CN117185898A - Preparation method of hexafluorobutadiene - Google Patents
Preparation method of hexafluorobutadiene Download PDFInfo
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- CN117185898A CN117185898A CN202210610373.5A CN202210610373A CN117185898A CN 117185898 A CN117185898 A CN 117185898A CN 202210610373 A CN202210610373 A CN 202210610373A CN 117185898 A CN117185898 A CN 117185898A
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- cuprous
- hexafluorobutadiene
- reaction
- zinc bromide
- catalyst
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- LGPPATCNSOSOQH-UHFFFAOYSA-N 1,1,2,3,4,4-hexafluorobuta-1,3-diene Chemical compound FC(F)=C(F)C(F)=C(F)F LGPPATCNSOSOQH-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 81
- AYCANDRGVPTASA-UHFFFAOYSA-N 1-bromo-1,2,2-trifluoroethene Chemical group FC(F)=C(F)Br AYCANDRGVPTASA-UHFFFAOYSA-N 0.000 claims abstract description 41
- HUIOAUQSDRXHEQ-UHFFFAOYSA-M FC(F)=C(F)[Zn]Br Chemical compound FC(F)=C(F)[Zn]Br HUIOAUQSDRXHEQ-UHFFFAOYSA-M 0.000 claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- 150000003839 salts Chemical class 0.000 claims abstract description 17
- 238000005859 coupling reaction Methods 0.000 claims abstract description 15
- 230000009471 action Effects 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims description 47
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 16
- 239000003960 organic solvent Substances 0.000 claims description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- RFKZUAOAYVHBOY-UHFFFAOYSA-M copper(1+);acetate Chemical compound [Cu+].CC([O-])=O RFKZUAOAYVHBOY-UHFFFAOYSA-M 0.000 claims description 4
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 4
- WIVXEZIMDUGYRW-UHFFFAOYSA-L copper(i) sulfate Chemical compound [Cu+].[Cu+].[O-]S([O-])(=O)=O WIVXEZIMDUGYRW-UHFFFAOYSA-L 0.000 claims description 4
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 4
- 229940112669 cuprous oxide Drugs 0.000 claims description 4
- 150000004820 halides Chemical class 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 3
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- PDZKZMQQDCHTNF-UHFFFAOYSA-M copper(1+);thiocyanate Chemical compound [Cu+].[S-]C#N PDZKZMQQDCHTNF-UHFFFAOYSA-M 0.000 claims description 2
- AQMRBJNRFUQADD-UHFFFAOYSA-N copper(I) sulfide Chemical compound [S-2].[Cu+].[Cu+] AQMRBJNRFUQADD-UHFFFAOYSA-N 0.000 claims description 2
- 150000004767 nitrides Chemical class 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 38
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 25
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 24
- 229910052757 nitrogen Inorganic materials 0.000 description 19
- 239000007788 liquid Substances 0.000 description 18
- 239000000203 mixture Substances 0.000 description 17
- 239000003153 chemical reaction reagent Substances 0.000 description 16
- 238000004817 gas chromatography Methods 0.000 description 16
- -1 zinc trifluorovinylbromide Chemical compound 0.000 description 16
- 238000010168 coupling process Methods 0.000 description 14
- 239000011701 zinc Substances 0.000 description 13
- 229910052725 zinc Inorganic materials 0.000 description 13
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 9
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 230000008878 coupling Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 4
- 238000005695 dehalogenation reaction Methods 0.000 description 4
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 4
- RDIGOBBBXBALIC-UHFFFAOYSA-L [Zn+2].[Br-].[Br-].FC=C(F)F Chemical compound [Zn+2].[Br-].[Br-].FC=C(F)F RDIGOBBBXBALIC-UHFFFAOYSA-L 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 2
- IRHYACQPDDXBCB-UHFFFAOYSA-N 1,2,3,4-tetrachloro-1,1,2,3,4,4-hexafluorobutane Chemical compound FC(F)(Cl)C(F)(Cl)C(F)(Cl)C(F)(F)Cl IRHYACQPDDXBCB-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 2
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 2
- YRJQVLUPWDWHHE-UHFFFAOYSA-N copper(1+);1,1,2-trifluoroethene Chemical compound [Cu+].F[C-]=C(F)F YRJQVLUPWDWHHE-UHFFFAOYSA-N 0.000 description 2
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 2
- 229940045803 cuprous chloride Drugs 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- WXGNWUVNYMJENI-UHFFFAOYSA-N 1,1,2,2-tetrafluoroethane Chemical compound FC(F)C(F)F WXGNWUVNYMJENI-UHFFFAOYSA-N 0.000 description 1
- JLGADZLAECENGR-UHFFFAOYSA-N 1,1-dibromo-1,2,2,2-tetrafluoroethane Chemical compound FC(F)(F)C(F)(Br)Br JLGADZLAECENGR-UHFFFAOYSA-N 0.000 description 1
- ORENISVHLBKRCV-UHFFFAOYSA-N 1-chloro-1,2,2-trifluoroethene;zinc Chemical compound [Zn].FC(F)=C(F)Cl ORENISVHLBKRCV-UHFFFAOYSA-N 0.000 description 1
- KWXXMLHQBFNLOR-UHFFFAOYSA-N 3,4-dichloro-1,1,2,3,4,4-hexafluorobut-1-ene Chemical compound FC(F)=C(F)C(F)(Cl)C(F)(F)Cl KWXXMLHQBFNLOR-UHFFFAOYSA-N 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- AFLIPEBFYDIRNJ-UHFFFAOYSA-N FC(F)=C(F)[Zn] Chemical compound FC(F)=C(F)[Zn] AFLIPEBFYDIRNJ-UHFFFAOYSA-N 0.000 description 1
- QZRGKCOWNLSUDK-UHFFFAOYSA-N Iodochlorine Chemical compound ICl QZRGKCOWNLSUDK-UHFFFAOYSA-N 0.000 description 1
- BOUARFRGCVOQDU-UHFFFAOYSA-M [Br-].[Zn+]C=C Chemical compound [Br-].[Zn+]C=C BOUARFRGCVOQDU-UHFFFAOYSA-M 0.000 description 1
- BAWRBXGQZOIZMJ-UHFFFAOYSA-M [Cl-].FC(F)=C(F)[Zn+] Chemical compound [Cl-].FC(F)=C(F)[Zn+] BAWRBXGQZOIZMJ-UHFFFAOYSA-M 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000009270 solid waste treatment Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Abstract
The invention discloses a preparation method of hexafluorobutadiene, which comprises the following steps: under the action of a catalyst, the trifluorobromoethylene and the trifluorovinyl zinc bromide are subjected to coupling reaction in a reactor to obtain hexafluorobutadiene, wherein the catalyst is a cuprous salt catalyst, and the reaction temperature is 25-150 ℃. The invention has the advantages of simple operation, low raw material cost, high product yield and the like.
Description
Technical Field
The invention relates to fluorine-containing electronic gas, in particular to a preparation method of hexafluorobutadiene.
Background
Hexafluorobutadiene, chemical name: 1,2,3, 4-Hexafluorobutadiene, called Hexafluorobutadiene, called perfluorobutadiene, HFBD for short, has a low fluorocarbon ratio (F: C=1.5), ODP of 0, GWP 100 290, the time of existence in the atmosphere is only 1.9d, the environment performance is excellent, and the etching gas is an etching gas with extremely low greenhouse effect and environmental protection, and is also an important synthesis intermediate. The global use amount of hexafluorobutadiene is large, and the hexafluorobutadiene is commonly used for high-end chip etching, and the preparation and purification process is a research hot spot in recent years.
At present, the preparation process of hexafluorobutadiene mainly comprises the following steps:
1. zinc reagent coupling process
The patent CN110590495A of Hangzhou fluorine electronic materials of Fujian province discloses a preparation method of hexafluorobutadiene, which specifically comprises the following steps: 1) Taking trifluorochloroethylene as a raw material to perform hydrogenation reaction under the action of a catalyst to obtain trifluoroethylene; 2) Adding trifluoroethylene and liquid bromine to obtain 1, 2-dibromo-1, 2-trifluoroethane, and then dehydrobrominating alkali liquor to obtain trifluorobromoethylene; 3) Reacting trifluorobromoethylene in a reaction kettle filled with a solvent, an initiator and zinc powder to generate zinc reagent trifluorovinyl zinc bromide; 4) And (3) carrying out a coupling reaction on the trifluoro vinyl zinc bromide under the action of copper chloride and copper bromide to obtain hexafluorobutadiene.
Patent CN104844411A of Beijing Yu Ji technology development Co., ltd discloses a method for preparing hexafluorobutadiene by using tetrafluoroethane (HFC-134 a) as raw material, which comprises the steps of preparing intermediate trifluoro vinyl zinc, and then adding zinc reagent into Fe 3+ And coupling under the action of the catalyst to obtain hexafluorobutadiene.
Burton's group of topics (Tetrahedron Lett.43 (2002) 2731-2733) discloses that HFC-134a is used as a starting material to react with zinc chloride in the presence of a strong base such as LDA (lithium diisopropylamide) to give zinc trifluorovinyl chloride, which is then coupled to produce hexafluorobutadiene under the catalysis of copper bromide.
However, the zinc reagent coupling process needs to synthesize the initial raw materials in multiple steps to obtain a high-activity zinc reagent, and finally the zinc reagent (trifluoro vinyl zinc chloride/trifluoro vinyl zinc bromide) is subjected to self-coupling under the action of an excessive metal coupling catalyst to prepare hexafluorobutadiene, so that two molecules of zinc reagent are needed in the self-coupling process to generate one molecule of hexafluorobutadiene, the disadvantage of low unit volume yield is caused, and meanwhile, the excessive coupling catalyst is needed in the production process, so that the raw material cost and the solid waste treatment cost are increased.
2. Zinc powder dehalogenation process
The seventh and eighth institute of technology patent CN112250541A of China shipping heavy industry group company discloses a method for preparing hexafluorobutadiene by dehalogenation of zinc powder, which specifically comprises the following steps: 1) Iodine monochloride and chlorotrifluoroethylene react to prepare 1, 2-dichloro-2-iodine-1, 2-trifluoroethane; 2) 1, 2-dichloro-2-iodo-1, 2-trifluoroethane and activated zinc are put into a reactor, and then polar base solution and ester catalyst are added for reaction to prepare 1,2,3, 4-tetrachloro hexafluorobutane; 3) Dehalogenation of 1,2,3, 4-tetrachloro hexafluorobutane and zinc powder produced hexafluorobutadiene.
Patent CN113061074A of Shanghai chemical industry institute of Limited discloses a method for obtaining hexafluorobutadiene product by taking 3, 4-dichloro hexafluoro-1-butene as raw material and performing zinc powder dechlorination reaction in organic solvent.
However, the zinc powder in the zinc powder dehalogenation process needs excessive feeding, so that waste is caused to a certain extent on the zinc powder, and the production cost is increased. More importantly, zinc powder has high density and is insoluble in a solvent, is easily unevenly distributed in the solution, and part of zinc powder can be deposited at the bottom of a reactor to cause blockage, so that the post-treatment is very difficult.
3. Coupling process of trifluoro bromoethylene and zinc reagent
Patent CN111187145A of Guangdong electric power science institute of electric power company discloses that 1, 1-dibromotetrafluoroethane is used as a raw material to react with zinc powder in the presence of aluminum trihalide in an aprotic polar solvent to generate an organic zinc reagent; then under the action of palladium catalyst, zinc reagent and trifluorobromoethylene react to produce hexafluorobutadiene.
Patent CN111320526A of Zhejiang blue sky environmental protection high tech Co., ltd discloses a method for preparing hexafluorobutadiene by coupling trifluorobromoethylene and trifluorovinyl zinc bromide under the action of a composite catalyst of noble metal palladium salt and an organic phosphorus compound.
However, coupling of trifluoroethylene and zinc reagents requires the use of precious metal palladium, which is expensive and difficult to recycle in the reaction, thus resulting in high production costs.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of hexafluorobutadiene, which has the advantages of simple reaction process, low raw material cost and high product yield and is suitable for industrial production.
The invention aims at realizing the following technical scheme:
a process for preparing hexafluorobutadiene, said process comprising: under the action of a catalyst, trifluoroethylene and trifluoroethylene zinc bromide are heated in a reactor and then undergo a coupling reaction to obtain hexafluorobutadiene, wherein the reaction formula is as follows:
the reaction is carried out under heating at a reaction temperature of 25 to 150 ℃, preferably at a reaction temperature of 60 to 130 ℃, more preferably at a reaction temperature of 80 to 110 ℃, most preferably at a reaction temperature of 80 to 100 ℃.
The catalyst is a cuprous salt catalyst and is selected from at least one of cuprous halide, cuprous sulfate, cuprous carbonate, cuprous acetate, cuprous nitride, cuprous cyanide, cuprous oxide, cuprous sulfide, cuprous thiocyanate or cuprous trifluoromethanesulfonic acid. Preferably, the catalyst is selected from at least one of cuprous halide, cuprous sulfate, cuprous carbonate, cuprous acetate, cuprous cyanide, cuprous oxide or cuprous triflate. More preferably, the catalyst is selected from at least one of cuprous bromide, cuprous chloride, cuprous iodide or cuprous cyanide.
Unlike the coupling reaction of 2 parts of trifluoro vinyl zinc bromide in low temperature, under the action of the cuprous salt catalyst, 1 part of trifluoro vinyl zinc bromide can react with 1 part of trifluoro vinyl bromide in a coupling way under the heating state, thereby improving the utilization rate of zinc reagent, reducing the cost and reducing the amount of three wastes.
In the reaction process of the invention, the cuprous salt catalyst can convert the trifluoro vinyl zinc bromide reagent into the trifluoro vinyl copper reagent, and the trifluoro vinyl copper reagent with higher activity is utilized to be more beneficial to the occurrence of trifluoro vinyl bromide coupling reaction.
Specifically, the molar ratio of the trifluoro vinyl zinc bromide to the cuprous salt catalyst is 1 (0.05-2.0), and the preferable molar ratio is 1: (0.05 to 1.2), more preferably the molar ratio is 1: (0.05-0.2).
Further, the molar ratio of the trifluorobromoethylene to the trifluorovinylzinc bromide is (0.8 to 10): 1, preferably (1 to 8): 1, and more preferably (1 to 2): 1.
In the reaction process of the invention, the trifluoro vinyl zinc bromide is added into the reactor in the form of trifluoro vinyl zinc bromide solution, wherein the trifluoro vinyl zinc bromide solution is formed by dissolving trifluoro vinyl zinc bromide in an organic solvent, and the organic solvent is a polar aprotic solvent. Preferably, the organic solvent is selected from at least one of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, 1, 3-dimethyl-2-imidazolidinone, N-methylpyrrolidone, diethyl ether, acetonitrile or tetrahydrofuran. More preferably, the organic solvent is selected from at least one of N, N-dimethylformamide, N-dimethylacetamide or tetrahydrofuran.
In order to ensure the stability of the raw material trifluoroethylene zinc bromide, the decomposition of the trifluoroethylene zinc bromide into trifluoroethylene is avoided, and the introduced trifluoroethylene is gas, wherein the water content of the trifluoroethylene gas is lower than 2000ppm, preferably lower than 1000ppm, and more preferably lower than 500ppm.
Further, in the trifluoro vinyl zinc bromide solution, the mass ratio of trifluoro vinyl zinc bromide to the organic solvent is 1 (3-12), preferably 1 (3-5).
In the reaction process of the present invention, it is preferable to conduct the reaction in the presence of an inert gas selected from at least one of nitrogen, argon and helium. When the reaction system is under the protection of inert gas, the inert gas can prevent the cuprous salt catalyst from being oxidized, keep the catalytic activity and simultaneously prevent oxygen from entering to cause the decomposition of the trifluorobromoethylene.
According to the preparation method of the hexafluorobutadiene, the preparation method sequentially comprises the following steps:
1) Adding cuprous salt catalyst into the reactor, wherein the cuprous salt catalyst is solid or solid powder or cuprous salt solution;
2) Adding a trifluoro vinyl zinc bromide solution into the reactor;
3) And introducing trifluorobromoethylene into the reactor, and heating to the reaction temperature to perform the reaction.
In the step 3), the reaction temperature is preferably 80-130 ℃, and the reaction time is preferably 6h. After the reaction is finished, the temperature is raised to 130 ℃, all the gas is distilled off, and the gas is collected by using liquid nitrogen to cool hydrazine, and the product hexafluorobutadiene is in the collected gas.
The preparation method of hexafluorobutadiene can be batch reaction or continuous reaction, and the correspondingly adopted reactor is a kettle reactor or a tubular reactor.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention adopts the cheap and easily available cuprous salt catalyst, realizes the preparation of hexafluorobutadiene by coupling the trifluorovinyl bromide and the trifluorovinyl zinc bromide under the heating condition, and compared with the process for preparing hexafluorobutadiene by self-coupling of the trifluorovinyl zinc bromide, the invention not only reduces the dosage of one molecule of zinc reagent, reduces the cost of raw materials and the amount of three wastes, but also improves the utilization rate of raw materials and the yield of products.
2. The coupling process has the advantages of simple reaction process, cheap and easily available raw materials and suitability for industrial amplification.
Detailed Description
The invention will be further illustrated with reference to the following specific examples, without limiting the invention to these specific embodiments. It will be appreciated by those skilled in the art that the invention encompasses all alternatives, modifications and equivalents as may be included within the scope of the claims.
Example 1
The embodiment provides a preparation method of hexafluorobutadiene, which comprises the following steps:
5.7g (0.04 mol) of cuprous bromide is added into a 1000mL reaction kettle, 450g (mass fraction 20%,0.4 mol) of N, N-dimethylformamide solution of trifluoro vinyl zinc bromide is added into the reaction kettle, 77.2g (0.48 mol, water content less than 500 ppm) of trifluoro vinyl bromide is introduced, and after the trifluoro vinyl bromide is introduced, the reaction temperature is controlled to 80 ℃, and the reaction is kept for 6 hours. After the reaction, the temperature is raised to 130 ℃, all the gas is distilled off, 57.3g of gas is collected by a liquid nitrogen cold trap, and the gas composition is as follows through gas chromatography analysis: 85.54% of hexafluorobutadiene, 10.20% of trifluorobromoethylene, 3.56% of trifluoroethylene and 0.70% of other components. Calculated as zinc trifluorovinylbromide, the reaction yield was 75.6%.
Example 2
The operation of this embodiment is identical to that of embodiment 1, except that: cuprous salt catalyst replaced cuprous bromide 5.7g (0.04 mol) with cuprous chloride 4.0g (0.04 mol) with the other conditions unchanged. After the reaction was completed, 55.6g of gas was collected by a liquid nitrogen cold trap, and analyzed by gas chromatography, the composition of the gas was as follows: 81.30% of hexafluorobutadiene, 11.50% of trifluorobromoethylene, 4.70% of trifluoroethylene and 2.50% of other components.
The reaction yield was calculated to be 69.7% based on the trifluorovinyl zinc bromide.
Example 3
The operation of this embodiment is identical to that of embodiment 1, except that: cuprous salt catalyst used 7.6g (0.04 mol) of cuprous iodide instead of 5.7g (0.04 mol) of cuprous bromide, with other conditions unchanged. After the reaction was completed, 56.6g of gas was collected by a liquid nitrogen cold trap, and analyzed by gas chromatography, the composition of the gas was as follows: 83.75% of hexafluorobutadiene, 11.06% of trifluorobromoethylene, 3.22% of trifluoroethylene and 1.97% of other components.
Calculated as zinc trifluorovinylbromide, the reaction yield was 73.1%.
Example 4
The operation of this embodiment is identical to that of embodiment 1, except that: cuprous salt catalyst used 3.6g (0.04 mol) of cuprous cyanide instead of 5.7g (0.04 mol) of cuprous bromide, with the other conditions unchanged. After the reaction was completed, 52.7g of gas was collected by a liquid nitrogen cold trap, and analyzed by gas chromatography, the composition of the gas was as follows: 76.20% of hexafluorobutadiene, 15.6% of trifluorobromoethylene, 3.50% of trifluoroethylene and 4.70% of other components.
The reaction yield was calculated to be 62.0% based on the zinc trifluorovinyl bromide.
Example 5
The operation of this embodiment is identical to that of embodiment 1, except that: the trifluorovinyl zinc bromide solution adopts 450g (mass fraction 20%,0.4 mol) of dimethyl sulfoxide solution of trifluorovinyl zinc bromide instead of 450g (mass fraction 20%,0.4 mol) of N, N-dimethylformamide solution of trifluorovinyl zinc bromide, and other conditions are unchanged. After the reaction was completed, 50.0g of gas was collected by a liquid nitrogen cold trap, and analyzed by gas chromatography, the composition of the gas was as follows: 75.60% of hexafluorobutadiene, 15.30% of trifluorobromoethylene, 3.44% of trifluoroethylene and 5.66% of other components.
The reaction yield was calculated to be 58.3% based on the zinc trifluorovinyl bromide.
Example 6
5.7g (0.04 mol) of cuprous bromide is added into a 1000mL reaction kettle, 450g (mass fraction 20%,0.4 mol) of N, N-dimethylformamide solution of trifluoro vinyl zinc bromide is added into the reaction kettle, 150g of N, N-dimethylformamide solution is continuously added, 77.2g (0.48 mol) of trifluoro vinyl bromide is added, and after the trifluoro vinyl bromide is completely introduced, the reaction temperature is controlled at 80 ℃, and the reaction is kept for 6 hours. After the reaction, the temperature is raised to 130 ℃, all the gas is distilled off, 59.4g of gas is collected by a liquid nitrogen cold trap, and the gas composition is as follows through gas chromatography analysis: 88.30% of hexafluorobutadiene, 7.43% of trifluorobromoethylene, 3.67% of trifluoroethylene and 0.60% of other components.
Calculated as zinc trifluorovinylbromide, the reaction yield was 80.9%.
Example 7
5.7g (0.04 mol) of cuprous bromide is added into a 1000mL reaction kettle, 450g (mass fraction 20%,0.4 mol) of N, N-dimethylformamide solution of trifluoro vinyl zinc bromide is added into the reaction kettle, 450g of N, N-dimethylformamide solution is continuously added, 77.2g (0.48 mol, water content less than 500 ppm) of trifluoro vinyl bromide is introduced, and after the trifluoro vinyl bromide is introduced, the reaction temperature is controlled to 80 ℃, and the reaction is kept for 6 hours. After the reaction, the temperature is raised to 130 ℃, all the gas is distilled off, 60.2g of gas is collected by a liquid nitrogen cold trap, and the gas composition is as follows through gas chromatography analysis: 89.40% of hexafluorobutadiene, 5.50% of trifluorobromoethylene, 4.70% of trifluoroethylene and 0.40% of other components.
Calculated as zinc trifluorovinyl bromide, the reaction yield was 83.1%.
Example 8
The operation of this embodiment is identical to that of embodiment 1, except that: the amount of trifluoroethylene was increased from 77.2g to 128.7g, the other conditions being unchanged. After the reaction was completed, 102.6g of gas was collected by a liquid nitrogen cold trap, and analyzed by gas chromatography, the composition of the gas was as follows: 56.00% of hexafluorobutadiene, 40.00% of trifluorobromoethylene, 2.10% of trifluoroethylene and 1.90% of other components.
Calculated as zinc trifluorovinyl bromide, the reaction yield was 88.7%
Example 9
The operation of this embodiment is identical to that of embodiment 1, except that: the reaction temperature is increased from 80 ℃ to 110 ℃ and other conditions are unchanged. After the reaction was completed, 54.2g of gas was collected by a liquid nitrogen cold trap, and analyzed by gas chromatography, the composition of the gas was as follows: 55.30% of hexafluorobutadiene, 16.3% of trifluorobromoethylene, 9.8% of trifluoroethylene and 18.6% of other components.
Calculated as zinc trifluorovinyl bromide, the reaction yield was 46.2%.
Example 10
The operation of this embodiment is identical to that of embodiment 1, except that: the reaction temperature is increased from 80 ℃ to 100 ℃ and other conditions are unchanged. After the reaction was completed, 55.2g of gas was collected by a liquid nitrogen cold trap, and analyzed by gas chromatography, the composition of the gas was as follows: 80.30% of hexafluorobutadiene, 8.70% of trifluorobromoethylene, 8.8% of trifluoroethylene and 2.2% of other components.
Calculated as zinc trifluorovinyl bromide, the reaction yield was 68.4%.
Example 11
The operation of this embodiment is identical to that of embodiment 1, except that: the amount of cuprous bromide was 28.7g (0.2 mol) with the other conditions unchanged. After the reaction was completed, 60.3g of gas was collected by a liquid nitrogen cold trap, and analyzed by gas chromatography, the composition of the gas was as follows: 87.55% of hexafluorobutadiene, 9.50% of trifluorobromoethylene, 2.75% of trifluoroethylene and 0.2% of other components.
Calculated as zinc trifluorovinyl bromide, the reaction yield was 81.5%.
Example 12
The operation of this embodiment is identical to that of embodiment 1, except that: the amount of cuprous bromide was 57.4g (0.4 mol) with the other conditions unchanged. After the reaction was completed, 62.4g of gas was collected by a liquid nitrogen cold trap, and analyzed by gas chromatography, the composition of the gas was as follows: 90.55% of hexafluorobutadiene, 6.50% of trifluorobromoethylene, 2.20% of trifluoroethylene and 0.75% of other components.
Calculated as zinc trifluorovinyl bromide, the reaction yield was 87.2%.
Comparative example 1
The operation of this comparative example is the same as in example 1, except that: copper oxide 3.2g (0.04 mol) was used instead of the cuprous salt catalyst, the other conditions being unchanged. After the reaction was completed, 66.7g of gas was collected by a liquid nitrogen cold trap, and analyzed by gas chromatography, the composition of the gas was as follows: 9.80% of hexafluorobutadiene, 78.3% of trifluorobromoethylene, 2.3% of trifluoroethylene and 9.6% of other components.
Calculated as zinc trifluorovinyl bromide, the reaction yield was 10.1%.
Comparative example 2
The operation of this comparative example is the same as in example 1, except that: copper hydroxide 3.9g (0.04 mol) was used instead of the cuprous salt catalyst, the other conditions being unchanged. After the reaction was completed, 63.2g of gas was collected by a liquid nitrogen cold trap, and analyzed by gas chromatography, the composition of the gas was as follows: 0.10% of hexafluorobutadiene, 92.4% of trifluorobromoethylene, 2.98% of trifluoroethylene and 4.52% of other components.
Calculated as zinc trifluorovinyl bromide, the reaction yield was 0.10%.
Comparative example 3
The operation of this embodiment is identical to that of embodiment 1, except that: the reaction problem is reduced from 80 ℃ to 5 ℃ and other conditions are unchanged. After the reaction was completed, 70.2g of gas was collected by a liquid nitrogen cold trap, and analyzed by gas chromatography, the composition of the gas was as follows: 0.80% of hexafluorobutadiene, 95.1% of trifluorobromoethylene, 3.6% of trifluoroethylene and 0.5% of other components.
Calculated as zinc trifluorovinyl bromide, the reaction yield was 0.87%.
Comparative example 4
450g (mass fraction: 20%,0.4 mol) of N, N-dimethylformamide solution of zinc trifluorovinyl bromide was charged into a 1000mL reaction vessel, the reaction system was cooled to-5℃and 64.5g of CuCl was charged into the reaction vessel via an addition funnel 2 Control of CuCl 2 The reaction temperature is controlled at 0 ℃ by the feeding speed of (2)And (3) downwards. After 2h of reaction, the temperature is raised to 130 ℃ after the reaction is finished, all gas is distilled off, 24.8g of gas is collected by a liquid nitrogen cold trap, and the gas composition is as follows: 91.0% of hexafluorobutadiene, 4.5% of trifluorobromoethylene, 2.5% of trifluoroethylene and 2.0% of other components.
The reaction yield was calculated to be 69.6% based on the trifluorovinyl zinc bromide.
Comparative example 5
The operation of this embodiment is identical to that of embodiment 1, except that: the water content of the trifluorobromoethylene is 5000ppm, and other conditions are unchanged. After the reaction was completed, 60.3g of gas was collected by a liquid nitrogen cold trap, and analyzed by gas chromatography, the composition of the gas was as follows: 54.70% of hexafluorobutadiene, 17.80% of trifluorobromoethylene, 25.30% of trifluoroethylene and 2.20% of other components.
Calculated as zinc trifluorovinylbromide, the reaction yield was 50.9%.
Claims (12)
1. A preparation method of hexafluorobutadiene is characterized in that: the preparation method comprises the following steps: under the action of a catalyst, the trifluorobromoethylene and the trifluorovinyl zinc bromide are subjected to coupling reaction in a reactor to obtain hexafluorobutadiene, wherein the catalyst is a cuprous salt catalyst, and the reaction temperature is 25-150 ℃.
2. The method for producing hexafluorobutadiene as claimed in claim 1, wherein: the catalyst is at least one of cuprous halide, cuprous sulfate, cuprous carbonate, cuprous acetate, cuprous nitride, cuprous cyanide, cuprous oxide, cuprous sulfide, cuprous thiocyanate or cuprous triflate.
3. The method for producing hexafluorobutadiene as claimed in claim 2, wherein: the catalyst is at least one of cuprous halide, cuprous sulfate, cuprous carbonate, cuprous acetate, cuprous cyanide, cuprous oxide or cuprous triflate.
4. The method for producing hexafluorobutadiene as claimed in claim 1, wherein: the reaction temperature is 60 to 130 ℃, preferably 80 to 110 ℃.
5. The method for producing hexafluorobutadiene as claimed in claim 1, wherein: in the preparation method, the trifluoro vinyl zinc bromide is added into a reactor in the form of trifluoro vinyl zinc bromide solution, wherein the trifluoro vinyl zinc bromide solution is formed by dissolving trifluoro vinyl zinc bromide in an organic solvent, and the organic solvent is at least one selected from N, N-dimethylformamide, N-dimethylacetamide, hexamethylphosphoramide, dimethyl sulfoxide, 1, 3-dimethyl-2-imidazolidinone, N-methylpyrrolidone, diethyl ether, acetonitrile or tetrahydrofuran.
6. The method for producing hexafluorobutadiene as claimed in claim 5, wherein: the trifluorobromoethylene is a trifluorobromoethylene gas having a water content of less than 2000ppm, preferably less than 1000ppm, more preferably less than 500ppm.
7. The method for producing hexafluorobutadiene as claimed in claim 5, wherein: in the trifluoro vinyl zinc bromide solution, the mass ratio of trifluoro vinyl zinc bromide to organic solvent is 1 (3-12).
8. The method for producing hexafluorobutadiene as claimed in claim 1, wherein: the molar ratio of the trifluorobromoethylene to the trifluorovinyl zinc bromide is (0.8-10): 1.
9. The method for producing hexafluorobutadiene as claimed in claim 1, wherein: the molar ratio of the trifluoro vinyl zinc bromide to the catalyst is 1 (0.05-2.0).
10. The method for producing hexafluorobutadiene as claimed in claim 1, wherein: the preparation of the hexafluorobutadiene is carried out under inert gas.
11. The method for producing hexafluorobutadiene as claimed in claim 1, wherein: the preparation method sequentially comprises the following steps:
adding cuprous salt catalyst into the reactor, wherein the cuprous salt catalyst is solid or cuprous salt solution;
adding a trifluoro vinyl zinc bromide solution into the reactor;
and introducing trifluorobromoethylene into the reactor, and heating to the reaction temperature to perform the reaction.
12. The method for producing hexafluorobutadiene as claimed in claim 1, wherein: the reactor is a kettle type reactor or a tubular reactor.
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