CN1241886C - Preparation of saturated fluorine contained paraffins from halogen olefin by addition of hydrogen fluoride - Google Patents
Preparation of saturated fluorine contained paraffins from halogen olefin by addition of hydrogen fluoride Download PDFInfo
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- CN1241886C CN1241886C CN 200410041218 CN200410041218A CN1241886C CN 1241886 C CN1241886 C CN 1241886C CN 200410041218 CN200410041218 CN 200410041218 CN 200410041218 A CN200410041218 A CN 200410041218A CN 1241886 C CN1241886 C CN 1241886C
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- Prior art keywords
- reaction
- fluoride
- ammonium fluoride
- neutral ammonium
- hydrogen fluoride
- Prior art date
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- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 229910000040 hydrogen fluoride Inorganic materials 0.000 title claims abstract description 75
- -1 halogen olefin Chemical class 0.000 title claims abstract description 21
- 150000002221 fluorine Chemical class 0.000 title description 11
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title description 5
- 238000002360 preparation method Methods 0.000 title description 4
- 229910052736 halogen Inorganic materials 0.000 title 1
- 238000006243 chemical reaction Methods 0.000 claims abstract description 145
- 150000001336 alkenes Chemical class 0.000 claims abstract description 42
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000007259 addition reaction Methods 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 150000003839 salts Chemical group 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 230000035484 reaction time Effects 0.000 claims abstract description 3
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 43
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 42
- 150000002431 hydrogen Chemical class 0.000 claims description 21
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 21
- YFMFNYKEUDLDTL-UHFFFAOYSA-N 1,1,1,2,3,3,3-heptafluoropropane Chemical compound FC(F)(F)C(F)C(F)(F)F YFMFNYKEUDLDTL-UHFFFAOYSA-N 0.000 claims description 20
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 claims description 16
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 14
- 125000001153 fluoro group Chemical class F* 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 8
- QSUJAUYJBJRLKV-UHFFFAOYSA-M tetraethylazanium;fluoride Chemical compound [F-].CC[N+](CC)(CC)CC QSUJAUYJBJRLKV-UHFFFAOYSA-M 0.000 claims description 7
- QBTUCBKAWGUMMK-UHFFFAOYSA-N C=CC.[F] Chemical group C=CC.[F] QBTUCBKAWGUMMK-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical class CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 229910001867 inorganic solvent Inorganic materials 0.000 claims description 6
- 239000003049 inorganic solvent Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- IDSKMUOSMAUASS-UHFFFAOYSA-N 1,2-dichloro-1,2-difluoroethane Chemical compound FC(Cl)C(F)Cl IDSKMUOSMAUASS-UHFFFAOYSA-N 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 239000011833 salt mixture Substances 0.000 claims description 5
- GTDKXDWWMOMSFL-UHFFFAOYSA-M tetramethylazanium;fluoride Chemical compound [F-].C[N+](C)(C)C GTDKXDWWMOMSFL-UHFFFAOYSA-M 0.000 claims description 5
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 claims description 4
- KLZDCUBZWUSEGO-UHFFFAOYSA-N CC.F.F.F.F.F Chemical compound CC.F.F.F.F.F KLZDCUBZWUSEGO-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical class CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- VBQDSLGFSUGBBE-UHFFFAOYSA-N benzyl(triethyl)azanium Chemical compound CC[N+](CC)(CC)CC1=CC=CC=C1 VBQDSLGFSUGBBE-UHFFFAOYSA-N 0.000 claims description 4
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- GLFDLEXFOHUASB-UHFFFAOYSA-N trimethyl(tetradecyl)azanium Chemical compound CCCCCCCCCCCCCC[N+](C)(C)C GLFDLEXFOHUASB-UHFFFAOYSA-N 0.000 claims description 4
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 claims description 4
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 4
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 claims description 3
- RGZHHTKDHXSAQQ-UHFFFAOYSA-N 1,1-dichloro-2-fluoroethane Chemical compound FCC(Cl)Cl RGZHHTKDHXSAQQ-UHFFFAOYSA-N 0.000 claims description 3
- XRPKRSLLVXAECN-UHFFFAOYSA-N CCCC.[F] Chemical compound CCCC.[F] XRPKRSLLVXAECN-UHFFFAOYSA-N 0.000 claims description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 150000002825 nitriles Chemical class 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 17
- 239000006227 byproduct Substances 0.000 abstract description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 abstract description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract 2
- 229920006395 saturated elastomer Polymers 0.000 abstract 2
- 239000002994 raw material Substances 0.000 abstract 1
- 230000009257 reactivity Effects 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 47
- 239000007789 gas Substances 0.000 description 26
- 239000000463 material Substances 0.000 description 24
- 238000005070 sampling Methods 0.000 description 21
- 238000013019 agitation Methods 0.000 description 20
- 238000004587 chromatography analysis Methods 0.000 description 20
- 229910052731 fluorine Inorganic materials 0.000 description 20
- 239000010935 stainless steel Substances 0.000 description 20
- 229910001220 stainless steel Inorganic materials 0.000 description 20
- 150000001298 alcohols Chemical class 0.000 description 18
- 239000007791 liquid phase Substances 0.000 description 17
- 229910000831 Steel Inorganic materials 0.000 description 16
- 239000010959 steel Substances 0.000 description 16
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 15
- 239000011737 fluorine Substances 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- BAVYZALUXZFZLV-UHFFFAOYSA-O Methylammonium ion Chemical compound [NH3+]C BAVYZALUXZFZLV-UHFFFAOYSA-O 0.000 description 12
- 150000002222 fluorine compounds Chemical class 0.000 description 12
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical class CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000036571 hydration Effects 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000036039 immunity Effects 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 3
- NDKGUMMLYBINOC-UHFFFAOYSA-N 1,2-dichloro-1-fluoroethane Chemical compound FC(Cl)CCl NDKGUMMLYBINOC-UHFFFAOYSA-N 0.000 description 2
- 229910021630 Antimony pentafluoride Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- VBVBHWZYQGJZLR-UHFFFAOYSA-I antimony pentafluoride Chemical compound F[Sb](F)(F)(F)F VBVBHWZYQGJZLR-UHFFFAOYSA-I 0.000 description 2
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 description 2
- 238000007337 electrophilic addition reaction Methods 0.000 description 2
- 125000001188 haloalkyl group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 2
- GTLACDSXYULKMZ-UHFFFAOYSA-N pentafluoroethane Chemical compound FC(F)C(F)(F)F GTLACDSXYULKMZ-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine group Chemical class C(CCC)N(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- YMRMDGSNYHCUCL-UHFFFAOYSA-N 1,2-dichloro-1,1,2-trifluoroethane Chemical compound FC(Cl)C(F)(F)Cl YMRMDGSNYHCUCL-UHFFFAOYSA-N 0.000 description 1
- SKDFWEPBABSFMG-UHFFFAOYSA-N 1,2-dichloro-1,1-difluoroethane Chemical compound FC(F)(Cl)CCl SKDFWEPBABSFMG-UHFFFAOYSA-N 0.000 description 1
- BOUGCJDAQLKBQH-UHFFFAOYSA-N 1-chloro-1,2,2,2-tetrafluoroethane Chemical compound FC(Cl)C(F)(F)F BOUGCJDAQLKBQH-UHFFFAOYSA-N 0.000 description 1
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- CYXIKYKBLDZZNW-UHFFFAOYSA-N 2-Chloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)CCl CYXIKYKBLDZZNW-UHFFFAOYSA-N 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 229930013930 alkaloid Natural products 0.000 description 1
- 150000003797 alkaloid derivatives Chemical class 0.000 description 1
- ISQINHMJILFLAQ-UHFFFAOYSA-N argon hydrofluoride Chemical compound F.[Ar] ISQINHMJILFLAQ-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- WMIYKQLTONQJES-UHFFFAOYSA-N hexafluoroethane Chemical compound FC(F)(F)C(F)(F)F WMIYKQLTONQJES-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- UUEVFMOUBSLVJW-UHFFFAOYSA-N oxo-[[1-[2-[2-[2-[4-(oxoazaniumylmethylidene)pyridin-1-yl]ethoxy]ethoxy]ethyl]pyridin-4-ylidene]methyl]azanium;dibromide Chemical group [Br-].[Br-].C1=CC(=C[NH+]=O)C=CN1CCOCCOCCN1C=CC(=C[NH+]=O)C=C1 UUEVFMOUBSLVJW-UHFFFAOYSA-N 0.000 description 1
- DAFIBNSJXIGBQB-UHFFFAOYSA-N perfluoroisobutene Chemical compound FC(F)=C(C(F)(F)F)C(F)(F)F DAFIBNSJXIGBQB-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000001020 rhythmical effect Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229940096017 silver fluoride Drugs 0.000 description 1
- REYHXKZHIMGNSE-UHFFFAOYSA-M silver monofluoride Chemical compound [F-].[Ag+] REYHXKZHIMGNSE-UHFFFAOYSA-M 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a method for preparing saturated fluoroalkane by an addition reaction of alkenyl halide and hydrogen fluoride, particularly to a method for preparing corresponding fluoroalkane by an addition reaction of alkenyl halide and hydrogen fluoride through a hydrogen fluoride-quaternary salt fluoride-solvent fluoroalkane system. The present invention has the technical scheme that quaternary salt fluoride or a quaternary salt fluoride mixture, hydrogen fluoride and a solvent are mixed according to weight proportion of 1:0.1 to 1:1 to 4.5 to form a fluoroalkane system in a reaction container, then poly-fluoroolefin is put in the reaction container, the put substance amount of the poly-fluoroolefin does not exceed the substance amount of the fluorine hydride in the fluoroalkane system, the poly-fluoroolefin and the hydrogen fluoride generate the addition reaction at room temperature of-200 DEG C, the reaction pressure is autogenous pressure, the reaction time is from 0.5 to 72 hours, and a saturated fluoroalkane product is obtained. The present invention has the advantages that because the reaction is carried out at normal temperature and pressure and the corrosion of a reaction system is small, the reaction condition is mild; because the reaction temperature is low and by-products are few, the conversion rate of alkene raw materials is high, and the selectivity of goal alkane products is high; the reaction system is not influenced by water content, so the reactivity and the anti-interference capability of the reaction system are strong.
Description
Technical field
The present invention relates to the method that a kind of haloolefin addition hydrogen fluoride prepares saturated fluorine-containing alkane, is by hydrogen fluoride-fluoridize quaternary salt-solvent fluorinated hydrogen system prepares method from corresponding fluorine-containing alkane to haloolefin addition hydrogen fluoride more specifically.
Background technology
Fluorine is first element of VII main group, the electronegativity maximum, and atomic radius is little, and van der Waals radius is 0.135nm, and is only big slightly than hydrogen atom van der Waals radius 0.12nm.Hydrogen atom in the organic compound can be replaced by the fluorine atom that volume is more or less the same mostly, forms the organofluorine compound of One's name is legion.Because the electronegativity that fluorine is big, polarizability and weak Intermolecular Forces that little atomic radius, fluorine carbon bond is low, often change after introducing fluorine in the organic compound with remarkable physicochemical property, have various special propertys, therefore, organofluorine compound now has been widely used in the national economy every field.The organic fluorine product of scale operation at present has small molecules fluorochemicalss such as cooling agent, aerosol, whipping agent, fire-fighting medium, polymer fluorochemicalss such as fluoroplastics, fluoroelastomer, and fluoro-containing pesticide and medicine intermediate.
To unsaturated hydrocarbons addition hydrogen fluoride is the important channel of introducing fluorine in the organic compound.Easy and the alkene generation electrophilic addition of hydrogen fluoride.For haloolefin, along with the substituent increase of halogen atom on two keys, it is difficult that haloolefin and hydrogen fluoride addition become, and trieline does not also react with hydrogen fluoride at 160 ℃.When having the alkene of fluorine atom and hydrogen fluoride to carry out addition reaction on two keys, because the cloud density on two keys is low especially, electrophilic addition reaction is very difficult to carry out.The substituent polyfluoro of fluorine atom is arranged for alkene addition hydrogen fluoride difficulty especially on usually two keys, need carry out in very harsh conditions.
R 1216 gas phase addition hydrogen fluoride preparation 1,1,1,2,3,3,3-heptafluoro-propane (HFC-227ea): English Patent GB902590 is catalyzer with the activated carbon, temperature of reaction is 250-450 degree centigrade; U.S. Pat 6,187,975 is catalyzer with the aluminum fluoride, and temperature of reaction is 320-420 degree centigrade, and these inventions reaction at high temperature is easy to generate hypertoxic by products such as octafluoroisobutene.
R 1216 liquid phase addition hydrogen fluoride prepares HFC-227ea, U.S. Pat 5,689, and 019 is main catalyzer with antimony pentafluoride, temperature of reaction is lower than 100 degrees centigrade.But, there is heavy corrosion in equipment, the reaction pair equipment requirements harshness of this invention because antimony pentafluoride and hydrogen fluoride form super acids.
For molecular formula is CF
2The Fluorine containing olefine addition hydrogen fluoride of=CXY (X is H or F, and Y is H, F, Cl, Br, I) prepares corresponding alkane: German patent DE 3009760 is a catalyzer with fluorine chromic oxide, and temperature of reaction is 20-200 degree centigrade, and gas phase is CF to molecular formula
2The alkene addition hydrogen fluoride of=CXY prepares corresponding alkane.But catalyzer need be handled with fluorine simple substance, and side reactions such as substitution reaction, cyclization have taken place in addition reaction, and this method is to CF
2The hydrofluoric target product selectivity of=CXY addition is poor.
Trifluorochloroethylene and hydrogen fluoride addition reaction preparation 1,1,1,2-tetrafluoro-2-monochloroethane (HCFC-124): U.S. Pat 3,755,477 is catalyzer with the chromic salts, temperature of reaction 320 degree, trifluorochloroethylene and excessive hydrogen fluoride reaction, adduct HCFC-124 has only 13%, tetrafluoroethylene has contained 20% on the contrary in the reaction product, and this reaction is not only poor to target product selectivity, and feed stock conversion is not high yet.
Trifluoro-ethylene and hydrogen fluoride gas phase addition reaction preparation 1,1,1,2-Tetrafluoroethane (HFC-134a): English Patent GB2004539 (A) is catalyzer with chromic oxide, at 200-500 degree centigrade of trifluoro-ethylene and excessive hydrogen fluoride reaction, but reaction has generated multiple by products such as methylene fluoride, tetrafluoromethane, pentafluoride ethane, hexafluoroethane under the high temperature.This method temperature of reaction height, by product is many, and is poor to target product selectivity.
U.S. Pat 5,399,795 is that the ion exchange resin of chain carrier is catalyzer so that tertiary amine to be arranged, under mild reaction conditions, R 1216 and hydrogen fluoride addition prepare HFC-227ea, the shortcoming of this method is that the unit volume reaction yield is little, drops into the hydrogen fluoride excessive catalyst deactivation that causes easily.U.S. Pat 5,847,245 and US5,969,199 provide a kind of alkaloid and hydrofluoric adducts to the hydrofluoric method of haloolefin addition.And the ratio of hydrogen fluoride and tertiary amine amount of substance reacted completely above 4 o'clock and stops the reaction system poor anti jamming capability in the system that this method is used.
For perfluoroolefines such as R 1216, tetrafluoroethylene, it is handled in protonic solvent such as methane amide with anhydrous potassium fluoride, the two keys of fluorion in the Potassium monofluoride carry out addition, generation is with the intermediate of a negative charge, the atomic reaction of hydrogen that this intermediate and methane amide provide obtains HFC-227ea.The fluorochemical that this class " nucleophilic " addition reaction can take place also has cesium fluoride, tetraethyl ammonium fluoride, silver fluoride.But by wait protonic solvent provide hydrogen atom cause generating unwanted by product (MilosHudlicky.Fluorine Chemistry for Organic Chemists.Oxford New York:Oxford UniversityPress, 2000.54.).
Close state patent US 4,734,526 provide a kind of have fluoridize that quaternary ammonium salt is fluoridized existing under the situation of reagent and to there being hydrogen fluoride of the substituent alkynes addition of activation to prepare the method for corresponding Fluorine containing olefine on the triple bond, this patent points out that this method can not generate corresponding alkane to second hydrogen fluoride of the further addition of alkene.
Existing hydrogen fluoride is to the method for polyfluoro for the alkene addition, has individually or simultaneously that for example reaction needed is carried out under High Temperature High Pressure, the olefin feedstock transformation efficiency is low, target alkane selectivity of product is poor, the shortcoming of the reactive behavior poor anti jamming capability of reaction system.
Summary of the invention
The object of the present invention is to provide a kind of haloolefin addition hydrogen fluoride to prepare the method for saturated fluorine-containing alkane.This method reaction conditions gentleness, olefin feedstock transformation efficiency height, target alkane selectivity of product height, the reactive behavior immunity from interference of reaction system is strong.
The present invention seeks to reach like this, a kind of haloolefin addition hydrogen fluoride prepares the method for saturated fluorine-containing alkane, characteristics are: in reaction vessel, to fluoridize quaternary salt or fluoridize the quaternary salt mixture, hydrogen fluoride, the organic or inorganic solvent mixes formation fluorinated hydrogen system by weight 1: 0.1～1: 1～4.5, drop into polyfluoro then for alkene, polyfluoro is no more than hydrofluoric amount of substance in the fluorinated hydrogen system for the amount of substance of alkene input, at room temperature～200 ℃ polyfluoro for alkene and hydrogen fluoride generation addition reaction, reaction pressure is an autogenous pressure, reaction times is 0.5-72 hour, obtain saturated fluorine-containing alkane product, wherein: the described quaternary salt of fluoridizing is a Methanaminium, N,N,N-trimethyl-, fluoride, the ethyl-trimethyl Neutral ammonium fluoride, tetraethyl ammonium fluoride, methyl triethyl Neutral ammonium fluoride, the tetrapropyl Neutral ammonium fluoride, tetrabutyl ammonium fluoride, the benzyl trimethyl Neutral ammonium fluoride, the benzyl triethyl ammonium Neutral ammonium fluoride, benzyl tributyl Neutral ammonium fluoride, tetradecyl trimethylammonium Neutral ammonium fluoride, the cetyl trimethyl Neutral ammonium fluoride, dimethyl dibenzyl Neutral ammonium fluoride, trioctylphosphine methyl Neutral ammonium fluoride, tetraphenyl is fluoridized phosphine, trityl group is fluoridized phosphine, triphenyl ethyl is fluoridized phosphine, the triphenyl butyl is fluoridized phosphine, the triphenyl benzyl is fluoridized any one in the phosphine, the described quaternary salt mixture of fluoridizing is a Methanaminium, N,N,N-trimethyl-, fluoride, the ethyl-trimethyl Neutral ammonium fluoride, tetraethyl ammonium fluoride, methyl triethyl Neutral ammonium fluoride, the tetrapropyl Neutral ammonium fluoride, tetrabutyl ammonium fluoride, the benzyl trimethyl Neutral ammonium fluoride, the benzyl triethyl ammonium Neutral ammonium fluoride, benzyl tributyl Neutral ammonium fluoride, tetradecyl trimethylammonium Neutral ammonium fluoride, the cetyl trimethyl Neutral ammonium fluoride, dimethyl dibenzyl Neutral ammonium fluoride, trioctylphosphine methyl Neutral ammonium fluoride, tetraphenyl is fluoridized phosphine, trityl group is fluoridized phosphine, triphenyl ethyl is fluoridized phosphine, the triphenyl butyl is fluoridized phosphine, the triphenyl benzyl is fluoridized two or more mixture in the phosphine, described organic solvent is the carbonatoms that is in a liquid state under the reaction conditions less than 20 halo or non-halogenated aliphatic hydrocarbon, aromatic hydrocarbon, alcohol, ketone, ether, nitrile, amine, the mixed solvent of any one single solvent in the heterogeneous ring compound or two kinds or multiple solvent, described inorganic solvent is a water.
Polyfluoro of the present invention is tetrafluoroethylene, trifluorochloroethylene, trifluoro-ethylene, 1 for alkene, 1-difluoro Ethylene Dichloride, 1,2-difluoro Ethylene Dichloride, 1, any one in 1-difluoro one vinylchlorid, R 1216,2-hydrogen five fluorine propylene, 2-hydrogen-seven fluoro-2-propylene, perfluor-1-propylene, the perfluor-2-propylene.
Polyfluoro of the present invention for alkene and hydrogen fluoride addition after the saturated fluorine-containing alkane of gained be pentafluoride ethane, 1,1,1,2-Vcon, 1,1,1,2-Tetrafluoroethane, 1,1,1-three fluoro-2,2-ethylene dichloride, 1,1,2-three fluoro-1,2-ethylene dichloride, 1,1,1-trifluoro-chloroethane, 1,1,1,2,3,3,3-heptafluoro-propane, 1,1,1,3,3,3-HFC-236fa, 2, any one in 2-dihydro Octafluorobutane, the 2-hydrogen nine fluorine butane.
The mode that argon fluoride of the present invention and polyfluoro carry out addition reaction for alkene is any one mode in continous way or the intermittent type.
The invention has the advantages that owing to being reflected at normal temperature and pressure and also can carry out, and reaction system corrodibility is little, thereby the reaction conditions gentleness; Low because of temperature of reaction, by product is few, so olefin feedstock transformation efficiency height, target alkane selectivity of product height; Reaction system is not influenced by moisture content, so the reactive behavior immunity from interference of reaction system is strong.
Embodiment
Following applicant more is described in detail invention, to help to understand the present invention.
A kind of reactive mode is: a kind ofly fluoridize quaternary salt or two kinds or multiple mixture, the organic or inorganic solvent of fluoridizing quaternary salt joins in reaction vessel such as the tank reactor with aforesaid, in whipped state downhill reaction device, feed hydrogen fluoride then, their weight ratios each other are 1: 0.1～1: 1～4.5, mix to form the fluorinated hydrogen system.Then aforesaid any one polyfluoro is pressed into reactor continuously or off and on for alkene, is pressed into the unsaturated hydrocarbons amount of substance and is no more than hydrogen fluoride amount of substance in the fluorinated hydrogen system.Is room temperature to 200 ℃ following addition reaction for alkene and hydrogen fluoride in temperature by polyfluoro, and reaction pressure is the autogenous pressure of reactant under the temperature of reaction, after keeping 0.5～72 hour, by heating up or aforesaid any one the saturated fluorine-containing alkane of decompression taking-up.
If used solvent inorganics solvent in aforesaid addition reaction, be that water is during as inorganic solvent, can reduce the solubleness of reaction product in the fluorinated hydrogen system, especially from the fluorinated hydrogen system, take out reactant when using when can tolerate hydrofluoric acid corrosive reaction vessel, use water as solvent in the time of can being convenient to react.And, the inventive method uses water as that solvent means the material hydrogen fluoride that is used for addition reaction, fluoridizes quaternary salt, polyfluoro all can be aqueous for alkene and solvent, and known to polyfluoro for olefin catalytic addition hydrogen fluoride method, the consequence of introducing water in the reaction system normally causes catalyzer to lose activity.This illustrates also with prior art and compares that the reactive behavior immunity from interference of reaction system of the present invention is strong.
If the organic solvent that in aforesaid addition reaction, is in a liquid state under the used solvent reaction conditions, promptly be not more than 20 halo or non-halogenated aliphatic hydrocarbon, aromatic hydrocarbon, alcohol, ketone, ether, nitrile, amine, heterogeneous ring compound with carbonatoms, with organic substance during as solvent, can improve reaction mass and the product solubleness in the fluorinated hydrogen system, be convenient to reduce reaction pressure, improve speed of response and transformation efficiency.
In the addition reaction of the present invention, fluoridize quaternary salt: hydrogen fluoride: the weight ratio of solvent meets 1: 0.1～and 1: 1～4.5 systems of fluoridizing quaternary salt mixture and hydrogen fluoride, solvent composition are called the fluorinated hydrogen system.
Addition reaction temperature of the present invention is room temperature～200 ℃.
Addition reaction of the present invention just can be carried out under normal pressure, also can under high pressure carry out.When using seal-off pressure container rhythmic reaction, reaction can be carried out under the material autogenous pressure.
Addition reactor of the present invention can be tank reactor, tower reactor, tubular reactor, which kind of no matter uses anti-
Answer container, should adopt suitable means to guarantee polyfluoro fully contacting for alkene and fluorinated hydrogen system.For example adopt the circulation of material or product gas flow to stir reaction system, in tank reactor, also can adopt alr mode to promote polyfluoro fully contacting for alkene and fluorinated hydrogen system.
Addition reaction of the present invention can be carried out continuously, also may be carried out batchwise.
The present invention is if get intermittently addition reaction mode: will fluoridize quaternary salt, hydrogen fluoride, solvent earlier and prepare in proportion under good stirring state, and add reaction vessel.Disposable then or drop into an amount of polyfluoro in batches for alkene, temperature is controlled at the desired reaction temperature reaction.Can adopt the circulation of material or product gas flow to stir reaction system in the reaction, or adopt alr mode to promote the abundant contact reacts of polyfluoro for alkene and fluorinated hydrogen system, by the time material component reaches desired requirement in the reactor, takes out product by the method that reduces pressure or intensification from the fluorinated hydrogen system.After taking out product, add the hydrogen fluoride that falls into reaction consumes to the fluorinated hydrogen system, the fluorinated hydrogen system just can be used for reacting next time.
The present invention is if get continuous addition reaction mode: will fluoridize quaternary salt, hydrogen fluoride, solvent earlier and prepare in proportion under good stirring state, and add reaction vessel.Temperature is controlled at desired reaction temperature, and polyfluoro drops into reaction vessel continuously for alkene, and hydrogen fluoride is added continuously into the fluorinated hydrogen system, polyfluoro for alkene and add into the hydrogen fluoride mol ratio be 1: 1.Adduct takes out from reaction system continuously, if contain in the adduct unreacted completely polyfluoro for alkene, can with unreacted completely polyfluoro for alkene separate with product the back Returning reactor in circulating reaction.Can adopt the circulation of material or product gas flow to stir reaction system in the reaction, or adopt alr mode to promote the abundant contact reacts of polyfluoro for alkene and fluorinated hydrogen system.
For the present invention cited in front fluoridize quaternary salt, polyfluoro for alkene, fluorine-containing alkane list, they do not limit and are not put in list other and fluoridize quaternary salt, polyfluoro accordingly for alkene, fluorine-containing alkane.
For example: satisfy general formula (II) and all should think row at its list as long as fluoridize quaternary salt:
Q, R in the formula (II)
6, R
7, R
8, R
9The meaning of representative is: Q is N atom, P atom, R
6, R
7, R
8, R
9Can be identical substituting group, also can for or different substituting groups, they are selected from carbonatoms is 1 to 20 alkyl or aromatic base.
And for example: all should think row at its list as long as polyfluoro satisfies general formula (I) for alkene:
R in the formula (I)
1, R
2, R
3, R
4The meaning of representative is: R
1Be the F atom; R
2Be F atom, CF
3Or CF
2R
5, R wherein
5For carbonatoms 1 to 20 alkyl or haloalkyl; R
3And R
4Can be identical substituting group, also can for or different substituting groups, they are selected from H atom, halogen atom, CF
3Or CF
2R
5, R wherein
5For carbonatoms is 1 to 20 alkyl or haloalkyl, but R
3, R
4In have a substituting group implication and R at least
2Identical.So polyfluoro is not limited to aforesaid CF for alkene
2=CF
2(tetrafluoroethylene), CF
2=CFCl (trifluorochloroethylene), CF
2=CFH (trifluoro-ethylene), CF
2=CCl
2(1,1-difluoro Ethylene Dichloride), CClF=CClF (1,2-difluoro Ethylene Dichloride), CF
2=CHCl (1,1-difluoro one vinylchlorid), CF
2=CF-CF
3(R 1216), CF
2=CH-CF
3(2-hydrogen five fluorine propylene), CF
3-CF=CH-CF
3(2-hydrogen-seven fluoro-2-propylene), CF
2=CF-CF
2-CF
3(perfluor-1-propylene), CF
3-CF=CF-CF
3(perfluor-2-propylene).
Also as: all should think row at its list as long as saturated fluorine-containing alkane satisfies general formula (III):
R in the formula (III)
1, R
2, R
3, R
4R in the meaning of representative and the general formula (I)
1, R
2, R
3, R
4The same meaning of representative.So saturated fluorine-containing alkane is not limited to aforesaid CF
3-CHF
2(pentafluoride ethane), CF
3-CHFCl (1,1,1, the 2-Vcon), CF
3-CFH
2(1,1,1, the 2-Tetrafluoroethane), CF
3-CHCl
2(1,1,1-three fluoro-2,2-ethylene dichloride), CClF
2-CHClF (1,1,2-three fluoro-1,2-ethylene dichloride), CF
3-CH
2Cl (1,1, the 1-trifluoro-chloroethane), CF
3-CHF-CF
3(1,1,1,2,3,3, the 3-heptafluoro-propane), CF
3-CH
2-CF
3(1,1,1,3,3, the 3-HFC-236fa), CF
3-CF
2-CH
2-CF
3(2,2-dihydro Octafluorobutane), CF
3-CF
2-CFH-CF
3(2-hydrogen nine fluorine butane).
Embodiment
Following embodiment will help to understand the present invention more, but not limit content of the present invention.
Embodiment 1:
Reaction vessel stirs 5 liters of autoclaves for band, and body material mainly adopts the 1Cr18Ni9Ti stainless steel.186 gram Methanaminium, N,N,N-trimethyl-, fluorides and 500 gram dehydrated alcohols are added autoclave, under agitation slowly feed 80 gram hydrogen fluoride then.150 gram R 1216s are pressed into autoclave with liquid phase from the R 1216 steel cylinder then.Shut the autoclave valve, stir down autoclave is warmed up to 100 degrees centigrade, reaction pressure is a reaction system autogenous pressure under the temperature of reaction, keeps 2 hours.The sampling gas chromatographic analysis, R 1216 adduct HFC-227ea content is 98%, all the other are unreacted R 1216.
Embodiment 2:
Reaction vessel stirs 5 liters of autoclaves for band, and body material mainly adopts the 1Cr18Ni9Ti stainless steel.186 gram Methanaminium, N,N,N-trimethyl-, fluorides, 20 grams, three hydration tetrabutyl ammonium fluorides, 500 gram dehydrated alcohols are added autoclave, under agitation slowly logical then
Go into 140 gram hydrogen fluoride.150 gram R 1216s are pressed into autoclave with liquid phase from the R 1216 steel cylinder then.Shut the autoclave valve, stir down autoclave is warmed up to 100 degrees centigrade, reaction pressure is a reaction system autogenous pressure under the temperature of reaction, keeps 8 hours.The sampling gas chromatographic analysis, R 1216 adduct HFC-227ea content is 72%, all the other are unreacted R 1216.
Embodiment 3:
Reaction vessel is lined with the tetrafluoroethylene stainless steel autoclave for band stirs 5 liters.186 gram Methanaminium, N,N,N-trimethyl-, fluorides, 20 grams, three hydration tetrabutyl ammonium fluorides, 20 gram tetraethyl ammonium fluorides, 500 gram dehydrated alcohols and 100 gram water are added autoclave, under agitation slowly feed 140 gram hydrogen fluoride then.150 gram R 1216s are pressed into autoclave with liquid phase from the R 1216 steel cylinder then.Shut the autoclave valve, stir down autoclave is warmed up to 100 degrees centigrade, reaction pressure is a reaction system autogenous pressure under the temperature of reaction, keeps 2 hours.The sampling gas chromatographic analysis, R 1216 adduct HFC-227ea content is 94%, all the other are unreacted R 1216.
Embodiment 4:
Reaction vessel stirs 5 liters of autoclaves for band, and body material mainly adopts the 1Cr18Ni9Ti stainless steel.186 gram Methanaminium, N,N,N-trimethyl-, fluorides, 20 grams, three hydration tetrabutyl ammonium fluorides, 20 gram tetraethyl ammonium fluorides, 20 gram methyl triethyl Neutral ammonium fluorides, 500 gram dehydrated alcohols and 100 gram triethylamines are added autoclave, under agitation slowly feed 140 gram hydrogen fluoride then.150 restrain 1,1,2,3,3,4,4 then, 4-octafluoro-1-butylene is pressed into autoclave with liquid phase from steel cylinder with nitrogen.Shut the autoclave valve, stir down autoclave is warmed up to 150 degrees centigrade, reaction pressure is a reaction system autogenous pressure under the temperature of reaction, keeps 72 hours.The sampling gas chromatographic analysis, 1,1,2,3,3,4,4,4-octafluoro-1-butylene adduct 2-hydrogen nine fluorine normal butane content are 99%, all the other are unreacted alkene.
Embodiment 5:
Reaction vessel stirs 5 liters of autoclaves for band, and body material mainly adopts the 1Cr18Ni9Ti stainless steel.186 gram Methanaminium, N,N,N-trimethyl-, fluorides, 500 gram dehydrated alcohols and 100 gram methyl iso-butyl ketone (MIBK) are added autoclave, under agitation slowly feed 80 gram hydrogen fluoride then.100 gram CClF=CClF (1,2-difluoro Ethylene Dichloride) are pressed into autoclave with liquid phase from steel cylinder with nitrogen then.Shut the autoclave valve, stir down autoclave is warmed up to 130 degrees centigrade, reaction pressure is a reaction system autogenous pressure under the temperature of reaction, keeps 48 hours.The sampling gas chromatographic analysis, 1,2-difluoro Ethylene Dichloride adduct 1,1,2-trifluoro Ethylene Dichloride content is 98%, all the other are unreacted alkene.
Embodiment 6:
Reaction vessel is lined with the tetrafluoroethylene stainless steel autoclave for band stirs 5 liters, and temperature is by inner coil pipe fluid and the control of outer heating unit.
186 gram Methanaminium, N,N,N-trimethyl-, fluorides, 500 gram dehydrated alcohols, 100 gram water, 100 gram triethylamines are added autoclave, under agitation slowly feed 80 gram hydrogen fluoride then.150 restrain 1,1,1,2,3,4,4 then, 4-octafluoro-2-butylene is pressed into autoclave with liquid phase from steel cylinder with nitrogen.Shut the autoclave valve, stir down autoclave is warmed up to 150 degrees centigrade, reaction pressure is a reaction system autogenous pressure under the temperature of reaction, keeps 50 hours.The sampling gas chromatographic analysis, 1,1,1,2,3,4,4,4-octafluoro-2-butylene adduct 2-hydrogen nine fluorine normal butane content are 99%, all the other are unreacted alkene.
Embodiment 7:
Reaction vessel stirs 5 liters of autoclaves for band, and body material mainly adopts the 1Cr18Ni9Ti stainless steel.186 gram Methanaminium, N,N,N-trimethyl-, fluorides, 50 gram triethylamines, 50 gram Tributylamines, 500 gram dehydrated alcohols and 100 gram pimelinketone are added autoclave, under agitation slowly feed 80 gram hydrogen fluoride then.150 gram R 1216s are pressed into autoclave with liquid phase from the R 1216 steel cylinder then.Shut the autoclave valve, stir down autoclave temp is remained on room temperature, reaction pressure is a reaction system autogenous pressure under the temperature of reaction, keeps 24 hours.The sampling gas chromatographic analysis, R 1216 adduct HFC-227ea content is 90%, all the other are unreacted R 1216.
Embodiment 8:
Reaction vessel stirs 5 liters of autoclaves for band, and body material mainly adopts the 1Cr18Ni9Ti stainless steel.186 gram Methanaminium, N,N,N-trimethyl-, fluorides, 500 gram dehydrated alcohols, 100 gram hexanaphthenes and 100 gram tetrahydrofuran (THF)s are added autoclave, under agitation slowly feed 80 gram hydrogen fluoride then.150 gram R 1216s are pressed into autoclave with liquid phase from the R 1216 steel cylinder then.Shut the autoclave valve, stir down autoclave is warmed up to 100 degrees centigrade, reaction pressure is a reaction system autogenous pressure under the temperature of reaction, keeps 2 hours.The sampling gas chromatographic analysis, R 1216 adduct HFC-227ea content is 98%, all the other are unreacted R 1216.
Embodiment 9:
Reaction vessel stirs 5 liters of autoclaves for band, and body material mainly adopts the 1Cr18Ni9Ti stainless steel.630 grams, three hydration tetrabutyl ammonium fluorides, 1000 gram dehydrated alcohols are added autoclave, under agitation slowly feed 80 gram hydrogen fluoride then.150 gram R 1216s are pressed into autoclave with liquid phase from the R 1216 steel cylinder then.Shut the autoclave valve, stir down autoclave is warmed up to 100 degrees centigrade, reaction pressure is a reaction system autogenous pressure under the temperature of reaction, keeps 8 hours.The sampling gas chromatographic analysis, R 1216 adduct HFC-227ea content is 99%, all the other are unreacted R 1216.
Embodiment 10:
Reaction vessel stirs 5 liters of autoclaves for band, and body material mainly adopts the 1Cr18Ni9Ti stainless steel.260 gram tetrabutyl ammonium fluorides, 500 gram dehydrated alcohols and 100 gram triethylamines are added autoclave, under agitation slowly feed 60 gram hydrogen fluoride then.150 gram R 1216s are pressed into autoclave with liquid phase from the R 1216 steel cylinder then.Shut the autoclave valve, stir down autoclave is warmed up to 50 degrees centigrade, reaction pressure is a reaction system autogenous pressure under the temperature of reaction, keeps 30 hours.The sampling gas chromatographic analysis, R 1216 adduct HFC-227ea content is 98%, all the other are unreacted R 1216.
Embodiment 11:
Reaction vessel stirs 5 liters of autoclaves for band, and body material mainly adopts the 1Cr18Ni9Ti stainless steel.260 gram tetrabutyl ammonium fluorides, 90 gram Methanaminium, N,N,N-trimethyl-, fluorides, 1000 gram dehydrated alcohols are added autoclave, under agitation slowly feed 60 gram hydrogen fluoride then.150 gram R 1216s are pressed into autoclave with liquid phase from the R 1216 steel cylinder then.Shut the autoclave valve, stir down autoclave is warmed up to 150 degrees centigrade, reaction pressure is a reaction system autogenous pressure under the temperature of reaction, keeps 2 hours.The sampling gas chromatographic analysis, R 1216 adduct HFC-227ea content is 98%, all the other are unreacted R 1216.
Embodiment 12:
Reaction vessel stirs 5 liters of autoclaves for band, and body material mainly adopts the 1Cr18Ni9Ti stainless steel.260 gram tetrabutyl ammonium fluorides, 90 gram Methanaminium, N,N,N-trimethyl-, fluorides, 135 gram methyl triethyl Neutral ammonium fluorides, 100 gram Tributylamines, 100 gram triethylamines, 1500 gram dehydrated alcohols are added autoclave, under agitation slowly feed 100 gram hydrogen fluoride then.150 gram R 1216s are pressed into autoclave with liquid phase from the R 1216 steel cylinder then.Shut the autoclave valve, stir down autoclave is warmed up to 130 degrees centigrade, reaction pressure is a reaction system autogenous pressure under the temperature of reaction, keeps 0.5 hour.The sampling gas chromatographic analysis, R 1216 adduct HFC-227ea content is 98%, all the other are unreacted R 1216.
Embodiment 13:
Reaction vessel stirs 5 liters of autoclaves for band, and body material mainly adopts the 1Cr18Ni9Ti stainless steel.260 gram tetrabutyl ammonium fluorides, 500 gram triethylamines are added autoclave, under agitation slowly feed 100 gram hydrogen fluoride then.150 gram R 1216s are pressed into autoclave with liquid phase from the R 1216 steel cylinder then.Shut the autoclave valve, stir down autoclave is warmed up to 70 degrees centigrade, reaction pressure is a reaction system autogenous pressure under the temperature of reaction, keeps 40 hours.The sampling gas chromatographic analysis, R 1216 adduct HFC-227ea content is 98%, all the other are unreacted R 1216.
Embodiment 14:
Reaction vessel stirs 5 liters of autoclaves for band, and body material mainly adopts the 1Cr18Ni9Ti stainless steel.270 gram methyl triethyl Neutral ammonium fluorides, 500 gram dehydrated alcohols are added autoclave, under agitation slowly feed 80 gram hydrogen fluoride then.With 60 grams 1,1,1,3,3-five fluorine propylene are pressed into autoclave then.Shut the autoclave valve, stir down autoclave is warmed up to 100 degrees centigrade, reaction pressure is a reaction system autogenous pressure under the temperature of reaction, keeps 7 hours.The sampling gas chromatographic analysis, 1,1,1,3,3-five fluorine propylene adduct HFC-236fa content are 99%, all the other are unreacted 1,1,1,3,3-five fluorine propylene.
Embodiment 15:
Reaction vessel stirs 5 liters of autoclaves for band, and body material mainly adopts the 1Cr18Ni9Ti stainless steel.186 gram Methanaminium, N,N,N-trimethyl-, fluorides, 500 gram dehydrated alcohols are added autoclave, under agitation slowly feed 80 gram hydrogen fluoride then.Then 116 gram trifluorochloroethylenes are pressed into autoclave.Shut the autoclave valve, stir down autoclave is warmed up to 200 Cuo Shi degree, reaction pressure is a reaction system autogenous pressure under the temperature of reaction, keeps 1 hour.The sampling gas chromatographic analysis, trifluorochloroethylene adduct HCFC-124 content is 99%, all the other are unreacted trifluorochloroethylene.
Embodiment 16:
Reaction vessel stirs 5 liters of autoclaves for band, and body material mainly adopts the 1Cr18Ni9Ti stainless steel.186 gram Methanaminium, N,N,N-trimethyl-, fluorides, 500 gram dehydrated alcohols are added autoclave, under agitation slowly feed 80 gram hydrogen fluoride then.Stirring down autoclave is warmed up to 120 degrees centigrade, is that the tetrafluoroethylene medial launder of 3.0Mpa adds tetrafluoroethylene and reaches 1.5Mpa from pressure, stirs 6 hours.The sampling gas chromatographic analysis, tetrafluoroethylene adduct HFC-125 content is 95%, all the other are unreacted tetrafluoroethylene.
Embodiment 17:
Reaction vessel stirs 5 liters of autoclaves for band, and body material mainly adopts the 1Cr18Ni9Ti stainless steel.180 gram tetraphenyls are fluoridized phosphine, 500 gram acetonitriles and 200 gram benzene add autoclave, under agitation slowly feed 20 gram hydrogen fluoride then.50 gram R 1216s are pressed into autoclave with liquid phase from the R 1216 steel cylinder then.Shut the autoclave valve, stir down autoclave is warmed up to 100 degrees centigrade, reaction pressure is a reaction system autogenous pressure under the temperature of reaction, keeps 2 hours.The sampling gas chromatographic analysis, R 1216 adduct HFC-227ea content is 90%, all the other are unreacted R 1216.
Embodiment 18:
Reaction vessel is the tyre steam jacket of vertically installing, 40 millimeters of internal diameters, long 10 meters carbon steel pipes.Add 8 liters by Methanaminium, N,N,N-trimethyl-, fluoride: dehydrated alcohol: the fluorinated hydrogen system that hydrogen fluoride=6: 15: 2 weight ratio prepares.Reaction tubes is heated to 70 degrees centigrade, and R 1216 feeds from the reaction tubes bottom continuously with the speed of 60 milliliters of per minutes, and from reactor head sampling gas chromatographic analysis, R 1216 adduct HFC-227ea content is 95%.
Haloolefin addition hydrogen fluoride of the present invention prepares in the saturated fluorine-containing alkane method, fluoridize quaternary salt or its mixture plays an important role, if do not fluoridize the existence of quaternary salt or its mixture, reaction can not achieve the goal so, and three comparative examples that the applicant provides below just can illustrate it.
Comparative example 1:
Reaction vessel stirs 5 liters of autoclaves for band, and body material mainly adopts the 1Cr18Ni9Ti stainless steel.500 gram dehydrated alcohols are added autoclave, under agitation slowly feed 80 gram hydrogen fluoride then.150 gram R 1216s are pressed into autoclave with liquid phase from the R 1216 steel cylinder then.Shut the autoclave valve, stir down autoclave is warmed up to 100 degrees centigrade, reaction pressure is a reaction system autogenous pressure under the temperature of reaction, keeps 2 hours.The sampling gas chromatographic analysis does not detect R 1216 adduct HFC-227ea.
Comparative example 2:
Reaction vessel stirs 5 liters of autoclaves for band, and body material mainly adopts the 1Cr18Ni9Ti stainless steel.500 gram dehydrated alcohols are added autoclave, under agitation slowly feed 80 gram hydrogen fluoride then.150 gram trifluorochloroethylenes are pressed into autoclave with liquid phase from the R 1216 steel cylinder then.Shut the autoclave valve, stir down autoclave is warmed up to 100 degrees centigrade, reaction pressure is a reaction system autogenous pressure under the temperature of reaction, keeps 2 hours.The sampling gas chromatographic analysis does not detect trifluorochloroethylene adduct HCFC-124.
Comparative example 3:
Reaction vessel stirs 5 liters of autoclaves for band, and body material mainly adopts the 1Cr18Ni9Ti stainless steel.500 gram dehydrated alcohols are added autoclave, under agitation slowly feed 80 gram hydrogen fluoride then.Stirring down autoclave is warmed up to 120 degrees centigrade, is that the tetrafluoroethylene medial launder of 3.0Mpa adds tetrafluoroethylene and reaches 1.5Mpa from pressure, stirs 6 hours.The sampling gas-chromatography is analysed, and does not detect tetrafluoroethylene adduct HFC-125.
Claims (4)
1, a kind of haloolefin addition hydrogen fluoride prepares the method for saturated fluorine-containing alkane, it is characterized in that in reaction vessel, to fluoridize quaternary salt or fluoridize the quaternary salt mixture, hydrogen fluoride, the organic or inorganic solvent mixes formation fluorinated hydrogen system by weight 1: 0.1～1: 1～4.5, drop into polyfluoro then for alkene, polyfluoro is no more than hydrofluoric amount of substance in the fluorinated hydrogen system for the amount of substance of alkene input, at room temperature～200 ℃ polyfluoro for alkene and hydrogen fluoride generation addition reaction, reaction pressure is an autogenous pressure, reaction times is 0.5-72 hour, obtain saturated fluorine-containing alkane product, wherein: the described quaternary salt of fluoridizing is a Methanaminium, N,N,N-trimethyl-, fluoride, the ethyl-trimethyl Neutral ammonium fluoride, tetraethyl ammonium fluoride, methyl triethyl Neutral ammonium fluoride, the tetrapropyl Neutral ammonium fluoride, tetrabutyl ammonium fluoride, the benzyl trimethyl Neutral ammonium fluoride, the benzyl triethyl ammonium Neutral ammonium fluoride, benzyl tributyl Neutral ammonium fluoride, tetradecyl trimethylammonium Neutral ammonium fluoride, the cetyl trimethyl Neutral ammonium fluoride, dimethyl dibenzyl Neutral ammonium fluoride, trioctylphosphine methyl Neutral ammonium fluoride, tetraphenyl is fluoridized phosphine, trityl group is fluoridized phosphine, triphenyl ethyl is fluoridized phosphine, the triphenyl butyl is fluoridized phosphine, the triphenyl benzyl is fluoridized any one in the phosphine, the described quaternary salt mixture of fluoridizing is a Methanaminium, N,N,N-trimethyl-, fluoride, the ethyl-trimethyl Neutral ammonium fluoride, tetraethyl ammonium fluoride, methyl triethyl Neutral ammonium fluoride, the tetrapropyl Neutral ammonium fluoride, tetrabutyl ammonium fluoride, the benzyl trimethyl Neutral ammonium fluoride, the benzyl triethyl ammonium Neutral ammonium fluoride, benzyl tributyl Neutral ammonium fluoride, tetradecyl trimethylammonium Neutral ammonium fluoride, the cetyl trimethyl Neutral ammonium fluoride, dimethyl dibenzyl Neutral ammonium fluoride, trioctylphosphine methyl Neutral ammonium fluoride, tetraphenyl is fluoridized phosphine, trityl group is fluoridized phosphine, triphenyl ethyl is fluoridized phosphine, the triphenyl butyl is fluoridized phosphine, the triphenyl benzyl is fluoridized two or more mixture in the phosphine, described organic solvent is the carbonatoms that is in a liquid state under the reaction conditions less than 20 halo or non-halogenated aliphatic hydrocarbon, aromatic hydrocarbon, alcohol, ketone, ether, nitrile, amine, the mixed solvent of any one single solvent in the heterogeneous ring compound or two kinds or multiple solvent, described inorganic solvent is a water.
2, a kind of haloolefin addition hydrogen fluoride according to claim 1 prepares the method for saturated fluorine-containing alkane, it is characterized in that described polyfluoro is tetrafluoroethylene, trifluorochloroethylene, trifluoro-ethylene, 1 for alkene, 1-difluoro Ethylene Dichloride, 1,2-difluoro Ethylene Dichloride, 1, any one in 1-difluoro one vinylchlorid, R 1216,2-hydrogen five fluorine propylene, 2-hydrogen-seven fluoro-2-propylene, perfluor-1-propylene, the perfluor-2-propylene.
3, a kind of haloolefin addition hydrogen fluoride according to claim 1 prepares the method for saturated fluorine-containing alkane, it is characterized in that the saturated fluorine-containing alkane of gained is pentafluoride ethane, 1,1 after described polyfluoro is for alkene and hydrogen fluoride addition, 1,2-Vcon, 1,1,1,2-Tetrafluoroethane, 1,1,1-three fluoro-2,2-ethylene dichloride, 1,1,2-three fluoro-1,2-ethylene dichloride 1,1,1-trifluoro-chloroethane, 1,1,1,2,3,3,3-heptafluoro-propane, 1,1,1,3,3,3-HFC-236fa, 2, any one in 2-dihydro Octafluorobutane, the 2-hydrogen nine fluorine butane.
4, a kind of haloolefin addition hydrogen fluoride according to claim 1 prepares the method for saturated fluorine-containing alkane, it is characterized in that mode that described hydrogen fluoride and polyfluoro carry out addition reaction for alkene is any one mode in continous way or the intermittent type.
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| EP3901124A4 (en) * | 2018-12-19 | 2022-10-05 | Daikin Industries, Ltd. | Fluoroethane production method and fluoroolefin production method |
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| CN112279944B (en) * | 2020-10-10 | 2022-10-18 | 沈阳化工大学 | Preparation method of high-performance carboxyl-terminated low-molecular-weight fluorine-containing polymer |
| CN112500259B (en) * | 2020-12-14 | 2023-09-22 | 常熟三爱富中昊化工新材料有限公司 | Process for the preparation of heptafluoropropane |
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