CN112194556A - Process for producing fluorinated vinyl compound - Google Patents
Process for producing fluorinated vinyl compound Download PDFInfo
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- CN112194556A CN112194556A CN202010650041.0A CN202010650041A CN112194556A CN 112194556 A CN112194556 A CN 112194556A CN 202010650041 A CN202010650041 A CN 202010650041A CN 112194556 A CN112194556 A CN 112194556A
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- vinyl compound
- general formula
- compound represented
- halogen atom
- fluorinated vinyl
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- -1 fluorinated vinyl compound Chemical class 0.000 title claims abstract description 119
- 238000000034 method Methods 0.000 title description 16
- 230000008569 process Effects 0.000 title description 10
- 125000005843 halogen group Chemical group 0.000 claims abstract description 66
- 125000003709 fluoroalkyl group Chemical group 0.000 claims abstract description 58
- 229910001515 alkali metal fluoride Inorganic materials 0.000 claims abstract description 54
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 42
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 41
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 26
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims description 77
- 239000007789 gas Substances 0.000 claims description 39
- 238000004519 manufacturing process Methods 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 25
- 239000003054 catalyst Substances 0.000 claims description 18
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 17
- 239000011737 fluorine Substances 0.000 claims description 17
- 238000005530 etching Methods 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 4
- 239000003507 refrigerant Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 28
- 229920002554 vinyl polymer Polymers 0.000 abstract 1
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 22
- 239000002994 raw material Substances 0.000 description 13
- 239000012071 phase Substances 0.000 description 12
- 239000011148 porous material Substances 0.000 description 11
- 239000000758 substrate Substances 0.000 description 11
- 229910052801 chlorine Inorganic materials 0.000 description 10
- 125000001309 chloro group Chemical group Cl* 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 10
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 9
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 239000011698 potassium fluoride Substances 0.000 description 6
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229910015900 BF3 Inorganic materials 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 235000003270 potassium fluoride Nutrition 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 238000004438 BET method Methods 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007792 gaseous phase Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000012916 structural analysis Methods 0.000 description 2
- 229950011008 tetrachloroethylene Drugs 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- 229910020323 ClF3 Inorganic materials 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910007161 Si(CH3)3 Inorganic materials 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005796 dehydrofluorination reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 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
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 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
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001256 stainless steel alloy Inorganic materials 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 239000013598 vector Substances 0.000 description 1
- 238000006886 vinylation reaction Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/12—Fluorides
-
- B01J35/617—
-
- B01J35/635—
-
- B01J35/657—
Abstract
Reacting CHR in the presence of alkali metal fluoride1＝CXR3[ in the formula, R1Represents a hydrogen atom, a halogen atom, an alkyl group or a fluoroalkyl group. R3Represents a halogen atom, an alkyl group or a fluoroalkyl group. Wherein R is3When it is fluoroalkyl, R1Is a halogen atom, an alkyl group or a fluoroalkyl group. X represents a halogen atom other than a fluorine atom.]The halogenated vinyl compound can be reacted to obtain CHR with high yield and high selectivity1＝CFR2[ in the formula, R1Represents a hydrogen atom, a halogen atom, an alkyl group or a fluoroalkyl group. R2Represents a halogen atom, an alkyl group or a fluoroalkyl group. Wherein R is2When it is fluoroalkyl, R1Is a halogen atom, an alkyl group or a fluoroalkyl group.]Fluorinated vinyl compounds are shown.
Description
Technical Field
The present invention relates to a method for producing a fluorinated vinyl compound.
Background
When a halogen atom other than the fluorine atom bonded to the carbon atom of SP2 in the halogenated vinyl compound is substituted by a fluorine atom,for example, for tetrachloroethylene (PCE), it is also known to utilize hydrogen fluoride and boron trifluoride (BF)3) A method of fluorinating a chlorine atom (for example, see non-patent document 1).
Documents of the prior art
Non-patent document
Non-patent document 1: journal of American Chemical Society,1948,70(2), pp 758-.
Disclosure of Invention
Technical problem to be solved by the invention
The purpose of the present invention is to provide a method capable of obtaining a fluorinated vinyl compound with high yield and high selectivity.
Technical solution for solving technical problem
The present invention includes the following configurations.
Item 1. a method for producing a fluorinated vinyl compound represented by the general formula (1), which comprises:
a reaction step of reacting a halogenated vinyl compound represented by the general formula (2) in the presence of an alkali metal fluoride to obtain a fluorinated vinyl compound represented by the general formula (1),
CHR1＝CFR2 (1)
[ in the formula, R1Represents a hydrogen atom, a halogen atom, an alkyl group or a fluoroalkyl group. R2Represents a halogen atom, an alkyl group or a fluoroalkyl group. Wherein R is2When it is fluoroalkyl, R1Is a halogen atom, an alkyl group or a fluoroalkyl group.]
CHR1＝CXR3 (2)
[ in the formula, R1Represents a hydrogen atom, a halogen atom, an alkyl group or a fluoroalkyl group. R3Represents a halogen atom, an alkyl group or a fluoroalkyl group. Wherein R is3When it is fluoroalkyl, R1Is a halogen atom, an alkyl group or a fluoroalkyl group. X represents a halogen atom other than a fluorine atom.]
Item 2. the production method according to item 1, wherein the fluorinated vinyl compound represented by the general formula (1) is a fluorinated vinyl compound represented by the general formula (1A):
[ in the formula, R1And R2The meaning of (a) is the same as above.]
Item 3. the production method according to item 1 or 2, wherein the halogenated vinyl compound represented by the above general formula (2) is a halogenated vinyl compound represented by the general formula (2A):
[ in the formula, R1、R3And X have the same meanings as described above.]
The process according to any one of items 1 to 3, wherein the alkali metal fluoride has a specific surface area of 500 to 2000m2/g。
The process according to any one of claims 1 to 4, wherein the alkali metal fluoride is supported on a carrier.
The process according to item 6, wherein the total amount of the carrier and the alkali metal fluoride is 100% by mass, and the content of the alkali metal fluoride is 0.1 to 75% by mass.
The process according to any one of claims 1 to 6, wherein the reaction step is carried out in the presence of a fluorine-containing gas.
Item 8 the production method according to any one of items 1 to 7, wherein in the reaction step, a contact time (W/F) of the halogenated vinyl compound with respect to the catalyst containing the alkali metal fluoride is 5 to 200g sec/cc.
The process according to any one of claims 1 to 8, wherein the reaction temperature in the reaction step is 200 to 500 ℃.
Item 10. A composition containing a fluorinated vinyl compound represented by the general formula (1A) and an alkyne compound represented by the general formula (3),
[ in the formula, R1Represents a hydrogen atom, a halogen atom, an alkyl group or a fluoroalkyl group. R2Represents a halogen atom, an alkyl group or a fluoroalkyl group. Wherein R is2When it is fluoroalkyl, R1Is a halogen atom, an alkyl group or a fluoroalkyl group.]
R1－C≡C－R2 (3)
[ in the formula, R1And R2The meaning of (a) is the same as above.]
The composition according to item 11, 10, wherein the total amount of the composition is 100 mol%, the content of the fluorinated vinyl compound represented by the general formula (1) is 60 to 99.9 mol%, and the content of the alkyne compound represented by the general formula (3) is 0.1 to 20 mol%.
Item 12 the composition according to item 10 or 11, wherein the fluorinated vinyl compound represented by the above general formula (1A) comprises a difluorovinyl compound represented by the general formula (1A1) and a fluorinated vinyl compound represented by the general formula (1A2),
[ in the formula, R1The meaning of (a) is the same as above.]
[ in the formula, R1The meaning of (a) is the same as above. X1Represents a halogen atom other than a fluorine atom.]
The composition according to item 12, wherein the total amount of the composition is 100 mol%, the content of the difluorovinyl compound represented by the general formula (1A1) is 40 to 98 mol%, and the content of the fluorinated vinyl compound represented by the general formula (1A2) is 2 to 30 mol%.
Item 14. the composition of any one of items 10 to 13, which is used as a cleaning gas, an etching gas, a refrigerant, or a building block (building block) for organic synthesis.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a fluorinated vinyl compound can be obtained in a high yield and with a high selectivity.
Detailed Description
In the present specification, "containing" is a concept including any of "containing (contains)", "consisting essentially of only … (consistency orientation of)", and "consisting of only … (consistency of)". In the present specification, the numerical range of "a to B" means a range from a to B.
In the present invention, the "selectivity" refers to the ratio (mol%) of the total molar amount of the target compound contained in the effluent gas from the reactor outlet to the total molar amount of the compounds other than the raw material compound in the effluent gas.
In the present invention, the "conversion" means a ratio (mol%) of a total molar amount of compounds other than the raw material compound contained in the effluent gas from the outlet of the reactor to a molar amount of the raw material compound supplied to the reactor.
In the present invention, the "yield" refers to the ratio (mol%) of the total molar amount of the target compound contained in the effluent gas from the reactor outlet relative to the molar amount of the raw material compound supplied to the reactor.
1. Process for producing fluorinated vinyl compound
The method for producing a fluorinated vinyl compound of the present invention is a method for producing a fluorinated vinyl compound represented by general formula (1), and comprises:
a reaction step of reacting a halogenated vinyl compound represented by the general formula (2) in the presence of an alkali metal fluoride to obtain a fluorinated vinyl compound represented by the general formula (1),
CHR1＝CFR2 (1)
[ in the formula, R1Represents a hydrogen atom, a halogen atom, an alkyl group or a fluoroalkyl group. R2Represents a halogen atom, an alkyl group or a fluoroalkyl group. Wherein R is2When it is fluoroalkyl, R1Is a halogen atom, an alkyl group or a fluoroalkyl group.]
CHR1＝CXR3 (2)
[ in the formula, R1Represents a hydrogen atom, a halogen atom, an alkyl group or a fluoroalkyl group. R3Represents a halogen atom, an alkyl group or a fluoroalkyl group. Wherein R is3When it is fluoroalkyl, R1Is a halogen atom, an alkyl group or a fluoroalkyl group. X represents a halogen atom other than a fluorine atom.]
Conventionally, fluorine atoms have been introduced by performing a hydrogen fluoride addition reaction and then a dehydrohalogenation reaction. This method requires not only a single 2-stage reaction step, but also a dehydrofluorination reaction which occurs simultaneously with the dehydrohalogenation reaction to produce a large amount of by-products, and therefore, the selectivity of the target product is low. Further, as in non-patent document 1, it is also known to use hydrogen fluoride and boron trifluoride (BF) for tetrachloroethylene (PCE)3) The method of fluorinating a chlorine atom, however, the yield at this time was only about 20%.
According to the present invention, as described above, a fluorinated vinyl compound can be obtained in a single step and with high yield and high selectivity by reacting a halogenated vinyl compound having a halogen atom other than a fluorine atom as a substrate in the presence of an alkali metal fluoride.
(1-1) halogenated vinyl Compound
As described above, the halogenated vinyl compound as a substrate usable in the production method of the present invention is a halogenated vinyl compound represented by the general formula (2):
CHR1＝CXR3 (2)
[ in the formula, R1Represents a hydrogen atom, a halogen atom, an alkyl group or a fluoroalkyl group. R3Represents a halogen atom, an alkyl group or a fluoroalkyl group. Wherein R is3When it is fluoroalkyl, R1Is a halogen atom, an alkyl group or a fluoroalkyl group. X represents a halogen atom other than a fluorine atom.]
The halogenated vinyl compound may include both cis-form and trans-form, but particularly in view of being able to produce a fluorinated vinyl compound with high conversion, yield and selectivity, the trans-form is preferred, and the halogenated vinyl compound represented by the general formula (2A) is preferred:
[ in the formula, R1、R3And X have the same meanings as described above.]
In the general formulae (2) and (2A), as R1And R3Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
In the general formulae (2) and (2A), as R1And R3Examples of the alkyl group include alkyl groups having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl groups. The alkyl group may have 1 to 6, particularly 1 to 3 substituents such as the halogen atom.
In the general formulae (2) and (2A), as R1And R3Examples of the fluoroalkyl group include fluoroalkyl groups having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms (particularly perfluoroalkyl groups) such as a trifluoromethyl group and a pentafluoroethyl group.
Wherein, in R1Is a hydrogen atom and R3In the case of a fluoroalkyl group, it is easy to synthesize an alkyne compound represented by the general formula (3) instead of the fluorinated vinyl compound represented by the general formula (1),
R1－C≡C－R2 (3)
[ in the formula, R1And R2The meaning of (a) is the same as above.]
Thus, at R3When it is fluoroalkyl, R1Is a halogen atom, an alkyl group or a fluoroalkyl group.
In the general formulae (2) and (2A), examples of the halogen atom represented by X include a chlorine atom, a bromine atom and an iodine atom.
Halogenated vinyl compounds as substrates, in particular in the context of fluorinated vinylations which can be produced with high conversions, yields and selectivitiesFrom the viewpoint of the compound, R is preferred1And R3Are each a fluoroalkyl group (particularly a perfluoroalkyl group), and preferably X is a chlorine atom.
Furthermore, R3When both X and X are halogen atoms other than fluorine atom, CHR in which only 1 halogen atom is substituted with fluorine atom can be synthesized by the reaction of the halogenated vinyl compounds represented by the above general formulae (2) and (2A)1＝CFX1Particularly a fluorinated vinyl compound represented by the general formula (1A2) and a difluorovinyl compound represented by the general formula (1A1) wherein 2 halogen atoms are replaced by fluorine atoms,
[ in the formula, R1The meaning of (a) is the same as above. X1Represents a halogen atom other than the above-mentioned fluorine atom.]
[ in the formula, R1The meaning of (a) is the same as above.]
Both of the difluorovinyl compound represented by the general formula (1A1) and the fluorinated vinyl compound represented by the general formula (1A2) are target compounds.
R is as defined above1、R3And X may be the same or different.
As the halogenated vinyl compound as the substrate satisfying the above-mentioned conditions, specifically, there can be mentioned:
These halogenated vinyl compounds can be used alone, and can also be used in combination of 2 or more. The halogenated vinyl compound can be a known or commercially available compound.
(1-2) substitution reaction
In the reaction step of reacting the halogenated vinyl compound represented by the general formula (2) in the present invention, for example, R is preferably selected from the halogenated vinyl compounds represented by the general formula (2) as the substrate1And R3All trifluoromethyl, preferably X is a chlorine atom, preferably the trans form. In addition, among the halogenated vinyl compounds represented by the general formula (2), R is also preferable as the substrate1Is a hydrogen atom, R3And X is a chlorine atom.
That is, it is preferable to obtain a fluorinated vinyl compound in one step according to the following reaction formula,
(1-3) alkali metal fluoride
The reaction step of reacting the halogenated vinyl compound represented by the general formula (2) in the present invention is a step of substituting a halogen atom with a fluorine atom in one step in the presence of an alkali metal fluoride. The alkali metal fluoride functions as a catalyst, and in particular, a fluorinated vinyl compound can be produced with high conversion, yield and selectivity.
The alkali metal fluoride is not particularly limited, but particularly in view of producing a fluorinated vinyl compound with high conversion, yield and selectivity, alkali metal fluorides of the 4 th to 7 th periods are preferable, and for example, potassium fluoride (KF), cesium fluoride (CsF) and the like are more preferable, and cesium fluoride (CsF) is further preferable. These alkali metal fluorides may be used alone, or 2 or more kinds may be used in combination.
Particularly, the specific surface area of the alkali metal fluoride is preferably 500 to 2000m from the viewpoint of producing a fluorinated vinyl compound with high conversion, yield and selectivity2A concentration of 800 to 1500m2(ii) in terms of/g. In the present invention, the specific surface area of the alkali metal fluoride is measured by the BET method. When the specific surface area of the alkali metal fluoride is in such a range, particles of the alkali metal fluorideSince the particle density is not too small, the target compound can be obtained with a higher selectivity. In addition, the conversion rate of the substrate can be further improved. As described later, the difference in specific surface area is not so large when the alkali metal fluoride is supported on the carrier, and the specific surface area when the alkali metal fluoride is supported on the carrier is preferably in the above range.
In the present invention, the substrate is contacted with the fluorine source when the reaction is carried out in a gas phase, and in this case, it is preferable that the alkali metal fluoride is contacted with the substrate in a solid state (solid phase) from the viewpoint of reactivity.
In the present invention, for example, when the gas phase continuous flow reaction is carried out, the alkali metal fluoride may be in a powder form, preferably in a pellet form, from the viewpoint of reactivity. The above-mentioned alkali metal fluoride may be used as it is or may be supported on a carrier (hereinafter, the alkali metal fluoride supported on the carrier may be referred to as "supported alkali metal fluoride"). This increases the specific surface area of the fluorine source, improves the reaction efficiency, and particularly enables the production of a fluorinated vinyl compound with high conversion, yield, and selectivity. The carrier to be carried is not particularly limited, and examples thereof include carbon, alumina, zirconia, silica (silica), titania (titania), zeolite, silica alumina, and chromium oxide. Examples of carbon include activated carbon, amorphous carbon, carbon black, and diamond. These vectors can be used alone, or in combination of 2 or more. Among them, carbon is preferable, and activated carbon is more preferable, from the viewpoint of a large specific surface area and ease of supporting the alkali metal fluoride.
When the alkali metal fluoride is supported on the carrier, the amount of the supported alkali metal fluoride is not particularly limited, and from the viewpoint of particularly enabling production of a fluorinated vinyl compound with a high conversion rate, yield and selectivity, the total amount of the alkali metal fluoride supported on the carrier is 100% by mass, and the alkali metal fluoride is preferably contained in an amount of 0.1 to 75% by mass, more preferably 1 to 60% by mass.
The volume density of the alkali metal fluoride supported on the carrier is preferably 0.01 to 10g/mL, more preferably 0.1 to 5g/mL, from the viewpoint of enabling the production of a fluorinated vinyl compound particularly with high conversion, yield and selectivity. In the present invention, the bulk density of the alkali metal fluoride carried on the carrier is measured by a bulk density measuring instrument. When the bulk density of the alkali metal fluoride supported by the carrier is in such a range, the density of the particles supporting the alkali metal fluoride is not excessively low, and therefore the target compound can be obtained with a higher selectivity. In addition, the conversion rate of the substrate can be further improved.
From the viewpoint of enabling the production of a fluorinated vinyl compound particularly with high conversion, yield and selectivity, the pore volume of the alkali metal fluoride supported on the carrier is preferably 0.1 to 1.5mL/g, more preferably 0.25 to 1.0 mL/g. In the present invention, the pore volume of the alkali metal fluoride supported by the carrier is measured by the BET method. When the pore volume of the alkali metal fluoride supported by the carrier is in such a range, the density of the particles supporting the alkali metal fluoride on the carrier is not excessively low, and therefore the target compound can be obtained with a higher selectivity. In addition, the conversion rate of the substrate can be further improved.
The average pore diameter of the alkali metal fluoride supported on the carrier is preferably 5 to 20 μm, more preferably 8 to 15 μm, from the viewpoint of particularly enabling the production of a fluorinated vinyl compound with high conversion, yield and selectivity. In the present invention, the average pore diameter of the alkali metal fluoride supported on the carrier is measured by the BET method.
(1-4) fluorine-containing gas
The alkali metal fluoride also functions as a catalyst, and in particular, a fluorinated vinyl compound can be produced with high conversion, yield and selectivity. However, the alkali metal fluoride contains a fluorine atom, and the fluorine atom is released when the fluorinated vinyl compound represented by the general formula (1) is obtained. Therefore, as the reaction proceeds for a long time, the amount of the alkali metal fluoride which can effectively function as a catalyst may decrease. Therefore, in order to supplement the fluorine atom, the reaction is preferably carried out in the presence of a gas containing fluorine.
Such a fluorine-containing gas is not particularly limited, and includes, for example, F2、HF、CFCl3、CF2Cl2、CFHCl2、CF2HCl、CF3H、NF3、IF5、IF7、FCl、ClF3And the like.
In the present invention, it is preferable that the fluorine-containing gas is blown in a gaseous state (gaseous phase) when the reaction is carried out in a gaseous phase.
(1-5) reaction temperature
In the step of reacting a halogenated vinyl compound to obtain a fluorinated vinyl compound in the present invention, the reaction temperature is preferably 200 to 500 ℃, more preferably 250 to 450 ℃, and still more preferably 300 to 400 ℃ in view of enabling the fluorinated vinyl compound to be produced particularly with high conversion, yield, and selectivity.
(1-6) reaction time
In the present invention, in the case where the reaction is carried out in a gas phase, the reaction time is, for example, a contact time (W/F) of the raw material compound (halogenated vinyl compound) with respect to the catalyst (alkali metal fluoride) [ W: weight of the alkali metal fluoride-containing catalyst (total amount of the support including the support when the support carries the alkali metal fluoride) (g), F: the flow rate (cc/sec) ] of the raw material compound (halogenated vinyl compound) is preferably 5 to 200g sec./cc, more preferably 10 to 150g sec./cc, and still more preferably 15 to 100g sec./cc. The contact time is a time during which the starting compound and the catalyst are in contact with each other.
The contact time mentioned above represents conditions for carrying out the reaction in a gas phase, particularly in a gas phase continuous flow type, and can be suitably adjusted even when the reaction is carried out in a batch type.
In the present invention, from the viewpoint that the conversion rate of the reaction is particularly high, and the fluorinated vinyl compound can be obtained with a higher yield and a high selectivity, when the reaction step is carried out in the presence of a fluorine-containing gas, the content of the fluorine-containing gas is preferably 0.1 to 10 mol, more preferably 0.5 to 5 mol, and still more preferably 1 to 2.5 mol, relative to 1 mol of the raw material compound (halogenated vinyl compound).
(1-7) reaction pressure
In the present invention, the reaction pressure for obtaining the fluorinated vinyl compound by reacting the halogenated vinyl compound is preferably-0.05 to 2MPa, more preferably-0.01 to 1MPa, and still more preferably normal pressure to 0.5MPa, from the viewpoint of particularly enabling the production of the fluorinated vinyl compound with high conversion, yield, and selectivity. In the present invention, when the pressure is not particularly indicated, it is a gauge pressure.
In the reaction of the present invention, the reactor for reacting the raw material compound (halogenated vinyl compound) in the presence of the alkali metal fluoride and, if necessary, a fluorine-containing gas is not particularly limited in shape and structure as long as it can withstand the above-mentioned temperature and pressure. Examples of the reactor include a vertical reactor, a horizontal reactor, and a multitubular reactor. Examples of the material of the reactor include glass, stainless steel, iron, nickel, and iron-nickel alloy.
(1-8) reaction example
The reaction step of reacting a halogenated vinyl compound to obtain a fluorinated vinyl compound in the present invention can be carried out in any manner of a gas-phase continuous flow method or a batch method, in which a raw material compound (halogenated vinyl compound) is continuously supplied to a reactor and a target compound (fluorinated vinyl compound) is continuously withdrawn from the reactor. If the target compound accumulates in the reactor, the elimination reaction proceeds further, and therefore, it is preferable to carry out the reaction in a gas-phase continuous flow scheme. In the reaction step of reacting a halogenated vinyl compound to obtain a fluorinated vinyl compound in the present invention, it is preferable to carry out the reaction in a gas phase, particularly in a gas phase continuous flow system using a fixed bed reactor. When the reaction is carried out in a gas-phase continuous flow mode, the apparatus, operation, and the like can be simplified, and the reaction is economically advantageous.
The atmosphere in the reaction step of reacting the halogenated vinyl compound to obtain the fluorinated vinyl compound in the present invention is preferably an inert gas atmosphere in view of suppressing deterioration of the alkali metal fluoride. Examples of the inert gas include nitrogen, helium, and argon. Among these inert gases, nitrogen gas is preferable from the viewpoint of cost reduction. The concentration of the inert gas is preferably 0 to 50 mol% of the gas component introduced into the reactor. The reaction may be performed in the presence of a fluorine-containing gas under an atmosphere of the fluorine-containing gas or under a mixed atmosphere of the inert gas and the fluorine-containing gas. The concentration of the fluorine-containing gas is preferably 0.1 to 90 mol% based on the gas component introduced into the reactor.
After completion of the reaction, the fluorinated vinyl compound represented by the general formula (1) can be obtained by purification treatment according to a conventional method, if necessary.
(1-9) target Compound
The object compound of the present invention thus obtained is a fluorinated vinyl compound represented by the general formula (1),
CHR1＝CFR2 (1)
[ in the formula, R1Represents a hydrogen atom, a halogen atom, an alkyl group or a fluoroalkyl group. R2Represents a halogen atom, an alkyl group or a fluoroalkyl group. Wherein R is2When it is fluoroalkyl, R1Is a halogen atom, an alkyl group or a fluoroalkyl group.]
The fluorinated vinyl compound may include both cis-form and trans-form, and the trans-form is preferred from the viewpoint of enabling production with high conversion, yield and selectivity, and the fluorinated vinyl compound represented by the general formula (1A) is preferred,
[ in the formula, R1And R2The meaning of (a) is the same as above.]
R in the general formulae (1) and (1A)1And R2Corresponding to R in the above general formulae (2) and (2A)1And R3. Further, R in the general formulae (2) and (2A)3When the halogen atom is a halogen atom other than a fluorine atom, the fluorinated vinyl compound as the target compound may be one containing the aboveA compound in which a halogen atom is substituted with a fluorine atom and a compound in which the halogen atom remains as it is. Thus, specifically, examples of the fluorinated vinyl compounds represented by the general formulae (1) and (1A) to be produced include
The fluorinated vinyl compound obtained in this way can be effectively used in various applications such as etching gases, cleaning gases, and organic synthesis blocks for forming the foremost fine structures of semiconductors, liquid crystals, and the like. The organic synthesis block will be described later.
2. Composition comprising a metal oxide and a metal oxide
In the above-described manner, the fluorinated vinyl compound can be obtained, and may be obtained as a composition containing the fluorinated vinyl compound represented by the general formulae (1) and (1A) and the alkyne compound represented by the general formula (3).
R1－C≡C－R2 (3)
[ in the formula, R1And R2The meaning of (a) is the same as above.]
In this case, the content of the fluorinated vinyl compound represented by the general formula (1) is preferably 60 to 99.9 mol%, more preferably 80 to 99 mol%, based on 100 mol% of the total amount of the composition of the present invention. The content of the alkyne compound represented by the general formula (3) is preferably 0.1 to 20 mol%, more preferably 0.2 to 10 mol%, based on 100 mol% of the total amount of the composition of the present invention. When the fluorinated vinyl compound represented by the general formula (1) contains both of the general formulae (1a1) and (1a2) described later, the content is the total amount thereof.
Further, as described above, R in the general formulae (2) and (2A)3When the halogen atom is a halogen atom other than a fluorine atom, the fluorine atom may be substituted for the halogen atom in the target fluorinated vinyl compoundA compound and a compound in which the halogen atom remains as it is.
Therefore, the fluorinated vinyl compounds represented by the general formulae (1) and (1A) may contain a difluorovinyl compound represented by the general formula (1A1) and a fluorinated vinyl compound represented by the general formula (1A2),
[ in the formula, R1Represents a hydrogen atom, a halogen atom, an alkyl group or a fluoroalkyl group.]
[ in the formula, R1Represents a hydrogen atom, a halogen atom, an alkyl group or a fluoroalkyl group. X1Represents a halogen atom other than a fluorine atom.]
In the general formulae (1A) and (1B), as R1It is possible to use the abovementioned radicals as X1Examples of the halogen atom other than the fluorine atom include a chlorine atom, a bromine atom and an iodine atom.
In this case, the content of the difluorovinyl compound represented by the general formula (1a1) is preferably 40 to 98 mol%, more preferably 50 to 90 mol%, based on 100 mol% of the total amount of the composition of the present invention. The content of the difluorovinyl compound represented by the general formula (1a2) is preferably 2 to 30 mol%, more preferably 3 to 20 mol%, based on 100 mol% of the total amount of the composition of the present invention.
Furthermore, according to the production method of the present invention, even in the case of obtaining the above-mentioned composition, the fluorinated vinyl compound represented by the general formula (1) can be obtained in one step, with a high conversion rate of reaction, and with a high yield and a high selectivity, and therefore, components other than the fluorinated vinyl compound represented by the general formula (1) in the composition can be reduced, and therefore, the labor for purification for obtaining the fluorinated vinyl compound represented by the general formula (1) can be reduced.
Such a composition of the invention not onlyThe etching gas can be effectively used for etching gases for forming the forefront fine structures of semiconductors, liquid crystals, and the like, and can also be effectively used for various applications such as organic synthesis blocks, cleaning gases, and the like. The organic synthesis block is a substance that can be a precursor of a compound having a highly reactive skeleton. For example, the composition of the present invention is reacted with CF3Si(CH3)3When a fluorine-containing organosilicon compound is reacted, CF can be introduced3A fluoroalkyl group such as a fluoroalkyl group, and the like to be converted into a substance which can be used as a cleaning agent or a fluorine-containing pharmaceutical intermediate.
Although the embodiments of the present invention have been described above, various modifications can be made in the embodiments and the details without departing from the spirit and scope of the claims.
Examples
The features of the present invention will be clarified by the following examples. The present invention is not limited to these examples.
Synthesis example 1: 50% CsF/AC
When the total amount of the activated carbon and cesium fluoride is 100 mass%, the activated carbon (specific surface area 1200 m) is mixed so that the amount of cesium fluoride used is 50 mass%2/g) and cesium fluoride to give a 50% CsF/AC catalyst with cesium fluoride supported on activated carbon. The specific surface area of the resulting catalyst was 600cm2(ii)/g, pore volume was 0.7mL/g, and pore diameter was 10 μm.
Synthesis example 2: 5% CsF/AC
When the total amount of the activated carbon and cesium fluoride is 100 mass%, the activated carbon (specific surface area 1200 m) is mixed so that the amount of cesium fluoride used is 5 mass%2/g) and cesium fluoride to give a 5% CsF/AC catalyst with cesium fluoride supported on activated carbon. The specific surface area of the resulting catalyst was 900cm2(ii)/g, pore volume was 0.8mL/g, and pore diameter was 10 μm.
Synthesis example 3: 5% KF/AC
When the total amount of the activated carbon and the potassium fluoride is 100 mass%, the mixture is activated so that the amount of potassium fluoride used is 5 mass%Charcoal (specific surface area 1200 m)2/g) and potassium fluoride to give a 5% KF/AC catalyst with potassium fluoride supported on activated carbon. The specific surface area of the resulting catalyst was 900cm2(ii)/g, pore volume was 0.8mL/g, and pore diameter was 10 μm.
Examples 1 to 5
In the process for producing fluorinated vinyl compounds of examples 1 to 5, R is added to a halogenated vinyl compound represented by the general formula (2) as a raw material compound1And R3A fluorinated vinyl compound was obtained according to the following reaction formula, wherein X is a chlorine atom.
10g of the catalyst obtained in Synthesis example 1, 2 or 3 was added to a SUS pipe (outer diameter: 1/2 inches) as a reaction tube. After drying at 200 ℃ for 2 hours under a nitrogen atmosphere, the pressure was set to normal pressure and CF was used3CH＝CClCF3(raw Material Compound) and catalyst contact time (W/F) of 16.0g sec/cc or 42.0g sec/cc, in the reaction tube flow CF3CH＝CClCF3(starting Compound).
The reaction is carried out in a gas phase continuous flow mode.
The reaction was started by heating the reaction tube at 300 ℃ or 400 ℃.
After the start of the reaction, the distillate was collected by a harm removal column after 1 hour.
Then, mass analysis was performed by gas chromatography/mass spectrometry (GC/MS) using a gas chromatograph (product name "GC-2014" manufactured by shimadzu corporation), and structural analysis by NMR spectroscopy was performed using NMR (product name "400 YH" manufactured by JEOL corporation).
From the results of mass analysis and structure analysis, it was confirmed that CF was produced as a target compound3CH＝CFCF3. The results are shown in Table 1.
[ TABLE 1 ]
Examples 6 to 8
In the process for producing fluorinated vinyl compounds of examples 6 to 8, R is added to a halogenated vinyl compound represented by the general formula (2) as a raw material compound1Is a hydrogen atom, R3And X is a chlorine atom, and a fluorinated vinyl compound is obtained according to the following reaction formula.
10g of the catalyst obtained in Synthesis example 1 or 3 was added to a SUS pipe (outer diameter: 1/2 inches) as a reaction tube. Drying at 200 deg.C for 2 hr under nitrogen atmosphere, and making the pressure normal pressure by CH2＝CCl2The reaction tube was allowed to flow CH so that the contact time (W/F) between the (raw material compound) and the catalyst was 10.0g sec/cc or 20.0g sec/cc2＝CCl2(starting Compound).
The reaction is carried out in a gas phase continuous flow mode.
The reaction tube was heated at 400 ℃ to start the reaction.
After the start of the reaction, the distillate was collected by a harm removal column after 1 hour.
Then, mass analysis was performed by gas chromatography/mass spectrometry (GC/MS) using a gas chromatograph (product name "GC-2014" manufactured by shimadzu corporation), and structural analysis by NMR spectroscopy was performed using NMR (product name "400 YH" manufactured by JEOL corporation).
From the results of mass analysis and structure analysis, it was confirmed that CH was produced as a target compound2CClF and CH2＝CF2. The results are shown in Table 2.
[ TABLE 2 ]
Claims (14)
1. A method for producing a fluorinated vinyl compound represented by the general formula (1), which comprises:
a reaction step of reacting a halogenated vinyl compound represented by the general formula (2) in the presence of an alkali metal fluoride to obtain a fluorinated vinyl compound represented by the general formula (1),
CHR1＝CFR2 (1)
in the formula (1), R1Represents a hydrogen atom, a halogen atom, an alkyl group or a fluoroalkyl group, R2Represents a halogen atom, an alkyl group or a fluoroalkyl group, wherein R2When it is fluoroalkyl, R1Is a halogen atom, an alkyl group or a fluoroalkyl group,
CHR1＝CXR3 (2)
in the formula (2), R1Represents a hydrogen atom, a halogen atom, an alkyl group or a fluoroalkyl group, R3Represents a halogen atom, an alkyl group or a fluoroalkyl group, wherein R3When it is fluoroalkyl, R1Is a halogen atom, an alkyl group or a fluoroalkyl group, and X represents a halogen atom other than a fluorine atom.
2. The manufacturing method according to claim 1, wherein:
the fluorinated vinyl compound represented by the general formula (1) is a fluorinated vinyl compound represented by the general formula (1A):
in the formula, R1And R2The meaning of (a) is the same as above.
3. The manufacturing method according to claim 1 or 2, characterized in that:
the halogenated vinyl compound represented by the general formula (2) is a halogenated vinyl compound represented by the general formula (2A):
in the formula, R1、R3And X have the same meanings as described above.
4. The production method according to any one of claims 1 to 3, characterized in that:
the specific surface area of the alkali metal fluoride is 500-2000 m2/g。
5. The production method according to any one of claims 1 to 4, characterized in that:
the alkali metal fluoride is supported on a carrier.
6. The manufacturing method according to claim 5, wherein:
the total amount of the support and the alkali metal fluoride is 100 mass%, and the content of the alkali metal fluoride is 0.1 to 75 mass%.
7. The production method according to any one of claims 1 to 6, characterized in that:
the reaction step is carried out in the presence of a fluorine-containing gas.
8. The manufacturing method according to any one of claims 1 to 7, characterized in that:
in the reaction step, the contact time (W/F) of the halogenated vinyl compound with respect to the catalyst containing the alkali metal fluoride is 5 to 200g sec/cc.
9. The production method according to any one of claims 1 to 8, characterized in that:
the reaction temperature in the reaction process is 200-500 ℃.
10. A composition characterized by:
containing a fluorinated vinyl compound represented by the general formula (1A) and an alkyne compound represented by the general formula (3),
in the formula (1A), R1Represents a hydrogen atom, a halogen atom, an alkyl group or a fluoroalkyl group, R2Represents a halogen atom, an alkyl group or a fluoroalkyl group, wherein R2When it is fluoroalkyl, R1Is a halogen atom, an alkyl group or a fluoroalkyl group,
R1－C≡C－R2 (3)
in the formula (3), R1And R2The meaning of (a) is the same as above.
11. The composition of claim 10, wherein:
the total amount of the composition is 100 mol%, the content of the fluorinated vinyl compound represented by the general formula (1) is 60 to 99.9 mol%, and the content of the alkyne compound represented by the general formula (3) is 0.1 to 20 mol%.
12. The composition of claim 10 or 11, wherein:
the fluorinated vinyl compound represented by the general formula (1A) contains a difluorovinyl compound represented by the general formula (1A1) and a fluorinated vinyl compound represented by the general formula (1A2),
in the formula (1A1), R1The meaning of (a) is the same as above,
in the formula (1A2), R1The meaning of (A) is the same as above, X1To representA halogen atom other than a fluorine atom.
13. The composition of claim 12, wherein:
the total amount of the composition is 100 mol%, the content of the difluorovinyl compound represented by the general formula (1A1) is 40-98 mol%, and the content of the fluorinated vinyl compound represented by the general formula (1A2) is 2-30 mol%.
14. The composition of any one of claims 10 to 13, wherein:
used as cleaning gas, etching gas, refrigerant or organic synthetic block.
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| JP2007320896A (en) * | 2006-05-31 | 2007-12-13 | Central Glass Co Ltd | Method for producing 1, 3, 3, 3-tetrafluoropropene |
| JP2009132626A (en) * | 2007-11-28 | 2009-06-18 | Central Glass Co Ltd | Method for producing 1,3,3,3-tetrafluoropropene |
| WO2010095764A1 (en) * | 2009-02-23 | 2010-08-26 | Daikin Industries, Ltd. | Process for preparing fluorine-containing alkyne compound |
| JP2010229116A (en) * | 2009-03-30 | 2010-10-14 | Nippon Zeon Co Ltd | Method for producing 2-halogeno-3-hydroperfluoroalkene compound |
| CN107614469A (en) * | 2015-05-29 | 2018-01-19 | 大金工业株式会社 | The manufacture method of Fluorine containing olefine |
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|---|---|---|---|---|
| JP2007320896A (en) * | 2006-05-31 | 2007-12-13 | Central Glass Co Ltd | Method for producing 1, 3, 3, 3-tetrafluoropropene |
| JP2009132626A (en) * | 2007-11-28 | 2009-06-18 | Central Glass Co Ltd | Method for producing 1,3,3,3-tetrafluoropropene |
| WO2010095764A1 (en) * | 2009-02-23 | 2010-08-26 | Daikin Industries, Ltd. | Process for preparing fluorine-containing alkyne compound |
| JP2010229116A (en) * | 2009-03-30 | 2010-10-14 | Nippon Zeon Co Ltd | Method for producing 2-halogeno-3-hydroperfluoroalkene compound |
| CN107614469A (en) * | 2015-05-29 | 2018-01-19 | 大金工业株式会社 | The manufacture method of Fluorine containing olefine |
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