TWI777113B - The production method of cyclobutene - Google Patents
The production method of cyclobutene Download PDFInfo
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- TWI777113B TWI777113B TW108147731A TW108147731A TWI777113B TW I777113 B TWI777113 B TW I777113B TW 108147731 A TW108147731 A TW 108147731A TW 108147731 A TW108147731 A TW 108147731A TW I777113 B TWI777113 B TW I777113B
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- oxide
- halogen atom
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- CFBGXYDUODCMNS-UHFFFAOYSA-N cyclobutene Chemical compound C1CC=C1 CFBGXYDUODCMNS-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 125000005843 halogen group Chemical group 0.000 claims abstract description 70
- 238000006243 chemical reaction Methods 0.000 claims abstract description 68
- 238000003795 desorption Methods 0.000 claims abstract description 29
- 239000007789 gas Substances 0.000 claims abstract description 28
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 24
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims abstract description 20
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims description 58
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 35
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 18
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- UOUJSJZBMCDAEU-UHFFFAOYSA-N chromium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Cr+3].[Cr+3] UOUJSJZBMCDAEU-UHFFFAOYSA-N 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 5
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- WTKBYUSJUDBTIS-UHFFFAOYSA-N [O-2].F.[Mg+2] Chemical compound [O-2].F.[Mg+2] WTKBYUSJUDBTIS-UHFFFAOYSA-N 0.000 claims description 3
- 229910021563 chromium fluoride Inorganic materials 0.000 claims description 3
- 238000006704 dehydrohalogenation reaction Methods 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- FTBATIJJKIIOTP-UHFFFAOYSA-K trifluorochromium Chemical compound F[Cr](F)F FTBATIJJKIIOTP-UHFFFAOYSA-K 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 2
- 229910003460 diamond Inorganic materials 0.000 claims description 2
- 239000010432 diamond Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- SHXXPRJOPFJRHA-UHFFFAOYSA-K iron(iii) fluoride Chemical compound F[Fe](F)F SHXXPRJOPFJRHA-UHFFFAOYSA-K 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims 2
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 claims 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical group [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 description 57
- 239000002994 raw material Substances 0.000 description 28
- 125000001153 fluoro group Chemical group F* 0.000 description 22
- 229910052731 fluorine Inorganic materials 0.000 description 21
- 239000000203 mixture Substances 0.000 description 18
- 238000005796 dehydrofluorination reaction Methods 0.000 description 16
- 239000012071 phase Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 238000003682 fluorination reaction Methods 0.000 description 7
- 238000002474 experimental method Methods 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
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 238000010494 dissociation reaction Methods 0.000 description 5
- 208000018459 dissociative disease Diseases 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- -1 halogen atoms Chemical compound 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
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 3
- 239000007858 starting material 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
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 150000001931 cyclobutenes Chemical class 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 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 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 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
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- UHTBGZCYOATXPS-UHFFFAOYSA-M aluminum;oxygen(2-);fluoride Chemical compound [O-2].[F-].[Al+3] UHTBGZCYOATXPS-UHFFFAOYSA-M 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 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
- XKKQWEPXPQZMNH-UHFFFAOYSA-M chromium(3+);oxygen(2-);fluoride Chemical compound [O-2].[F-].[Cr+3] XKKQWEPXPQZMNH-UHFFFAOYSA-M 0.000 description 1
- 150000001930 cyclobutanes Chemical class 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000000354 decomposition reaction Methods 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
- 238000001312 dry etching Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 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
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052740 iodine 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
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- DBJLJFTWODWSOF-UHFFFAOYSA-L nickel(ii) fluoride Chemical compound F[Ni]F DBJLJFTWODWSOF-UHFFFAOYSA-L 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 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
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 230000000717 retained effect Effects 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
- 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
- C07C17/25—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
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- 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)
Abstract
本揭示之目的在於以高選擇率來製造包含鹵素原子之環丁烯。
一種一般式(1)所示之環丁烯之製造方法，其係包含使一般式(2)所示之環丁烷進行脫離反應之步驟，且係在氣相中進行前述脫離反應之步驟；
Description
本揭示係關於環丁烯之製造方法。The present disclosure relates to a method for producing cyclobutene.
包含鹵素原子之環丁烯係作為半導體用乾蝕刻氣體，以及各種冷媒、發泡劑、熱傳遞介質等而有用之化合物。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.
包含鹵素原子之環丁烯之中，關於1H-五氟環丁烯，已知有藉由脫氟化氫反應而從1H,2H-六氟環丁烷製造1H-五氟環丁烯的方法(例如，非專利文獻1及2)。該技術係在使用玻璃器具之開放反應系統下合成1H-五氟環丁烯。 [先前技術文獻] [非專利文獻]Among cyclobutenes containing halogen atoms, as for 1H-pentafluorocyclobutene, a method for producing 1H-pentafluorocyclobutene from 1H,2H-hexafluorocyclobutane by dehydrofluorination is known (for example, , Non-Patent Documents 1 and 2). This technique is for the synthesis of 1H-pentafluorocyclobutene in an open reaction system using glassware. [Prior Art Literature] [Non-patent literature]
[非專利文獻1] Buxton; Tatlow; Journal of the Chemical Society; (1954); p. 1177 - 1179 [非專利文獻2] Fuller,G.; Tatlow,J.C.; Journal of the Chemical Society; (1961); p. 3198 - 3203[Non-Patent Document 1] Buxton; Tatlow; Journal of the Chemical Society; (1954); p. 1177 - 1179 [Non-Patent Document 2] Fuller, G.; Tatlow, J.C.; Journal of the Chemical Society; (1961); p. 3198 - 3203
[發明所欲解決之課題][The problem to be solved by the invention]
本揭示之目的在於以高選擇率來製造包含鹵素原子之環丁烯。 [用以解決課題之手段]An object of the present disclosure is to produce a halogen atom-containing cyclobutene with high selectivity. [means to solve the problem]
本揭示包含以下之構成。The present disclosure includes the following constitutions.
項1. 一種一般式(1)所示之環丁烯之製造方法，其係包含使一般式(2)所示之環丁烷進行脫離反應之步驟，且係在氣相中進行前述脫離反應之步驟；Item 1. A method for producing cyclobutene represented by the general formula (1), comprising the step of making the cyclobutane represented by the general formula (2) carry out a desorption reaction, and the step of carrying out the aforementioned desorption reaction in a gas phase;
(式中，X1 、X2 、X3 及X4 係相同或係相異地表示氫原子、鹵素原子、或全氟烷基。Y表示鹵素原子。)(In the formula, X 1 , X 2 , X 3 and X 4 are the same or different, and represent a hydrogen atom, a halogen atom, or a perfluoroalkyl group. Y represents a halogen atom.)
(式中，X1 、X2 、X3 、X4 及Y係與前述相同。X5 及X6 係相同或相異地表示氫原子、鹵素原子、或全氟烷基。)(In the formula, X 1 , X 2 , X 3 , X 4 , and Y are the same as described above. X 5 and X 6 represent the same or different hydrogen atoms, halogen atoms, or perfluoroalkyl groups.)
項2. 如前述項1之製造方法，其中前述X5 為氫原子，前述X6 為鹵素原子，前述脫離反應為脫鹵氫反應。Item 2. The production method according to the aforementioned Item 1, wherein the X 5 is a hydrogen atom, the X 6 is a halogen atom, and the desorption reaction is a dehydrohalogenation reaction.
項3. 一種含有一般式(1)所示之環丁烯之組成物，其係將組成物總量設為100mol%，而前述一般式(1)所示之環丁烯之含量為95mol%以上；Item 3. A composition containing the cyclobutene represented by the general formula (1), the total amount of the composition is set as 100 mol%, and the content of the cyclobutene represented by the aforementioned general formula (1) is 95 mol% or more;
(式中，X1 、X2 、X3 及X4 係相同或相異地表示氫原子、鹵素原子或全氟烷基。Y表示鹵素原子。)(In the formula, X 1 , X 2 , X 3 and X 4 represent a hydrogen atom, a halogen atom or a perfluoroalkyl group identically or differently. Y represents a halogen atom.)
項4. 如前述項3之組成物，其中1H-全氟環丁烯(1H-cC4 F5 H)之含量為99mol%以上，3H-全氟環丁烯(3H-cC4 F5 H)之含量為1mol%以下。Item 4. The composition of item 3 above, wherein the content of 1H-perfluorocyclobutene (1H-cC 4 F 5 H) is 99 mol% or more, 3H-perfluorocyclobutene (3H-cC 4 F 5 H) ) is less than 1 mol%.
項5. 如前述項3或4之組成物，其係使用作為清洗氣體、蝕刻氣體、沉積氣體或有機合成用建構組元。 [發明之效果]Item 5. The composition according to the aforementioned item 3 or 4, which is used as a cleaning gas, an etching gas, a deposition gas, or a building element for organic synthesis. [Effect of invention]
根據本揭示，能以高選擇率來製造包含鹵素原子之環丁烯。According to the present disclosure, cyclobutene containing halogen atoms can be produced with high selectivity.
本發明者等經過精心研究之結果，發現藉由在氣相中實施使原料化合物進行脫離反應之步驟，即能以高選擇率來製造上述一般式(1)所示之包含鹵素原子之環丁烯。As a result of careful research by the present inventors, it was found that cyclobutane containing a halogen atom represented by the general formula (1) can be produced with high selectivity by carrying out the step of desorbing the raw material compound in the gas phase. ene.
本揭示係基於該知識見解，並更加進行重複研究之結果所完成者。The present disclosure is based on the knowledge and insights, and has been completed as a result of repeated research.
本揭示包括以下之實施形態。The present disclosure includes the following embodiments.
本揭示之一般式(1)所示之環丁烯之製造方法，其係包含：使一般式(2)所示之環丁烷進行脫離反應之步驟。The method for producing the cyclobutene represented by the general formula (1) of the present disclosure includes the step of subjecting the cyclobutane represented by the general formula (2) to a desorption reaction.
(式中，X1 、X2 、X3 及X4 係相同或相異地表示氫原子、鹵素原子或全氟烷基。Y表示鹵素原子。)(In the formula, X 1 , X 2 , X 3 and X 4 represent a hydrogen atom, a halogen atom or a perfluoroalkyl group identically or differently. Y represents a halogen atom.)
(式中，X1 、X2 、X3 、X4 及Y係與前述相同。X5 及X6 係相同或相異地表示氫原子、鹵素原子、或全氟烷基。)(In the formula, X 1 , X 2 , X 3 , X 4 , and Y are the same as described above. X 5 and X 6 represent the same or different hydrogen atoms, halogen atoms, or perfluoroalkyl groups.)
本揭示係在氣相中進行前述脫離反應之步驟。The present disclosure is to carry out the step of the aforementioned desorption reaction in the gas phase.
本揭示中，藉由滿足上述要件，即能以高選擇率來製造包含鹵素原子之環丁烯。In the present disclosure, by satisfying the above requirements, cyclobutene containing a halogen atom can be produced with high selectivity.
本揭示中，「選擇率」係意指相對於來自反應器出口之流出氣體中之原料化合物以外之化合物(包含鹵素原子之環丁烯等)之合計莫耳量的，該流出氣體所包含之目的化合物(包含鹵素原子之環丁烯)之合計莫耳量之比例(mol%)。In the present disclosure, "selectivity" means the total molar amount of compounds other than the raw material compounds (cyclobutene including halogen atoms, etc.) in the effluent gas from the reactor outlet, the effluent gas contained in the effluent gas. The ratio (mol%) of the total molar amount of the target compound (cyclobutene containing a halogen atom).
本揭示中，「轉化率」係意指相對於供給至反應器之原料化合物(包含鹵素原子之環丁烷)之莫耳量的，來自反應器出口之流出氣體所包含之原料化合物以外之化合物(包含鹵素原子之環丁烯等)之合計莫耳量之比例(mol%)。In the present disclosure, "conversion rate" means compounds 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 (cyclobutane containing halogen atoms) supplied to the reactor The ratio (mol %) of the total molar amount (such as cyclobutene including a halogen atom).
又，本揭示之環丁烯之製造方法由於並非係批次反應(batch reaction)而係流通系統之氣相反應，故具有並不需要使用溶劑，且不產生產業廢棄物之優點。In addition, since the method for producing cyclobutene of the present disclosure is not a batch reaction but a gas-phase reaction in a circulation system, it has the advantages that no solvent is required and no industrial waste is generated.
(1)原料化合物 本揭示中，原料化合物為一般式(2)所示之環丁烷。(1) Raw material compounds In the present disclosure, the starting compound is cyclobutane represented by the general formula (2).
(式中，X1 、X2 、X3 、X4 、X5 及X6 係相同或相異地表示氫原子、鹵素原子或全氟烷基。Y表示鹵素原子。)(In the formula, X 1 , X 2 , X 3 , X 4 , X 5 and X 6 represent a hydrogen atom, a halogen atom or a perfluoroalkyl group identically or differently. Y represents a halogen atom.)
X1 、X2 、X3 、X4 、X5 及X6 係相同或相異地表示氫原子、鹵素原子、或全氟烷基。X 1 , X 2 , X 3 , X 4 , X 5 and X 6 represent a hydrogen atom, a halogen atom, or a perfluoroalkyl group identically or differently.
Y表示鹵素原子。Y represents a halogen atom.
X1 、X2 、X3 、X4 、X5 、X6 及Y之鹵素原子，可舉出如氟原子、氯原子、溴原子、及碘原子。The halogen atoms of X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and Y include, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
X1 、X2 、X3 、X4 、X5 及X6 之全氟烷基係為全部氫原子被氟原子取代之烷基。全氟烷基係以例如，碳數1~20，較佳為碳數1~12，更佳為碳數1~6，較更佳為碳數1~4，特佳為碳數1~3之全氟烷基為佳。全氟烷基係以直鏈狀，或分枝鏈狀之全氟烷基為佳。作為前述全氟烷基，以三氟甲基(CF3 -)，及五氟乙基(C2 F5 -)為佳。The perfluoroalkyl groups of X 1 , X 2 , X 3 , X 4 , X 5 and X 6 are alkyl groups in which all hydrogen atoms are substituted with fluorine atoms. For example, the perfluoroalkyl group has 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and particularly preferably 1 to 3 carbon atoms. The perfluoroalkyl group is preferred. The perfluoroalkyl group is preferably a straight-chain or branched-chain perfluoroalkyl group. As the aforementioned perfluoroalkyl group, trifluoromethyl (CF 3 -) and pentafluoroethyl (C 2 F 5 -) are preferable.
作為原料化合物之一般式(2)所示之包含鹵素原子之環丁烷，從能以高選擇率來製造包含鹵素原子之環丁烯的觀點，以X1 、X2 、X3 及X4 係相同或相異地表示氫原子、鹵素原子或全氟烷基，且X5 為氫原子，X6 為氟原子，Y為氟原子為較佳。The halogen atom-containing cyclobutane represented by the general formula (2) as the raw material compound is represented by X 1 , X 2 , X 3 and X 4 from the viewpoint that the halogen atom-containing cyclobutene can be produced with high selectivity. The same or different represents a hydrogen atom, a halogen atom or a perfluoroalkyl group, and X 5 is a hydrogen atom, X 6 is a fluorine atom, and Y is preferably a fluorine atom.
作為原料化合物之一般式(2)所示之環丁烷，可舉出例如，The cyclobutane represented by the general formula (2) as the starting compound includes, for example,
等之化合物。and other compounds.
該等一般式(2)所示之環丁烷係能單獨使用，也能組合2種以上使用。此種環丁烷係可採用市售品。The cyclobutanes represented by the general formula (2) can be used alone or in combination of two or more. As such a cyclobutane system, a commercial item can be used.
一般式(2)所示之包含鹵素原子之環丁烷在從能以高選擇率來製造包含鹵素原子之環丁烯的觀點，以X1 、X2 、X3 、X4 及X6 為氟原子，X5 為氫原子，Y為氟原子為較佳。The halogen atom-containing cyclobutane represented by the general formula (2) is represented by X 1 , X 2 , X 3 , X 4 and X 6 from the viewpoint of producing a halogen atom-containing cyclobutene with high selectivity. A fluorine atom, X 5 is preferably a hydrogen atom, and Y is a fluorine atom.
(2)脫離反應 本揭示中進行脫離反應之步驟係在氣相中進行脫離反應。本揭示之進行脫離反應之步驟係在氣相中進行，尤其係以使用固定床反應器之氣相連續流通式來進行為佳。在以氣相連續流通式進行之情況，不僅能簡略化裝置、操作等，且有利於經濟性。(2) Detachment reaction The step of carrying out the dissociation reaction in the present disclosure is to carry out the dissociation reaction in the gas phase. The step of carrying out the desorption reaction of the present disclosure is carried out in the gas phase, especially preferably in a gas-phase continuous flow mode using a fixed bed reactor. When the gas-phase continuous flow type is used, not only the equipment, operation, etc. can be simplified, but also economical efficiency can be achieved.
本揭示中進行脫離反應之步驟係以前述X5 為氫原子，前述X6 為鹵素原子，前述脫離反應為脫鹵氫反應為佳。本揭示中進行脫離反應之步驟係以前述X5 為氫原子，前述X6 為氟原子，前述脫離反應為脫氟化氫反應為佳。In the present disclosure, in the step of performing the desorption reaction, the aforementioned X 5 is a hydrogen atom, the aforementioned X 6 is a halogen atom, and the aforementioned desorption reaction is preferably a dehydrohalogenation reaction. In the present disclosure, in the step of performing the desorption reaction, the aforementioned X 5 is a hydrogen atom, the aforementioned X 6 is a fluorine atom, and the aforementioned desorption reaction is preferably a dehydrofluorination reaction.
例如，作為原料化合物，以一般式(2)所示之包含鹵素原子之環丁烷中，X1 、X2 、X3 、X4 及X6 為氟原子，X5 為氫原子，Y為氟原子為佳。For example, as a starting compound, in the halogen atom-containing cyclobutane 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 A fluorine atom is preferred.
以根據以下之反應式，脫離反應係脫氟化氫反應為佳。Preferably, the desorption reaction is a dehydrofluorination reaction according to the following reaction formula.
觸媒 本揭示中進行脫離反應之步驟係以在觸媒存在下，在氣相下中進行脫離反應為佳。catalyst In the present disclosure, the step of carrying out the desorption reaction is preferably carried out in the gas phase in the presence of a catalyst.
本步驟所使用之觸媒係以活性碳為佳。本步驟所使用之觸媒係以金屬觸媒為佳。作為金屬觸媒，以選自由氧化鉻、氟化氧化鉻、氟化鉻、氧化鋁、氟化氧化鋁、氟化鋁、氧化鐵、氟化氧化鐵、氟化鐵、氧化鎳、氟化氧化鎳、氟化鎳、氧化鎂、氟化氧化鎂及氟化鎂所成群之至少1種為佳。The catalyst used in this step is preferably activated carbon. The catalyst used in this step is preferably a metal catalyst. As a metal catalyst, selected from the group consisting of chromium oxide, chromium oxide fluoride, chromium fluoride, aluminum oxide, aluminum oxide fluoride, aluminum fluoride, iron oxide, iron oxide fluoride, iron fluoride, nickel oxide, oxide fluoride At least one of the group consisting of nickel, nickel fluoride, magnesium oxide, magnesium oxide fluoride and magnesium fluoride is preferred.
該等觸媒之中，從能以更高選擇率來取得目的化合物之觀點，以活性碳、氧化鉻、氟化氧化鉻、氧化鋁、氟化氧化鋁為較佳。又，也能更加提升原料化合物之轉化率。Among these catalysts, activated carbon, chromium oxide, fluorided chromium oxide, alumina, and fluorided alumina are preferred from the viewpoint of obtaining the target compound with a higher selectivity. In addition, the conversion rate of the raw material compound can be further improved.
本步驟中，在氣相中使原料化合物與觸媒接觸之際，以使觸媒在固體狀態(固相)下與原料化合物接觸為佳。In this step, when the raw material compound is brought into contact with the catalyst in the gas phase, the catalyst is preferably brought into contact with the raw material compound in a solid state (solid phase).
本步驟中，觸媒也可為粉末狀，但在氣相連續流通式之反應中則係以顆粒(pellet)狀為佳。In this step, the catalyst can also be in powder form, but in the gas-phase continuous flow reaction, it is preferably in the form of pellets.
前述觸媒在藉由BET法所測量之比表面積(以下，亦稱為BET比表面積)通常為10~3,000m2 ／g，以10~400m2 ／g為佳，較佳為20~375m2 ／g，更佳為30~350m2 ／g。觸媒之BET比表面積位在此種範圍時，由於觸媒之粒子密度不會有過小的情況，故能以高選擇率取得目的化合物。又，也能提升原料化合物之轉化率。The specific surface area of the catalyst (hereinafter, also referred to as BET specific surface area) measured by the BET method is usually 10 to 3,000 m 2 /g, preferably 10 to 400 m 2 /g, more preferably 20 to 375 m 2 /g, more preferably 30 to 350 m 2 /g. When the BET specific surface area of the catalyst is in this range, the target compound can be obtained with high selectivity because the particle density of the catalyst will not be too small. In addition, the conversion rate of the raw material compound can also be improved.
使用活性碳作為觸媒時，以使用破碎炭、成形炭、顆粒炭、球狀炭等之粉末活性碳為佳。粉末活性碳係以使用在JIS試驗下顯示4篩目(4.76mm)~100篩目(0.149mm)之粒度的粉末活性碳為佳。When using activated carbon as a catalyst, it is preferable to use powdered activated carbon such as crushed carbon, shaped carbon, granular carbon, spherical carbon, etc. The powdered activated carbon is preferably powdered activated carbon with a particle size of 4 meshes (4.76mm) to 100 meshes (0.149mm) under the JIS test.
使用金屬觸媒作為觸媒時，以被載持於載體上為佳。作為載體，可舉出例如，碳、氧化鋁(Al2 O3 )、氧化鋯(ZrO2 )、二氧化矽(SiO2 )、氧化鈦(TiO2 )等。作為碳，可舉出如活性碳、非定形碳、石墨、金剛石等。When a metal catalyst is used as a catalyst, it is preferable to carry it on a carrier. Examples of the carrier include carbon, aluminum oxide (Al 2 O 3 ), zirconium oxide (ZrO 2 ), silicon dioxide (SiO 2 ), titanium oxide (TiO 2 ), and the like. As carbon, activated carbon, amorphous carbon, graphite, diamond, etc. are mentioned, for example.
作為本揭示中之觸媒之一例，說明關於氧化鉻及經氟化之氧化鉻。氧化鉻在例如以Cr2 O3 ･nH2 O來表示氧化鉻時，n之值係以3以下為佳，以1~1.5為較佳。又，前述氧化鉻在組成式：CrOm 中，以m通常在1.5＜m＜3之範圍者為佳。作為觸媒，經氟化之氧化鉻係可藉由將氧化鉻予以氟化來調製。作為氟化，可舉出如利用氟化氫(HF)之氟化、利用氟碳等之氟化。As an example of the catalyst in the present disclosure, a description will be given of chromium oxide and fluorinated chromium oxide. When the chromium oxide is represented by Cr 2 O 3 ･nH 2 O as chromium oxide, for example, the value of n is preferably 3 or less, more preferably 1 to 1.5. In addition, in the composition formula of the chromium oxide: CrO m , it is preferable that m is usually in the range of 1.5<m<3. As a catalyst, fluorinated chromium oxide can be prepared by fluorinating chromium oxide. Examples of fluorination include fluorination with hydrogen fluoride (HF), fluorination with fluorocarbon, and the like.
作為觸媒之經氟化之氧化鉻係可依據例如日本專利第3412165號記載之方法來獲得。藉由利用氟化氫來對氧化鉻進行氟化(HF處理)，而可取得經氟化之氧化鉻。氟化之溫度係例如以100~460℃為佳。氟化之壓力係以供給至觸媒反應時之壓力為佳。本揭示中，以使用氟含量多之高氟化-氧化鉻觸媒為佳。高氟化-氧化鉻觸媒係可藉由在比通常還更高溫下長時間來將氧化鉻氟化而取得。The fluorinated chromium oxide system as a catalyst can be obtained by, for example, the method described in Japanese Patent No. 3412165 . Fluorinated chromium oxide can be obtained by fluorinating chromium oxide with hydrogen fluoride (HF treatment). The temperature of the fluorination is preferably 100 to 460°C, for example. The pressure of the fluorination is preferably the pressure supplied to the catalyst reaction. In the present disclosure, it is preferable to use a highly fluorinated-chromia catalyst with a large fluorine content. Highly fluorinated-chromia catalysts can be obtained by fluorination of chromium oxide at higher temperatures than usual for extended periods of time.
高氟化-氧化鉻觸媒之氟含量係以30質量%以上為佳，以30~45質量%為較佳。氟含量係可藉由觸媒之質量變化，或一般性鉻氧化物之定量分析法進行測量。The fluorine content of the highly fluorinated-chromium oxide catalyst is preferably 30% by mass or more, more preferably 30 to 45% by mass. The fluorine content can be measured by the mass change of the catalyst, or the quantitative analysis method of general chromium oxide.
脫離反應溫度 本揭示之進行脫離反應之步驟中，反應溫度之下限值在從能更有效率地使脫離反應進行，且能以更高選擇率取得目的化合物觀點，又從抑制轉化率降低之觀點，通常為50℃，以200℃為佳，較佳為250℃，更佳為300℃，特佳為350℃。release reaction temperature In the step of carrying out the dissociation reaction of the present disclosure, the lower limit of the reaction temperature is from the viewpoint of enabling the dissociation reaction to proceed more efficiently and obtaining the target compound with a higher selectivity, and from the viewpoint of suppressing the reduction of the conversion rate, usually It is 50°C, preferably 200°C, preferably 250°C, more preferably 300°C, and particularly preferably 350°C.
脫離反應之反應溫度之上限值在從能更有效率地使脫氟化氫反應進行，且能以更高選擇率取得目的化合物之觀點，且從抑制反應生成物進行分解或聚合所造成之選擇率降低的觀點，通常為500℃，以450℃為佳，較佳為400℃。The upper limit of the reaction temperature of the dehydrofluorination reaction is from the viewpoint that the dehydrofluorination reaction can be carried out more efficiently and the target compound can be obtained with a higher selectivity, and the selectivity caused by the inhibition of decomposition or polymerization of the reaction product From the viewpoint of lowering, it is usually 500°C, preferably 450°C, more preferably 400°C.
脫離反應時間 脫離反應之反應時間係只要拉長原料化合物對觸媒之接觸時間(W／F0 )[W：金屬觸媒之重量(g)，F0 ：原料化合物之流量(cc／sec)]就能提升原料化合物之轉化率，但觸媒之量會變多且設備會變大，故為非效率者。Detachment reaction time The reaction time of detachment reaction is as long as the contact time of the raw material compound to the catalyst (W/F 0 ) [W: the weight of the metal catalyst (g), F 0 : the flow rate of the raw material compound (cc/sec) ] can improve the conversion rate of raw material compounds, but the amount of catalyst will increase and the equipment will become larger, so it is not efficient.
因此，脫氟化氫反應之反應時間再從提升原料化合物之轉化率之觀點，及抑制設備成本之觀點，原料化合物對觸媒之接觸時間(W／F0 )係以5g･sec／cc~300g･sec／cc為佳，以10g･sec／cc~200g･sec／cc為較佳，以15g･sec／cc~ 150g･sec／cc為更佳，以20g･sec／cc~100g･sec／cc為特佳。Therefore, the reaction time of the dehydrofluorination reaction is from the viewpoint of improving the conversion rate of the raw material compound and reducing the equipment cost, and the contact time (W/F 0 ) of the raw material compound to the catalyst is 5g･sec/cc~300g･ sec/cc is better, 10g･sec/cc~200g･sec/cc is better, 15g･sec/cc~ 150g･sec/cc is better, 20g･sec/cc~100g･sec/cc Excellent.
上述原料化合物對觸媒之接觸時間係意指原料化合物及觸媒進行接觸之時間。The above-mentioned contact time between the raw material compound and the catalyst means the time during which the raw material compound and the catalyst are in contact.
本揭示之脫離反應在觸媒之存在下，且在氣相中進行之際，尤其係配合觸媒來適宜調整反應溫度與反應時間(接觸時間)，即能以更高選擇率取得目的化合物。When the dissociation reaction of the present disclosure is carried out in the gas phase in the presence of a catalyst, the reaction temperature and reaction time (contact time) can be appropriately adjusted with a catalyst, that is, the target compound can be obtained with a higher selectivity.
在使用氧化鉻作為觸媒時，反應溫度係以300℃以上為佳，以350℃以上為較佳。又，接觸時間係以10g･sec／cc以上為佳，以20g･sec／cc以上為較佳，以40g･sec／cc以上為更佳。When chromium oxide is used as a catalyst, the reaction temperature is preferably 300°C or higher, more preferably 350°C or higher. In addition, the contact time is preferably 10 g･sec/cc or more, more preferably 20 g･sec/cc or more, and more preferably 40 g･sec/cc or more.
使用氧化鋁作為觸媒時，反應溫度係以300℃以上為佳，又，接觸時間係以5g･sec／cc以上為佳。When alumina is used as a catalyst, the reaction temperature is preferably 300°C or more, and the contact time is preferably 5g･sec/cc or more.
使用活性碳作為觸媒時，反應溫度係以300℃以上為佳，以350℃以上為較佳，以400℃以上為更佳。又，接觸時間係以5g･sec／cc~55g･sec／cc為佳，以5g･sec／cc~ 50g･sec／cc為較佳，以5g･sec／cc~40g･sec／cc為更佳。When activated carbon is used as a catalyst, the reaction temperature is preferably 300°C or higher, more preferably 350°C or higher, and more preferably 400°C or higher. Also, the contact time is preferably 5g･sec/cc~55g･sec/cc, preferably 5g･sec/cc~50g･sec/cc, more preferably 5g･sec/cc~40g･sec/cc good.
脫離反應壓力 脫離反應之反應壓力在從能更有效率地脫離反應進行之觀點，以-0.05MPa~2MPa為佳，以-0.01MPa~1MPa為較佳，以常壓~0.5MPa為更佳。尚且，本揭示中，在並未標示關於壓力之情況，則為計示壓力。out of reaction pressure The reaction pressure of the desorption reaction is preferably -0.05MPa~2MPa, preferably -0.01MPa~1MPa, and more preferably normal pressure~0.5MPa, from the viewpoint of more efficient desorption reaction. Moreover, in the present disclosure, when the pressure is not indicated, it is the gauge pressure.
脫離反應中，作為使原料化合物與觸媒(金屬觸媒等)進行接觸而反應之反應器，只要能承受上述溫度及壓力者，形狀及構造即並無特別限定。作為反應器，可舉出例如，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，可舉出例如，玻璃、不鏽鋼、鐵、鎳、鐵鎳合金等。In the desorption reaction, the shape and structure are not particularly limited as long as the reactor for reacting the raw material compound and the catalyst (metal catalyst, etc.) can withstand the above-mentioned temperature and pressure. As a reactor, for example, a vertical reactor, a horizontal reactor, a multi-tubular reactor, etc. are mentioned. As a material of a reactor, glass, stainless steel, iron, nickel, iron-nickel alloy, etc. are mentioned, for example.
脫離反應之例示 脫離反應係藉由對反應器連續性投入原料化合物，並從該反應器連續性抽出目的化合物之流通式及批次式之任一方式皆能實施。目的化合物滯留於反應器時，由於脫離反應可能會更加進行，故以流通式來實施為佳。本揭示之進行脫離反應之步驟係以在氣相中進行，尤其係以使用固定床反應器之氣相連續流通式來進行為佳。以氣相連續流通式來進行之情況，不僅可簡略化裝置、操作等，且有利於經濟性。Example of a disengagement reaction The stripping reaction can be carried out by either a flow-through method or a batch method in which the raw material compound is continuously fed into the reactor and the target compound is continuously extracted from the reactor. When the target compound is retained in the reactor, since the desorption reaction may proceed further, it is preferable to carry out the flow-through method. The step of carrying out the desorption reaction of the present disclosure is carried out in the gas phase, especially in a gas-phase continuous flow type using a fixed-bed reactor. When it is carried out by the gas-phase continuous flow type, not only the equipment, operation, etc. can be simplified, but also economical efficiency is advantageous.
關於進行脫離反應時之環境，從抑制觸媒(金屬觸媒等)劣化之觀點，以在惰性氣體存在下及／或氟化氫存在下為佳。該惰性氣體係以選自由氮、氦、氬及二氧化碳所成群之至少1種為佳。該等惰性氣體之中，從抑制成本之觀點，以氮為較佳。該惰性氣體之濃度係作成導入至反應器中之氣體成分之0~50mol%為佳。The environment in which the desorption reaction is carried out is preferably in the presence of an inert gas and/or in the presence of hydrogen fluoride from the viewpoint of suppressing the deterioration of the catalyst (metal catalyst, etc.). The inert gas system is preferably at least one selected from the group consisting of nitrogen, helium, argon and carbon dioxide. Among these inert gases, nitrogen is preferable from the viewpoint of cost reduction. The concentration of the inert gas is preferably 0 to 50 mol% of the gas components introduced into the reactor.
脫離反應結束後係因應必要依據常法來進行純化處理，而可取得一般式(1)所示之包含鹵素原子之環丁烯。After completion of the desorption reaction, if necessary, purification treatment is carried out according to an ordinary method, and the halogen atom-containing cyclobutene represented by the general formula (1) can be obtained.
(3)目的化合物 本揭示之目的化合物為一般式(1)所示之包含鹵素原子之環丁烯。(3) target compound The objective compound of the present disclosure is a halogen atom-containing cyclobutene represented by the general formula (1).
(式中，X1 、X2 、X3 及X4 係相同或相異地表示氫原子、鹵素原子或全氟烷基。Y表示鹵素原子。)(In the formula, X 1 , X 2 , X 3 and X 4 represent a hydrogen atom, a halogen atom or a perfluoroalkyl group identically or differently. Y represents a halogen atom.)
X1 、X2 、X3 及X4 、以及Y係與前述相同。X 1 , X 2 , X 3 and X 4 , and Y are the same as described above.
所欲製造之一般式(1)所示之環丁烯係可舉出例如，以下The cyclobutenes represented by the general formula (1) to be produced include, for example, the following
等之化合物。and other compounds.
以一般式(1)所示之包含鹵素原子之環丁烯中，X1 、X2 、X3 及X4 係相同或相異地表示氫原子、鹵素原子或全氟烷基，Y係氟原子為佳。以一般式(1)所示之包含鹵素原子之環丁烯中，X1 、X2 、X3 及X4 係氟原子，Y係氟原子為較佳。In the halogen atom-containing cyclobutene represented by the general formula (1), X 1 , X 2 , X 3 and X 4 represent a hydrogen atom, a halogen atom or a perfluoroalkyl group identically or differently, and Y represents a fluorine atom better. In the halogen atom-containing cyclobutene represented by the general formula (1), X 1 , X 2 , X 3 and X 4 are preferably fluorine atoms, and Y is preferably a fluorine atom.
本揭示之包含鹵素原子之環丁烯之製造方法中，以一般式(2)所示之包含鹵素原子之環丁烷作為原料化合物，且X1 、X2 、X3 、X4 及X6 係氟原子，X5 係氫原子，Y係氟原子時之脫離反應為佳。In the method for producing a halogen atom-containing cyclobutene of the present disclosure, the halogen atom-containing cyclobutane represented by the general formula (2) is used as a raw material compound, and X 1 , X 2 , X 3 , X 4 and X 6 The desorption reaction is preferable when X is a fluorine atom, X5 is a hydrogen atom, and Y is a fluorine atom.
以根據以下之反應式，且脫離反應係脫氟化氫反應為佳。It is preferable that the desorption reaction is a dehydrofluorination reaction according to the following reaction formula.
目的化合物係以一般式(1)所示之包含鹵素原子之環丁烯，且X1 、X2 、X3 及X4 係氟原子，Y係氟原子為佳。The target compound is a halogen atom-containing cyclobutene represented by the general formula (1), wherein X 1 , X 2 , X 3 and X 4 are fluorine atoms, and Y is preferably a fluorine atom.
(4)含有包含鹵素原子之環丁烯之組成物 藉由以上之操作而可取得一般式(1)所示之包含鹵素原子之環丁烯，又如上述般，也有以包含一般式(1)所示之包含鹵素原子之環丁烯，與一般式(2)所示之包含鹵素原子之環丁烷之組成物之形態來取得的情況。(4) Composition containing cyclobutene containing halogen atom Through the above operation, the cyclobutene containing halogen atoms represented by the general formula (1) can be obtained, and as above, there are also cyclobutene containing halogen atoms represented by the general formula (1), which is different from the general formula (1). The case where it is obtained in the form of the composition of cyclobutane containing a halogen atom represented by the formula (2).
作為組成物所包含之一般式(1)所示之包含鹵素原子之環丁烯，以X1 、X2 、X3 及X4 為氟原子，Y為氟原子為佳。The halogen atom-containing cyclobutene represented by the general formula (1) contained in the composition is preferably such that X 1 , X 2 , X 3 and X 4 are fluorine atoms, and Y is a fluorine atom.
本揭示之包含一般式(1)所示之包含鹵素原子之環丁烯之組成物中，將前述組成物之總量設為100mol%，一般式(1)所示之包含鹵素原子之環丁烯之含量係以95mol%以上為佳，以99mol%以上為較佳。In the composition comprising the halogen atom-containing cyclobutene represented by the general formula (1) of the present disclosure, the total amount of the aforementioned composition is set to 100 mol %, and the halogen atom-containing cyclobutene represented by the general formula (1) The content of alkene is preferably 95 mol% or more, preferably 99 mol% or more.
本揭示之包含一般式(1)所示之包含鹵素原子之環丁烯之組成物中，將前述組成物之總量設為100mol%，一般式(1)所示之包含鹵素原子之環丁烯之含量係以1mol%~99.9mol%為佳，以5mol%~99.9mol%為較佳，以10mol%~99.9mol%為更佳。In the composition comprising the halogen atom-containing cyclobutene represented by the general formula (1) of the present disclosure, the total amount of the aforementioned composition is set to 100 mol %, and the halogen atom-containing cyclobutene represented by the general formula (1) The content of alkene is preferably 1 mol % to 99.9 mol %, preferably 5 mol % to 99.9 mol %, and more preferably 10 mol % to 99.9 mol %.
本揭示之包含鹵素原子之環丁烯之製造方法中，上述脫離反應係可能會生成以下之化合物作為雜質。In the method for producing a halogen atom-containing cyclobutene of the present disclosure, the above-mentioned desorption reaction system may generate the following compounds as impurities.
本揭示之包含一般式(1)所示之包含鹵素原子之環丁烯之組成物中，將前述組成物之總量設為100mol%，以1H-全氟環丁烯(1H-cC4 F5 H)之含量為99mol%以上，3H-全氟環丁烯(3H-cC4 F5 H)之含量為1mol%以下為佳。In the composition comprising the halogen atom-containing cyclobutene represented by the general formula (1) of the present disclosure, the total amount of the aforementioned composition is set as 100 mol %, and 1H-perfluorocyclobutene (1H-cC 4 F The content of 5 H) is 99 mol% or more, and the content of 3H-perfluorocyclobutene (3H-cC 4 F 5 H) is preferably 1 mol % or less.
根據本揭示之製造方法，即使係取得作為包含一般式(1)所示之包含鹵素原子之環丁烯之組成物的情況，也能以特高選擇率來取得一般式(1)所示之包含鹵素原子之環丁烯，其結果係能減少前述組成物中之一般式(1)所示之包含鹵素原子之環丁烯以外之成分。根據本揭示之製造方法，可削減為了取得一般式(1)所示之包含鹵素原子之環丁烯用之純化之勞力。According to the production method of the present disclosure, even if it is obtained as a composition containing the halogen atom-containing cyclobutene represented by the general formula (1), the compound represented by the general formula (1) can be obtained with an extremely high selectivity. As a result of the halogen atom-containing cyclobutene, components other than the halogen atom-containing cyclobutene represented by the general formula (1) in the aforementioned composition can be reduced. According to the production method of the present disclosure, the labor for purification to obtain the halogen atom-containing cyclobutene represented by the general formula (1) can be reduced.
本揭示之包含一般式(1)所示之包含鹵素原子之環丁烯之組成物係與單獨一般式(1)所示之包含鹵素原子之環丁烯之情況同樣地，能有效利用於形成半導體、液晶等之最先端微細構造用之蝕刻氣體，以及沉積氣體、有機合成用建構組元、清洗氣體等之各種用途。The composition containing the halogen atom-containing cyclobutene represented by the general formula (1) of the present disclosure can be effectively used to form the same as the case of the halogen atom-containing cyclobutene represented by the general formula (1) alone. Etching gas for cutting-edge microstructures such as semiconductors and liquid crystals, and various applications such as deposition gas, structural components for organic synthesis, and cleaning gas.
前述沉積氣體係意指使蝕刻耐性聚合物層堆積之氣體。The aforementioned deposition gas system means a gas for depositing the etch-resistant polymer layer.
前述有機合成用建構組元係意指能成為具有高反應性骨架之化合物前驅物的物質。例如，在使本揭示之一般式(1)所示之包含鹵素原子之環丁烯，及包含此之組成物，與CF3 Si(CH3 )3 等之含氟有機矽化合物反應時，導入CF3 基等之氟烷基而能轉換成洗淨劑或能成為含氟醫藥中間體的物質。The aforementioned building block for organic synthesis means a substance that can become a precursor of a compound having a highly reactive skeleton. For example, when cyclobutene containing a halogen atom represented by the general formula (1) of the present disclosure, and a composition containing the same, are reacted with a fluorine-containing organosilicon compound such as CF 3 Si(CH 3 ) 3 , the introduction of A fluoroalkyl group such as a CF 3 group can be converted into a detergent or a substance that can become a fluorine-containing pharmaceutical intermediate.
以上，說明了本揭示之實施形態，但只要不超出申請專利範圍之要旨及範圍，即能賦予形態或詳細之各種變更。 [實施例]The embodiment of the present disclosure has been described above, but various changes in form and detail can be added as long as they do not depart from the gist and scope of the scope of the patent application. [Example]
以下例舉實施例，具體地說明本揭示，但本揭示並非係受到該等實施例所任何限定者。The following examples are given to specifically illustrate the present disclosure, but the present disclosure is not limited by these examples.
實施例 實施例之包含鹵素原子之環丁烯之製造方法中，原料化合物係作成一般式(2)所示之包含鹵素原子之環丁烷中，X1 、X2 、X3 、X4 及X6 為氟原子，X5 為氫原子，Y為氟原子。EXAMPLES In the method for producing cyclobutene containing a halogen atom of the embodiment, the raw material compound is prepared as the cyclobutane containing a halogen atom represented by the general formula (2), X 1 , X 2 , X 3 , X 4 and X 6 is a fluorine atom, X 5 is a hydrogen atom, and Y is a fluorine atom.
根據以下之反應式，脫離反應係利用脫氟化氫反應。According to the following reaction formula, the desorption reaction utilizes a dehydrofluorination reaction.
目的化合物係作成一般式(1)所示之包含鹵素原子之環丁烯中，X1 、X2 、X3 及X4 為氟原子，Y為氟原子。The target compound is prepared as a halogen atom-containing cyclobutene 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.
又，上述脫離反應中，可能會生成以下之化合物作為雜質。In addition, in the above-mentioned desorption reaction, the following compounds may be produced as impurities.
實施例1~3(氧化鉻觸媒) 使用SUS配管(外徑：1／2吋)作為反應管，且填充以Cr2 O3 為主成分之氧化鉻10g作為觸媒。作為將前述觸媒使用於脫離反應(脫氟化氫反應)之前處理，使反應器流通無水氟化氫，並將反應器之溫度從200℃提升至300℃來進行氟化處理。取出經氟化之氧化鉻，而使用於脫氟化氫反應。經氟化之氧化鉻之BET比表面積為75m2 ／g。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. As a treatment before using the aforementioned catalyst for the desorption reaction (dehydrofluorination reaction), anhydrous hydrogen fluoride was circulated in the reactor, and the temperature of the reactor was raised from 200°C to 300°C to perform the fluorination treatment. The fluorinated chromium oxide is taken out and used in the dehydrofluorination reaction. The BET specific surface area of the fluorinated chromium oxide was 75 m 2 /g.
對反應器之SUS配管(外徑：1／2吋)添加觸媒之經氟化之氧化鉻(氟化氧化鉻)10g。氮環境下，以200℃乾燥2小時後，以壓力為常壓，cC4 F6 H2 (原料化合物)與經氟化之氧化鉻(觸媒)之接觸時間(W／F0 )成為20g･sec／cc或40g･sec／cc之方式使原料化合物(cC4 F6 H2 )流通於反應器中。To the SUS piping (outer diameter: 1/2 inch) of the reactor, 10 g of fluorinated chromium oxide (fluorinated chromium oxide) as a catalyst was added. Under nitrogen atmosphere, after drying at 200°C for 2 hours, the pressure is normal pressure, and the contact time (W/F 0 ) of cC 4 F 6 H 2 (raw material compound) and fluorinated chromium oxide (catalyst) becomes 20 g The raw material compound (cC 4 F 6 H 2 ) was circulated in the reactor in the manner of ･sec/cc or 40g･sec/cc.
以氣相連續流通式來進行反應。The reaction is carried out in a gas-phase continuous flow system.
在250℃或350℃下加熱反應器並開始脫氟化氫反應。The reactor was heated at 250°C or 350°C and the dehydrofluorination reaction started.
開始脫氟化氫反應直至1小時後，收集通過除害塔之餾出分。The dehydrofluorination reaction was started until 1 hour later, and the distillate passing through the detoxification tower was collected.
其後，使用氣相層析儀(島津製作所公司製，商品名「GC-2014」)藉由氣相層析／質量分析法(GC／MS)進行質量分析，使用NMR(JEOL公司製，商品名「400YH」)進行利用NMR光譜之構造解析。After that, mass analysis was performed by gas chromatography/mass spectrometry (GC/MS) using a gas chromatograph (manufactured by Shimadzu Corporation, trade name "GC-2014"), and mass analysis was performed using NMR (manufactured by JEOL Corporation, trade name "GC-2014"). Name "400YH") was subjected to structural analysis using NMR spectroscopy.
從質量分析及構造解析之結果，確認到已生成cC4 F5 H作為目的化合物。實施例1中，從cC4 F6 H2 (原料化合物)之轉化率為3.34mol%，cC4 F5 H(目的化合物)之選擇率(收率)為45.9mol%。實施例2中，轉化率：29.1mol%，選擇率：98.6mol%。實施例3中，轉化率：26.1mol%，選擇率：97.2mol%。From the results of mass analysis and structural analysis, it was confirmed that cC 4 F 5 H was produced as the target compound. In Example 1, the conversion rate from cC 4 F 6 H 2 (raw compound) was 3.34 mol %, and the selectivity (yield) of cC 4 F 5 H (object compound) was 45.9 mol %. In Example 2, conversion rate: 29.1 mol%, selectivity: 98.6 mol%. In Example 3, conversion rate: 26.1 mol%, selectivity: 97.2 mol%.
實施例4及5(氧化鋁觸媒) 仿效前述實施例1之實驗方法，使用以Al2 O3 為主成分之氧化鋁作為觸媒。仿效前述實施例1之實驗方法，以cC4 F6 H2 (原料化合物)與氧化鋁(觸媒)之接觸時間(W／F0 )成為10g･sec／cc或40g･sec／cc之方式，使原料化合物流通於反應器中。仿效前述實施例1之實驗方法，在400℃下加熱反應器並開始脫氟化氫反應。除前述條件以外，其他係與實施例1同樣地操作來實施脫氟化氫反應、質量分析及構造解析。Examples 4 and 5 (alumina catalyst) Following the experimental method of the aforementioned Example 1, alumina with Al 2 O 3 as the main component was used as the catalyst. Following the experimental method of Example 1, the contact time (W/F 0 ) of cC 4 F 6 H 2 (raw compound) and alumina (catalyst) was 10g･sec/cc or 40g･sec/cc , so that the raw material compound is circulated in the reactor. Following the experimental method of Example 1 above, the reactor was heated at 400°C and the dehydrofluorination reaction was started. Except for the above-mentioned conditions, the dehydrofluorination reaction, mass analysis, and structural analysis were carried out in the same manner as in Example 1.
從質量分析及構造解析之結果，確認到已生成cC4 F5 H作為目的化合物。實施例4中，從cC4 F6 H2 (原料化合物)之轉化率為7.92mol%，cC4 F5 H(目的化合物)之選擇率為45.1mol%。實施例5中，轉化率：4.11mol%，選擇率：35.0mol%。From the results of mass analysis and structural analysis, it was confirmed that cC 4 F 5 H was produced as the target compound. In Example 4, the conversion rate from cC 4 F 6 H 2 (raw compound) was 7.92 mol %, and the selectivity of cC 4 F 5 H (object compound) was 45.1 mol %. In Example 5, conversion rate: 4.11 mol%, selectivity: 35.0 mol%.
實施例6~10(活性碳觸媒) 仿效前述實施例1之實驗方法，使用活性碳作為觸媒。仿效前述實施例1之實驗方法，以cC4 F6 H2 (原料化合物)與活性碳(觸媒)之接觸時間(W／F0 )成為10g･sec／cc、27g･sec／cc或47g･sec／cc之方式，使原料化合物流通於反應器中。仿效前述實施例1之實驗方法，在300℃、350℃或400℃下加熱反應器並開始脫氟化氫反應。除前述條件以外，其他係與實施例1同樣地操作來實施脫氟化氫反應、質量分析及構造解析。Examples 6 to 10 (Activated carbon catalyst) Following the experimental method of the aforementioned Example 1, activated carbon was used as a catalyst. Following the experimental method of Example 1, the contact time (W/F 0 ) of cC 4 F 6 H 2 (raw compound) and activated carbon (catalyst) was 10g･sec/cc, 27g･sec/cc or 47g ･Sec/cc method, the raw material compound is circulated in the reactor. Following the experimental method of Example 1 above, the reactor was heated at 300°C, 350°C or 400°C and the dehydrofluorination reaction was started. Except for the above-mentioned conditions, the dehydrofluorination reaction, mass analysis, and structural analysis were carried out in the same manner as in Example 1.
從質量分析及構造解析之結果，確認到已生成cC4 F5 H作為目的化合物。實施例6中，從cC4 F6 H2 (原料化合物)之轉化率為57.6mol%，cC4 F5 H(目的化合物)之選擇率為95.3mol%。實施例7中，轉化率：97.7mol%，選擇率：68.3mol%。實施例8中，轉化率：84.1mol%，選擇率：83.8mol%。實施例9中，轉化率：72.3mol%，選擇率：94.6mol%。實施例10中，轉化率：84.7mol%、選擇率：95.7mol%。From the results of mass analysis and structural analysis, it was confirmed that cC 4 F 5 H was produced as the target compound. In Example 6, the conversion rate from cC 4 F 6 H 2 (raw material compound) was 57.6 mol %, and the selectivity of cC 4 F 5 H (object compound) was 95.3 mol %. In Example 7, conversion rate: 97.7 mol%, selectivity: 68.3 mol%. In Example 8, conversion rate: 84.1 mol%, selectivity: 83.8 mol%. In Example 9, conversion rate: 72.3 mol%, selectivity: 94.6 mol%. In Example 10, the conversion rate: 84.7 mol%, and the selectivity: 95.7 mol%.
將各實施例之結果展示於以下之表1。表1中，接觸時間(W／F0 )係意指進行流通之原料氣體係以何種程度之速度來放流，即，觸媒及原料氣體進行接觸之時間。The results of each example are shown in Table 1 below. In Table 1, the contact time (W/F 0 ) means the speed at which the circulating raw material gas system is released, that is, the time during which the catalyst and the raw material gas are brought into contact.
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| WO2023049513A1 (en) * | 2021-09-27 | 2023-03-30 | Honeywell International Inc. | Fluorine substituted cyclobutene compounds, and compositions, methods and uses including same |
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| TW201202172A (en) * | 2010-04-02 | 2012-01-16 | Solvay | Process for dehydrofluorinating hydrochlorofluoroalkanes and products obtained thereby |
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| 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 |
| JPH07100673B2 (en) * | 1986-08-19 | 1995-11-01 | 旭化成工業株式会社 | Process for producing 1-fluorocyclohexene |
| KR940002713B1 (en) * | 1991-12-03 | 1994-03-31 | 주식회사 코오롱 | Process for the preparation of photosensitive diazo-type compounds |
| TWI298716B (en) * | 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 |
| JP5477290B2 (en) * | 2008-07-18 | 2014-04-23 | 日本ゼオン株式会社 | Method for producing hydrogen-containing fluoroolefin compound |
| JP5311009B2 (en) * | 2008-08-14 | 2013-10-09 | 日本ゼオン株式会社 | Method for producing hydrogen-containing fluoroolefin compound |
| JP5158366B2 (en) * | 2008-11-25 | 2013-03-06 | 日本ゼオン株式会社 | Method for producing hydrogen-containing fluoroolefin compound |
| JP5056963B2 (en) * | 2010-03-31 | 2012-10-24 | ダイキン工業株式会社 | Method for producing fluorine-containing alkane |
| WO2011140013A1 (en) * | 2010-05-03 | 2011-11-10 | Arkema Inc. | Dehydrofluorination of pentafluoroalkanes to form tetrafluoroolefins |
| CN102836722B (en) * | 2012-09-06 | 2014-10-15 | 西安近代化学研究所 | Catalyst used in preparation of fluorine-containing olefin through dehydrohalogenation of halohydrofluoroalkane and preparation method of catalyst |
| EP3040327B1 (en) * | 2013-08-26 | 2018-02-28 | Asahi Glass Company, Limited | Method for producing fluorinated compound |
| CN105107533B (en) * | 2015-08-18 | 2019-04-09 | 巨化集团技术中心 | A kind of preparation method of vapor phase dehydrofluorination catalysts |
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| JP7166911B2 (en) * | 2018-12-25 | 2022-11-08 | ダイキン工業株式会社 | Method for producing cyclobutene |
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| TW201202172A (en) * | 2010-04-02 | 2012-01-16 | Solvay | Process for dehydrofluorinating hydrochlorofluoroalkanes and products obtained thereby |
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| JP6835060B2 (en) | 2021-02-24 |
| KR20210108993A (en) | 2021-09-03 |
| WO2020137825A1 (en) | 2020-07-02 |
| KR102566765B1 (en) | 2023-08-16 |
| SG11202106891PA (en) | 2021-07-29 |
| CN113227026A (en) | 2021-08-06 |
| JP2020105114A (en) | 2020-07-09 |
| TW202035349A (en) | 2020-10-01 |
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