, chromium fluoride oxide, aluminum oxide, and aluminum fluoride oxide are more preferable because the target compound can be obtained with higher selectivity. It is also possible to further improve the conversion rate of the raw material compound.
- the catalyst may be in powder form, but pellet form is preferable for gas phase continuous flow reaction.
- the specific surface area of the catalyst measured by the BET method (hereinafter, also referred to as BET specific surface area) is usually 10 to 3,000 m 2 /g, preferably 10 to 400 m 2 /g, and more preferably 20 to 375 m. 2 /g, more preferably 30 to 350 m 2 /g.
- BET specific surface area of the catalyst is in such a range, the density of the catalyst particles is not too small, and thus the target compound can be obtained with high selectivity. It is also possible to improve the conversion rate of the raw material compound.
- powdered activated carbon such as crushed coal, shaped coal, granulated coal, spherical charcoal.
- powdered activated carbon it is preferable to use powdered activated carbon having a particle size of 4 mesh (4.76 mm) to 100 mesh (0.149 mm) in the JIS test.
- a metal catalyst When a metal catalyst is used as the catalyst, it is preferably supported on a carrier.
- the carrier include carbon, alumina (Al 2 O 3 ), zirconia (ZrO 2 ), silica (SiO 2 ), titania (TiO 2 ), and the like.
- carbon activated carbon, amorphous carbon, graphite, diamond or the like can be used.
- Chromium oxide and fluorinated chromium oxide will be described as an example of the catalyst in the present disclosure.
- chromium oxide for example, when chromium oxide is represented by Cr 2 O 3 .nH 2 O, the value of n is preferably 3 or less, more preferably 1 to 1.5.
- the chromium oxide is preferably one in which m is usually in the range of 1.5 ⁇ m ⁇ 3.
- fluorinated chromium oxide can be prepared by fluorinating chromium oxide. Examples of the fluorination include fluorination with hydrogen fluoride (HF) and fluorination with fluorocarbon and the like.
- Fluorinated chromium oxide as a catalyst can be obtained, for example, according to the method described in Japanese Patent No. 3412165.
- a fluorinated chromium oxide can be obtained by fluorinating chromium oxide with hydrogen fluoride (HF treatment).
- the fluorination temperature is preferably 100 to 460° C., for example.
- the pressure for fluorination is preferably the pressure at which it is subjected to a catalytic reaction.
- the highly fluorinated-chromium oxide catalyst can be obtained by fluorinating chromium oxide at a higher temperature than usual for a long time.
- the highly fluorinated-chromium oxide catalyst preferably has a fluorine content of 30% by mass or more, more preferably 30 to 45% by mass.
- the fluorine content can be measured by a mass change of the catalyst or a general quantitative analysis method of chromium oxide.
- the lower limit of the reaction temperature is such that the elimination reaction proceeds more efficiently and the target compound can be obtained with higher selectivity, and the conversion rate decreases. From the viewpoint of suppressing the above, it is usually 50° C., preferably 200° C., more preferably 250° C., further preferably 300° C., particularly preferably 350° C.
- the upper limit of the reaction temperature in the elimination reaction is selected from the viewpoint that the dehydrofluorination reaction can proceed more efficiently and the target compound can be obtained with higher selectivity, and that the reaction product decomposes or polymerizes. From the viewpoint of suppressing the decrease in the rate, it is usually 500° C., preferably 450° C., and more preferably 400° C.
- the reaction time of the desorption reaction is defined as the contact time of the starting compound with the catalyst (W/F 0 )[W: weight of metal catalyst (g), F 0 : flow rate of starting compound (cc/sec)] If the length is increased, the conversion rate of the raw material compound can be increased, but the amount of the catalyst is increased and the equipment becomes large, which is inefficient.
- the reaction time of the dehydrofluorination reaction is 5 g ⁇ sec for the contact time (W/F 0 ) of the raw material compound with the catalyst from the viewpoint of improving the conversion rate of the raw material compound and suppressing the equipment cost.
- /Cc to 300 g ⁇ sec/cc is preferable, 10 g ⁇ sec/cc to 200 g ⁇ sec/cc is more preferable, 15 g ⁇ sec/cc to 150 g ⁇ sec/cc is further preferable, It is particularly preferable that it is 20 g ⁇ sec/cc to 100 g ⁇ sec/cc.
- the contact time of the raw material compound with the catalyst means the time of contact between the raw material compound and the catalyst.
- the reaction temperature and the reaction time are appropriately adjusted particularly according to the catalyst, so that the target compound can be obtained with higher selectivity. Obtainable.
- the reaction temperature is preferably 300°C or higher, more preferably 350°C or higher.
- the contact time is preferably 10 g ⁇ sec/cc or more, more preferably 20 g ⁇ sec/cc or more, and further preferably 40 g ⁇ sec/cc or more.
- the reaction temperature is preferably 300°C or higher, and the contact time is preferably 5 g ⁇ sec/cc or higher.
- the reaction temperature is preferably 300°C or higher, more preferably 350°C or higher, and further preferably 400°C or higher.
- the contact time is preferably 5 g ⁇ sec/cc to 55 g ⁇ sec/cc, more preferably 5 g ⁇ sec/cc to 50 g ⁇ sec/cc, and more preferably 5 g ⁇ sec/cc to 40 g ⁇ sec/ More preferably cc.
- the reaction pressure of the desorption reaction is preferably -0.05MPa to 2MPa, more preferably -0.01MPa to 1MPa, from the viewpoint of promoting the desorption reaction more efficiently, and at atmospheric pressure. More preferably, the pressure is up to 0.5 MPa. Note that in the present disclosure, the pressure is a gauge pressure unless otherwise noted.
- the reactor for contacting the raw material compound and the catalyst (metal catalyst etc.) to react with each other is not particularly limited in shape and structure as long as it can withstand the above temperature and pressure.
- the reactor include a vertical reactor, a horizontal reactor, a multitubular reactor and the like.
- the material of the reactor include glass, stainless steel, iron, nickel, iron-nickel alloy and the like.
- the desorption reaction can be carried out by any of a flow system and a batch system in which a starting compound is continuously charged into a reactor and the target compound is continuously withdrawn from the reactor. If the target compound remains in the reactor, the elimination reaction can proceed further, so that it is preferably carried out in a flow system.
- the step of the desorption reaction in the present disclosure is preferably carried out in a gas phase, particularly preferably in a gas phase continuous flow system using a fixed bed reactor. When the gas phase continuous flow system is used, the apparatus, operation, etc. can be simplified, and it is economically advantageous.
- the atmosphere during the desorption reaction is preferably in the presence of an inert gas and/or hydrogen fluoride from the viewpoint of suppressing the deterioration of the catalyst (metal catalyst etc.).
- the inert gas is preferably at least one selected from the group consisting of nitrogen, helium, argon and carbon dioxide. Among these inert gases, nitrogen is more 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.
- a cyclobutene containing a halogen atom represented by the general formula (1) can be obtained by performing a purification treatment according to a conventional method as needed.
- Target compound The target compound in the present disclosure has the general formula (1):
- X 1 , X 2 , X 3 and X 4 are the same or different and each represents a hydrogen atom, a halogen atom or a perfluoroalkyl group.
- Y represents a halogen atom.
- It is a cyclobutene containing a halogen atom represented by.
- X 1 , X 2 , X 3 and X 4 , and Y are the same as defined above.
- Cyclobutene represented by the general formula (1) to be produced is, for example,
- X 1 , X 2 , X 3 and X 4 are the same or different and each represents a hydrogen atom, a halogen atom, or a perfluoroalkyl group, and Y is It is preferably a fluorine atom.
- X 1 , X 2 , X 3 and X 4 are more preferably a fluorine atom, and Y is more preferably a fluorine atom.
- the starting compound is a cyclobutane containing a halogen atom represented by the general formula (2), X 1 , X 2 , X 3 , X 4 and X 6 are fluorine. Atoms, X 5 is a hydrogen atom, and Y is a fluorine atom, which is preferably an elimination reaction.
- the elimination reaction is preferably a dehydrofluorination reaction.
- X 1 , X 2 , X 3 and X 4 are fluorine atoms, and Y is a fluorine atom.
- a composition containing a cyclobutene containing a halogen atom As described above, a cyclobutene containing a halogen atom represented by the general formula (1) can be obtained. It may be obtained in the form of a composition containing a cyclobutene containing a halogen atom represented by the formula and a cyclobutane containing a halogen atom represented by the general formula (2).
- X 1 , X 2 , X 3 and X 4 are fluorine atoms and Y is a fluorine atom.
- the content of the cyclobutene containing a halogen atom represented by the general formula (1) with the total amount of the composition being 100 mol %. Is preferably 95 mol% or more, and more preferably 99 mol% or more.
- the content of the cyclobutene containing a halogen atom represented by the general formula (1) with the total amount of the composition being 100 mol %. Is preferably 1 mol% to 99.9 mol%, more preferably 5 mol% to 99.9 mol%, still more preferably 10 mol% to 99.9 mol%.
- the following compounds may be produced as impurities in the above elimination reaction.
- the content of 1H-perfluorocyclobutene (1H-cC 4 F 5 H) is defined as 100 mol% of the total amount of the composition.
- the amount is 99 mol% or more, and the content of 3H-perfluorocyclobutene (3H-cC 4 F 5 H) is preferably 1 mol% or less.
- the halogen atom represented by the general formula (1) is contained.
- Cyclobutene can be obtained with a particularly high selectivity, and as a result, it is possible to reduce the components other than cyclobutene containing the halogen atom represented by the general formula (1) in the composition.
- labor for purification for obtaining a cyclobutene containing a halogen atom represented by the general formula (1) can be reduced.
- a composition containing a cyclobutene containing a halogen atom represented by the general formula (1) of the present disclosure has the same composition as a semiconductor, a liquid crystal, etc., as in the case of cyclobutene containing a halogen atom represented by the general formula (1) alone.
- the etching gas for forming the fine structure of the tip it can be effectively used for various purposes such as a deposit gas, a building block for organic synthesis, and a cleaning gas.
- the deposit gas is a gas that deposits the etching resistant polymer layer.
- the building block for organic synthesis means a substance that can be a precursor of a compound having a highly reactive skeleton.
- a fluorine-containing organosilicon compound such as CF 3 Si(CH 3 ) 3 , CF 3
- a fluoroalkyl group such as a group into a substance that can be a detergent or a fluorine-containing pharmaceutical intermediate.
- the starting compound is a cyclobutane containing a halogen atom represented by the general formula (2), X 1 , X 2 , X 3 , X 4 and X 6 are , A fluorine atom, X 5 was a hydrogen atom, and Y was a fluorine atom.
- the desorption reaction was dehydrofluorination reaction.
- the target compound is a cyclobutene containing a halogen atom represented by the general formula (1), wherein X 1 , X 2 , X 3 and X 4 are fluorine atoms, and Y is a fluorine atom.
- the following compounds may be produced as impurities in the above elimination reaction.
- Examples 1 to 3 (chromium oxide catalyst)
- a SUS pipe (outer diameter: 1/2 inch) was used as a reaction tube, and 10 g of chromium oxide containing Cr 2 O 3 as a main component was filled as a catalyst.
- anhydrous hydrogen fluoride was passed through the reactor, and the fluorination treatment was performed by setting the temperature of the reactor to 200°C to 300°C.
- the fluorinated chromium oxide was taken out and used for the dehydrofluorination reaction.
- the BET specific surface area of the fluorinated chromium oxide was 75 m 2 /g.
- the reaction proceeded in the gas phase continuous flow system.
- the reactor was heated at 250°C or 350°C to start the dehydrofluorination reaction.
- mass spectrometry is performed by gas chromatography/mass spectrometry (GC/MS) using gas chromatography (manufactured by Shimadzu Corporation, product name “GC-2014”), and NMR (manufactured by JEOL, product name “400YH”). ]) was used for structural analysis by NMR spectrum.
- GC/MS gas chromatography/mass spectrometry
- Example 1 the conversion rate from cC 4 F 6 H 2 (raw material compound) was 3.34 mol%, and the selectivity (yield) for cC 4 F 5 H (target compound) was 45.9 mol%.
- Example 2 the conversion was 29.1 mol% and the selectivity was 98.6 mol%.
- Example 3 the conversion was 26.1 mol% and the selectivity was 97.2 mol%.
- Examples 4 and 5 (alumina catalyst) Following the experimental method of Example 1, alumina containing Al 2 O 3 as a main component was used as a catalyst. Following the experimental method of Example 1, the contact time (W/F 0 ) between cC 4 F 6 H 2 (raw material compound) and alumina (catalyst) should be 10 g ⁇ sec/cc or 40 g ⁇ sec/cc. Then, the raw material compound was passed through the reactor. Following the experimental method of Example 1, the reactor was heated at 400° C. to start the dehydrofluorination reaction. Dehydrofluorination reaction, mass spectrometry and structural analysis were carried out in the same manner as in Example 1 except for the above conditions.
- Example 4 From the results of mass spectrometry and structural analysis, it was confirmed that cC 4 F 5 H was produced as the target compound.
- the conversion from cC 4 F 6 H 2 (raw material compound) was 7.92 mol%, and the selectivity of cC 4 F 5 H (target compound) was 45.1 mol%.
- the conversion rate was 4.11 mol% and the selectivity rate was 35.0 mol%.
- Examples 6 to 10 (activated carbon catalyst) Following the experimental method of Example 1, activated carbon was used as a catalyst. Following the experimental method of Example 1, the contact time (W/F 0 ) between cC 4 F 6 H 2 (raw material compound) and activated carbon (catalyst) was 10 g ⁇ sec/cc, 27 g ⁇ sec/cc or 47 g ⁇ sec. The raw material compound was passed through the reactor so as to be sec/cc. Following the experimental method of Example 1, the reactor was heated at 300° C., 350° C. or 400° C. to start the dehydrofluorination reaction. Dehydrofluorination reaction, mass spectrometry and structural analysis were carried out in the same manner as in Example 1 except for the above conditions.
- Example 6 the conversion from cC 4 F 6 H 2 (raw material compound) was 57.6 mol%, and the selectivity of cC 4 F 5 H (target compound) was 95.3 mol%.
- Example 7 the conversion was 97.7 mol% and the selectivity was 68.3 mol%.
- Example 8 the conversion was 84.1 mol% and the selectivity was 83.8 mol%.
- Example 9 the conversion rate was 72.3 mol% and the selectivity was 94.6 mol%.
- Example 10 the conversion was 84.7 mol% and the selectivity was 95.7 mol%.
- the contact time (W/F 0 ) means at what rate the flowing raw material gas is flown, that is, the time during which the catalyst and the raw material gas are in contact with each other.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Plasma & Fusion (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
SG11202106891PA SG11202106891PA (en) | 2018-12-27 | 2019-12-19 | Method for producing cyclobutene |
CN201980086441.9A CN113227026A (zh) | 2018-12-27 | 2019-12-19 | 环丁烯的制造方法 |
KR1020217023297A KR102566765B1 (ko) | 2018-12-27 | 2019-12-19 | 시클로부텐의 제조 방법 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2018245665A JP6835060B2 (ja) | 2018-12-27 | 2018-12-27 | シクロブテンの製造方法 |
JP2018-245665 | 2018-12-27 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2020137825A1 true WO2020137825A1 (ja) | 2020-07-02 |
Family
ID=71127736
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2019/049900 WO2020137825A1 (ja) | 2018-12-27 | 2019-12-19 | シクロブテンの製造方法 |
Country Status (6)
Country | Link |
---|---|
JP (1) | JP6835060B2 (zh) |
KR (1) | KR102566765B1 (zh) |
CN (1) | CN113227026A (zh) |
SG (1) | SG11202106891PA (zh) |
TW (1) | TWI777113B (zh) |
WO (1) | WO2020137825A1 (zh) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023049515A1 (en) * | 2021-09-27 | 2023-03-30 | Honeywell International Inc. | Fluorine substituted cyclobutene compounds, and compositions, methods and uses including same |
WO2023049513A1 (en) * | 2021-09-27 | 2023-03-30 | Honeywell International Inc. | Fluorine substituted cyclobutene compounds, and compositions, methods and uses including same |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2891968A (en) * | 1955-08-12 | 1959-06-23 | Du Pont | Difluorobutenedioic acids, their alkali metal salts, their alkyl esters and anhydride, and process for preparing them |
GB844604A (en) * | 1955-09-14 | 1960-08-17 | Robert Neville Haszeldine | Halogenated organic compounds |
WO2010007968A1 (ja) * | 2008-07-18 | 2010-01-21 | 日本ゼオン株式会社 | 含水素フルオロオレフィン化合物の製造方法 |
JP2010043034A (ja) * | 2008-08-14 | 2010-02-25 | Nippon Zeon Co Ltd | 含水素フルオロオレフィン化合物の製造方法 |
JP2010126452A (ja) * | 2008-11-25 | 2010-06-10 | Nippon Zeon Co Ltd | 含水素フルオロオレフィン化合物の製造方法 |
CN107721810A (zh) * | 2017-11-07 | 2018-02-23 | 中国民航大学 | 一种合成灭火剂八氟环丁烷的方法 |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07100673B2 (ja) * | 1986-08-19 | 1995-11-01 | 旭化成工業株式会社 | 1−フルオロシクロヘキセンの製造法 |
KR940002713B1 (ko) * | 1991-12-03 | 1994-03-31 | 주식회사 코오롱 | 디아조타입 감광체 원료의 제조방법 |
TWI298716B (zh) * | 2001-08-06 | 2008-07-11 | Showa Denko Kk | |
US7560602B2 (en) * | 2005-11-03 | 2009-07-14 | Honeywell International Inc. | Process for manufacture of fluorinated olefins |
JP5056963B2 (ja) * | 2010-03-31 | 2012-10-24 | ダイキン工業株式会社 | 含フッ素アルカンの製造方法 |
CN102971279B (zh) * | 2010-04-02 | 2015-05-20 | 索尔维公司 | 用于对氢氯氟烷脱氟化氢的方法以及由此获得的产品 |
WO2011140013A1 (en) * | 2010-05-03 | 2011-11-10 | Arkema Inc. | Dehydrofluorination of pentafluoroalkanes to form tetrafluoroolefins |
CN102836722B (zh) * | 2012-09-06 | 2014-10-15 | 西安近代化学研究所 | 一种卤氟烷烃脱卤化氢制备含氟烯烃的催化剂及其制备方法 |
EP3040327B1 (en) * | 2013-08-26 | 2018-02-28 | Asahi Glass Company, Limited | Method for producing fluorinated compound |
CN105107533B (zh) * | 2015-08-18 | 2019-04-09 | 巨化集团技术中心 | 一种气相脱氟化氢催化剂的制备方法 |
CN107739294B (zh) * | 2017-10-17 | 2020-08-21 | 北京宇极科技发展有限公司 | 气相脱氟化氢制备氢氟环戊烯的方法 |
JP7166911B2 (ja) * | 2018-12-25 | 2022-11-08 | ダイキン工業株式会社 | シクロブテンの製造方法 |
-
2018
- 2018-12-27 JP JP2018245665A patent/JP6835060B2/ja active Active
-
2019
- 2019-12-19 CN CN201980086441.9A patent/CN113227026A/zh active Pending
- 2019-12-19 SG SG11202106891PA patent/SG11202106891PA/en unknown
- 2019-12-19 WO PCT/JP2019/049900 patent/WO2020137825A1/ja active Application Filing
- 2019-12-19 KR KR1020217023297A patent/KR102566765B1/ko active IP Right Grant
- 2019-12-26 TW TW108147731A patent/TWI777113B/zh active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2891968A (en) * | 1955-08-12 | 1959-06-23 | Du Pont | Difluorobutenedioic acids, their alkali metal salts, their alkyl esters and anhydride, and process for preparing them |
GB844604A (en) * | 1955-09-14 | 1960-08-17 | Robert Neville Haszeldine | Halogenated organic compounds |
WO2010007968A1 (ja) * | 2008-07-18 | 2010-01-21 | 日本ゼオン株式会社 | 含水素フルオロオレフィン化合物の製造方法 |
JP2010043034A (ja) * | 2008-08-14 | 2010-02-25 | Nippon Zeon Co Ltd | 含水素フルオロオレフィン化合物の製造方法 |
JP2010126452A (ja) * | 2008-11-25 | 2010-06-10 | Nippon Zeon Co Ltd | 含水素フルオロオレフィン化合物の製造方法 |
CN107721810A (zh) * | 2017-11-07 | 2018-02-23 | 中国民航大学 | 一种合成灭火剂八氟环丁烷的方法 |
Non-Patent Citations (2)
Title |
---|
BUXTON, M. W. ET AL.: "The reaction of highly fluorinated organic compounds. Part V. 1H: 2H-Hexafluorocyclobutane and 1H- Pentafluorocyclobut-1-ene", JOURNAL OF THE CHEMICAL SOCIETY, 1954, pages 1177 - 1179, XP055721537 * |
FULLER, G. ET AL.: "Some isomeric Hexafluorocyclobutanes and Pentafluorocyclobutenes", JOURNAL OF THE CHEMICAL SOCIETY, 1961, pages 3198 - 3203, XP055721540 * |
Also Published As
Publication number | Publication date |
---|---|
JP6835060B2 (ja) | 2021-02-24 |
KR20210108993A (ko) | 2021-09-03 |
KR102566765B1 (ko) | 2023-08-16 |
TWI777113B (zh) | 2022-09-11 |
SG11202106891PA (en) | 2021-07-29 |
CN113227026A (zh) | 2021-08-06 |
JP2020105114A (ja) | 2020-07-09 |
TW202035349A (zh) | 2020-10-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6673413B2 (ja) | フルオロオレフィンの製造方法 | |
JP6827246B2 (ja) | ハロゲン化ブテン化合物の製造方法 | |
WO2014077246A1 (ja) | ドライエッチングガスの製造方法 | |
KR102566765B1 (ko) | 시클로부텐의 제조 방법 | |
JP2016504326A (ja) | HFO−1234ze及びHFC−245faの共同製造方法 | |
JP2022087300A (ja) | フルオロエチレンの製造方法 | |
JP2023174809A (ja) | フルオロオレフィン化合物の製造方法 | |
JP6874778B2 (ja) | シクロブタンの製造方法 | |
CN112912360B (zh) | 全氟环烯烃化合物的制造方法 | |
JP2021014410A (ja) | ビニル化合物の製造方法 | |
RU2784315C1 (ru) | Способ получения циклобутена | |
RU2807184C2 (ru) | Способ получения циклобутана | |
RU2807184C9 (ru) | Способ получения циклобутана | |
JP2019151629A (ja) | 化合物の製造方法 | |
JP2021011474A (ja) | フッ化ビニル化合物の製造方法 | |
JP2024102305A (ja) | フッ化ビニル化合物の製造方法 | |
CN117597322A (zh) | 烯烃的制造方法 | |
KR20220019801A (ko) | 알칸의 제조 방법 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 19904214 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20217023297 Country of ref document: KR Kind code of ref document: A |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 19904214 Country of ref document: EP Kind code of ref document: A1 |