CN107235834A - A kind of preparation method of perfluorethyl isopropyl ketone - Google Patents
A kind of preparation method of perfluorethyl isopropyl ketone Download PDFInfo
- Publication number
- CN107235834A CN107235834A CN201710551049.XA CN201710551049A CN107235834A CN 107235834 A CN107235834 A CN 107235834A CN 201710551049 A CN201710551049 A CN 201710551049A CN 107235834 A CN107235834 A CN 107235834A
- Authority
- CN
- China
- Prior art keywords
- methyl
- perfluor
- amylene
- mixture
- isopropyl ketone
- Prior art date
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Links
- HXVNBWAKAOHACI-UHFFFAOYSA-N 2,4-dimethyl-3-pentanone Chemical compound CC(C)C(=O)C(C)C HXVNBWAKAOHACI-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 72
- 239000000203 mixture Substances 0.000 claims abstract description 29
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 27
- -1 tertiary amine nitrogen oxides Chemical class 0.000 claims abstract description 25
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 10
- 239000004593 Epoxy Substances 0.000 claims abstract description 8
- 238000006735 epoxidation reaction Methods 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 239000002798 polar solvent Substances 0.000 claims description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 11
- 239000003444 phase transfer catalyst Substances 0.000 claims description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 150000003983 crown ethers Chemical class 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 239000002841 Lewis acid Substances 0.000 claims description 7
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical group [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 7
- 150000007517 lewis acids Chemical class 0.000 claims description 7
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 229960003511 macrogol Drugs 0.000 claims description 6
- 150000007530 organic bases Chemical class 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 6
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 5
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 230000001737 promoting effect Effects 0.000 claims description 5
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical group CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 claims description 4
- 229910001515 alkali metal fluoride Inorganic materials 0.000 claims description 4
- 125000003368 amide group Chemical group 0.000 claims description 4
- VBVBHWZYQGJZLR-UHFFFAOYSA-I antimony pentafluoride Chemical compound F[Sb](F)(F)(F)F VBVBHWZYQGJZLR-UHFFFAOYSA-I 0.000 claims description 4
- 239000003426 co-catalyst Substances 0.000 claims description 4
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims description 4
- 229960004194 lidocaine Drugs 0.000 claims description 4
- 150000002825 nitriles Chemical class 0.000 claims description 4
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 3
- LUZMLJILUGSLNT-UHFFFAOYSA-M P.[Br-].C(CCC)[P+](CCCC)(CCCC)CCCC Chemical compound P.[Br-].C(CCC)[P+](CCCC)(CCCC)CCCC LUZMLJILUGSLNT-UHFFFAOYSA-M 0.000 claims description 3
- 125000002015 acyclic group Chemical group 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- AJSHDAOMUKXVDC-UHFFFAOYSA-N butan-1-amine;sulfuric acid Chemical compound CCCC[NH3+].OS([O-])(=O)=O AJSHDAOMUKXVDC-UHFFFAOYSA-N 0.000 claims description 3
- 238000003682 fluorination reaction Methods 0.000 claims description 3
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 3
- QRPRIOOKPZSVFN-UHFFFAOYSA-M methyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C)C1=CC=CC=C1 QRPRIOOKPZSVFN-UHFFFAOYSA-M 0.000 claims description 3
- TZBAVQKIEKDGFH-UHFFFAOYSA-N n-[2-(diethylamino)ethyl]-1-benzothiophene-2-carboxamide;hydrochloride Chemical compound [Cl-].C1=CC=C2SC(C(=O)NCC[NH+](CC)CC)=CC2=C1 TZBAVQKIEKDGFH-UHFFFAOYSA-N 0.000 claims description 3
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical group [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 claims description 3
- 229940116357 potassium thiocyanate Drugs 0.000 claims description 3
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 3
- IQXJCCZJOIKIAD-UHFFFAOYSA-N 1-(2-methoxyethoxy)hexadecane Chemical compound CCCCCCCCCCCCCCCCOCCOC IQXJCCZJOIKIAD-UHFFFAOYSA-N 0.000 claims description 2
- GVWBJJLCTWNTRU-UHFFFAOYSA-N 4-benzylmorpholine Chemical class C=1C=CC=CC=1CN1CCOCC1 GVWBJJLCTWNTRU-UHFFFAOYSA-N 0.000 claims description 2
- 229910021630 Antimony pentafluoride Inorganic materials 0.000 claims description 2
- HIWGAPGRRFBTED-UHFFFAOYSA-N C1(=CC=CC=C1)N.[N]=O Chemical class C1(=CC=CC=C1)N.[N]=O HIWGAPGRRFBTED-UHFFFAOYSA-N 0.000 claims description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- CMEWLCATCRTSGF-UHFFFAOYSA-N N,N-dimethyl-4-nitrosoaniline Chemical compound CN(C)C1=CC=C(N=O)C=C1 CMEWLCATCRTSGF-UHFFFAOYSA-N 0.000 claims description 2
- 229920002593 Polyethylene Glycol 800 Polymers 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- RNTLJIIHLNXXJX-UHFFFAOYSA-N [N]=O.N1CCOCC1 Chemical class [N]=O.N1CCOCC1 RNTLJIIHLNXXJX-UHFFFAOYSA-N 0.000 claims description 2
- 229950009789 cetomacrogol 1000 Drugs 0.000 claims description 2
- 230000002153 concerted effect Effects 0.000 claims description 2
- YSSSPARMOAYJTE-UHFFFAOYSA-N dibenzo-18-crown-6 Chemical compound O1CCOCCOC2=CC=CC=C2OCCOCCOC2=CC=CC=C21 YSSSPARMOAYJTE-UHFFFAOYSA-N 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 2
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 150000003053 piperidines Chemical class 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims description 2
- 229940085675 polyethylene glycol 800 Drugs 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- GKKCIDNWFBPDBW-UHFFFAOYSA-M potassium cyanate Chemical group [K]OC#N GKKCIDNWFBPDBW-UHFFFAOYSA-M 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000006462 rearrangement reaction Methods 0.000 claims description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical group N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 claims 1
- CADWTSSKOVRVJC-UHFFFAOYSA-N benzyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CC1=CC=CC=C1 CADWTSSKOVRVJC-UHFFFAOYSA-N 0.000 claims 1
- 150000004985 diamines Chemical class 0.000 claims 1
- WJLUBOLDZCQZEV-UHFFFAOYSA-M hexadecyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CCCCCCCCCCCCCCCC[N+](C)(C)C WJLUBOLDZCQZEV-UHFFFAOYSA-M 0.000 claims 1
- RIWRFSMVIUAEBX-UHFFFAOYSA-N n-methyl-1-phenylmethanamine Chemical group CNCC1=CC=CC=C1 RIWRFSMVIUAEBX-UHFFFAOYSA-N 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 14
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 238000012805 post-processing Methods 0.000 abstract description 3
- 231100000331 toxic Toxicity 0.000 abstract description 3
- 230000002588 toxic effect Effects 0.000 abstract description 3
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract 1
- 238000004458 analytical method Methods 0.000 description 18
- 238000003756 stirring Methods 0.000 description 17
- 238000000746 purification Methods 0.000 description 16
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- 150000002924 oxiranes Chemical class 0.000 description 5
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 5
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical class CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- USJRLGNYCQWLPF-UHFFFAOYSA-N chlorophosphane Chemical compound ClP USJRLGNYCQWLPF-UHFFFAOYSA-N 0.000 description 3
- YLCLKCNTDGWDMD-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanoyl fluoride Chemical compound FC(=O)C(F)(F)C(F)(F)F YLCLKCNTDGWDMD-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- HYTRYEXINDDXJK-UHFFFAOYSA-N Ethyl isopropyl ketone Chemical compound CCC(=O)C(C)C HYTRYEXINDDXJK-UHFFFAOYSA-N 0.000 description 2
- 229920004449 Halon® Polymers 0.000 description 2
- 241000165940 Houjia Species 0.000 description 2
- NNJVILVZKWQKPM-UHFFFAOYSA-N Lidocaine Chemical compound CCN(CC)CC(=O)NC1=C(C)C=CC=C1C NNJVILVZKWQKPM-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical group [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 239000011698 potassium fluoride Substances 0.000 description 2
- MTUARLUNITVZES-UHFFFAOYSA-N 1,1,1,2,2-pentafluorododecan-3-one Chemical compound CCCCCCCCCC(=O)C(F)(F)C(F)(F)F MTUARLUNITVZES-UHFFFAOYSA-N 0.000 description 1
- YLHYBZBPDWAWCY-UHFFFAOYSA-N 1,1,1,2,2-pentafluorononan-3-one Chemical compound CCCCCCC(=O)C(F)(F)C(F)(F)F YLHYBZBPDWAWCY-UHFFFAOYSA-N 0.000 description 1
- ZXIWYFCHHRVWOX-UHFFFAOYSA-N 1-fluoro-2-methylpentane Chemical class CCCC(C)CF ZXIWYFCHHRVWOX-UHFFFAOYSA-N 0.000 description 1
- VJGCZWVJDRIHNC-UHFFFAOYSA-N 1-fluoroprop-1-ene Chemical class CC=CF VJGCZWVJDRIHNC-UHFFFAOYSA-N 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical class CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910001618 alkaline earth metal fluoride Inorganic materials 0.000 description 1
- 239000004411 aluminium 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical group [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- UQXKXGWGFRWILX-UHFFFAOYSA-N ethylene glycol dinitrate Chemical compound O=N(=O)OCCON(=O)=O UQXKXGWGFRWILX-UHFFFAOYSA-N 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000006342 heptafluoro i-propyl group Chemical group FC(F)(F)C(F)(*)C(F)(F)F 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- IWPWMAJDSLSRIP-UHFFFAOYSA-N nezukone Chemical compound CC(C)C1=CC=CC(=O)C=C1 IWPWMAJDSLSRIP-UHFFFAOYSA-N 0.000 description 1
- 125000005004 perfluoroethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229940093429 polyethylene glycol 6000 Drugs 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- WMFABESKCHGSRC-UHFFFAOYSA-N propanoyl fluoride Chemical compound CCC(F)=O WMFABESKCHGSRC-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical class [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
- C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
- C07C45/58—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in three-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
- C07C17/358—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction by isomerisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/08—Compounds containing oxirane rings with hydrocarbon radicals, substituted by halogen atoms, nitro radicals or nitroso radicals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Epoxy Compounds (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of preparation method of perfluorethyl isopropyl ketone, mixture using the amylene of 4 methyl of perfluor 2 or the amylene of 4 methyl of perfluor 2 and the amylene of 2 methyl of perfluor 2 is raw material, the amylene of 4 methyl of perfluor 2 is first converted into the amylene of 2 methyl of perfluor 2 by isomerization reaction, the amylene epoxy of 2 methyl of perfluor 2 is turned into the methyl 2 of perfluor 2 again, 3 epoxypentanes, it is again perfluorethyl isopropyl ketone by the epoxypentane catalytically rearranging of 2 methyl of perfluor 2,3.The advantage of the invention is that：Isoversion reaction of the present invention can be in solvent-free lower progress, it is to avoid existing process largely uses toxic solvent, the problems such as recycling is difficult；Using tertiary amine nitrogen oxides or N, N dialkylhydroxyamines are epoxidation reagent, realize that the amylene of 2 methyl of perfluor 2 is quantitative in a mild condition to be converted into the methyl 2 of perfluor 2,3 epoxypentanes, avoid existing process and largely use liquor natrii hypochloritis, severe corrosion equipment, post processing produces a large amount of salt shipwrecks and reclaimed, the problems such as use condition is harsh.
Description
Technical field
The invention belongs to the preparation method technical field of perfluoroketone compound in organic fluorine chemistry,
More particularly to a kind of preparation method of perfluorethyl isopropyl ketone.
Background technology
Perfluorethyl isopropyl ketone is also known as 12 fluoro- 2- methylpentanes -3- ketone, is referred to as fluorinated hexanone, molecular formula
For CF3CF2C(O)CF(CF3)2, CAS numberings are 756-13-8.Perfluorethyl isopropyl ketone is as extinguishing chemical in use, tool
Have that extinguishing concentration is small, fire-fighting efficiency is high, good environmental protection, toxicity is low, security is good, influence to relevant device and material is small,
Noresidue, it is easy to store and transports and the series of advantages such as applied widely.While high fire-fighting efficiency is ensured, solve
Problem of the conventional fluoro alkanes Halon's succedaneum in terms of environmental protection, is a kind of really long-acting Halon Replacement product, has used
In the fire extinguishing system at important place or position.With the reduction of production cost, its application field will expand, and final application is arrived
In the fire extinguishing system of general industry and civil buildings, with vast potential for future development.
In addition to as extinguishing chemical, protective gas, cleaning agent when perfluorethyl isopropyl ketone is alternatively arranged as Melting Magnesium and molten
Agent is used, and can be also added to as fire resistant fluid in various inflammable hydraulic fluids flammable it is reduced or eliminated.
The former Soviet Union has synthesized perfluorethyl isopropyl ketone, but unrealized large-scale production in the 70's of 20th century.Until
2001,3M companies of the U.S. as after the extinguishing chemical for replacing Ha Long and fluoroalkane, its synthesis and application study just by
Gradually paid close attention to by people.
United States Patent (USP) US6478979B1 describes a kind of method for preparing perfluorethyl isopropyl ketone.In anhydrous condition
Under, using aprotic polar solvent diethylene glycol dimethyl ether as reaction medium, active potassium fluoride makees catalyst, adds in perfluoro-propionyl fluoride
Enter hexafluoropropene, perfluorethyl isopropyl ketone is made.Reaction temperature is 70 DEG C, pressure 1MPa.The crude product of acquisition contains perfluor
Ethyl isopropyl ketone 90.6%, hexafluoropropylene dimmer 0.37%.React to the yield of hexafluoropropene up to 98.8%, to perfluor
The yield of propionyl fluoride is 79.28%.A small amount of trimerization can be removed from perfluorethyl isopropyl ketone by washing, distillation and drying
The impurity such as body, are obtained containing hexafluoropropylene dimmer 0.4%, the perfluorethyl isopropyl ketone that purity is 99%.The reaction scheme
Yield and selectivity are higher, but raw material perfluoro-propionyl fluoride prepares difficulty greatly, and reaction yield is low, and cost is high, and the country is not implemented always
The industrialization of the product.
Vilenchik etc.（Zh.Khim,1978,23(2):236-237）One kind is reported using hexafluoropropene as raw material system
The method of standby perfluorethyl isopropyl ketone.At 20~25 DEG C, hexafluoropropene is first oxidized to perfluor epoxy third with oxygen
Alkane, the latter reacts under the catalysis of cesium fluoride with the hexafluoropropene of another molecule, and perfluorethyl isopropyl ketone is made.From molecule
The technology path is ideal from the perspective of utilization rate, and raw material and oxidant are easily obtained, but target product selectivity compared with
Difference, side reaction are more.Only contain perfluorethyl isopropyl ketone 34.6%, also 42.6% perfluoro-ethyl n-hexyl ketone in crude product
With 8% perfluoro-ethyl n-nonyl ketone, the oxide of tripolymer and the tetramer is more in accessory substance.Zapevalov etc.
（Izv.Akad.Nauk,1979,(12):2812）Perfluor -4- methyl -2- amylenes are oxidized to epoxy using liquor natrii hypochloritis
Compound, but the catalysis of the reaction is poor, while generating two kinds of epoxides.Wherein, a kind of epoxides need to be in fluorination
Perfluorethyl isopropyl ketone is rearranged under the catalysis of caesium；The activity of another epoxides is higher, in KF or the work of triethylamine
Rearrangeable under is target product, and yield is 93% or so, and reaction condition is gentleer.The characteristics of reaction is from six easily obtained
Fluoropropene dimer sets out, and reaction yield is higher, but reactivity is different during due to different epoxides catalytically rearrangings, need to be through oxygen
Change, separation, reset respectively, the stage such as refined could obtain target product, flow is excessively complicated.
For above-mentioned phenomenon, the B of patent CN 102992986 disclose a kind of method for preparing perfluorethyl isopropyl ketone.
Detailed process using hexafluoropropylene dimmer mixture, perfluor -4- methyl -2- amylenes or perfluoro-2-methyl-2-amylene as raw material,
Through courses of reaction such as alkene epoxidation, the structural rearrangements of epoxides, perfluorethyl isopropyl ketone is prepared.Used in preparation process
Aprotic polar solvent, catalyst and phase transfer catalyst, realize the high selectivity and high conversion of each step reaction, reaction
Mixture is after simple separation, you can obtain the intermediate and perfluorethyl isopropyl ketone product of high-quality.At the same time, set up
" one kettle way " technology of double-bond isomerization and epoxidation reaction.There is the technology of preparing that the invention is provided raw material to be easy to get, into
This is cheap, reaction condition is gentle, safe operation, simple, reaction selectivity and high conversion rate, the features such as ambient influnence is small be adapted to
Industrial applications；But the invention preparation method haves the shortcomings that certain：It is with perfluor -4- methyl -2- amylenes or perfluor -2- first
Base -2- amylenes are that raw material prepares perfluorethyl isopropyl ketone technology by steps such as epoxidation and isomerization, inevitably
Need largely to cause post processing using the toxic solvents such as acetonitrile and severe corrosive and irritating oxidising agent liquor natrii hypochloritis
Large amount of sewage and toxic solvent are produced, there is the shortcomings of complicated post processing and serious environmental pollution.
The content of the invention
It is above-mentioned to solve the technical problem to be solved in the present invention is to provide a kind of preparation method of perfluorethyl isopropyl ketone
Technical problem.
In order to solve the above technical problems, the technical scheme is that：A kind of preparation method of perfluorethyl isopropyl ketone,
Its innovative point is：The preparation method comprises the following steps：With perfluor -4- methyl -2- amylenes or perfluor -4- methyl -2-
The mixture of amylene and perfluoro-2-methyl-2-amylene is raw material, first that perfluor -4- methyl -2- amylenes is anti-by isomerisation of olefin
Perfluoro-2-methyl-2-amylene should be converted into, then perfluoro-2-methyl-2-amylene epoxy is turned into perfluor -2- methyl -2,3- epoxies
Pentane, is finally perfluorethyl isopropyl ketone by perfluor -2- methyl -2,3- epoxypentanes catalytically rearranging；Comprise the following steps：
（1）The isomerization reaction of perfluor -4- methyl -2- amylenes
Using the mixture of perfluor -4- methyl -2- amylenes or perfluor -4- methyl -2- amylenes and perfluoro-2-methyl-2-amylene as
Raw material, by perfluor -4- methyl -2- amylenes in solvent-free or aprotic polar solvent, carries out catalytic isomerization at 20~150 DEG C
Change 4~30h of reaction, reaction is converted into perfluoro-2-methyl-2-amylene；Wherein, catalytic isomerization reaction passes through major catalyst, helps and urge
Agent and catalyst promoting agent carry out concerted catalysis, and major catalyst, co-catalyst, catalyst promoting agent and aprotonic polar are molten
Agent mass ratio is：1:0.1~5:0.5~5:10~50；The mol ratio of major catalyst and raw material is：0.01~0.2；It is described to sponsor
Agent selects four（N, N- dialkyl amido）Ethene, cyanide salt, cyanate, thiocyanate, alkali metal fluoride, alkaline-earth metal
Fluoride, fluorine aluminium chloride, lewis acid or their mixture, the co-catalyst select organic base, and the catalyst promotes
Crown ether, polyethylene glycol, quaternary ammonium salt or their mixture are selected in agent；
（2）The epoxidation reaction of perfluoro-2-methyl-2-amylene
The mol ratio of oxidant and perfluoro-2-methyl-2-amylene is 1~5；The volume ratio of solvent and perfluoro-2-methyl-2-amylene
For 0.2~5；At -20 ~ 60 DEG C, 0.1~8h is reacted, it is perfluor -2- methyl -2 to make perfluoro-2-methyl-2-amylene Quantitative yield,
3- epoxypentanes；Wherein, the oxidant is tertiary amine nitrogen oxides, N, and N- dialkylhydroxyamines or their mixture are described molten
Agent is aprotic polar solvent；
（3）The rearrangement reaction of perfluor -2- methyl -2,3- epoxypentanes
The volume ratio of solvent and perfluor -2- methyl -2,3- epoxypentanes is 0.1~10, catalyst and perfluor -2- methyl -2,3-
The mol ratio of epoxypentane is 0.01~0.2, and the mol ratio of catalyst and phase transfer catalyst is 0. 05~0.15, reaction temperature
Spend for 10 ~ 250 DEG C, the reaction time is 0.5~12h, perfluor -2- methyl -2,3- epoxypentanes is converted into perfluoro-ethyl isopropyl
Base ketone；Wherein, the solvent is aprotic polar solvent, and the catalyst is organic base or lewis acid, described phase transfer
Catalyst is crown ether, polyethylene glycol, quaternary ammonium salt or quaternary alkylphosphonium salt or their mixture.
The preparation method of perfluorethyl isopropyl ketone of the present invention, wherein, step（1）Reaction temperature is but excellent at 20~150 DEG C
The temperature of choosing is 50 ~ 100 DEG C；Reaction can be carried out at ambient pressure, can also be entered under system self-pressurization or appropriate pressurized conditions
OK, but preferably under 0.2 ~ 1.0MPa carry out；Step（1）Can be carried out in aprotic polar solvent, but preferably with without using
Solvent, simply needs slightly to improve the temperature and pressure of reaction.
Further, in step（2）During epoxidation reaction, phase transfer catalyst, the phase transfer catalyst can be also added
Mol ratio with perfluoro-2-methyl-2-amylene is 0.01~0.5, and phase transfer catalyst is crown ether, polyethylene glycol, quaternary alkylphosphonium salts
Or their mixture.
Further, the step（1）In four（N, N- dialkyl amido）Ethene is four（N, N- dimethylamino）Ethene or
Four（N, N- lignocaine）Ethene, cyanide salt is potassium cyanide, and cyanate is potassium cyanate, and thiocyanate is potassium thiocyanate, alkali
Metal fluoride is cesium fluoride, and alkali earth metal fluoride is magnesium fluoride；Preferably select potassium thiocyanate or four（Lignocaine）
Ethene is the catalyst of this step, especially from four（Lignocaine）Ethene can be such that this reaction enters under condition of no solvent
OK, you can the conversion ratio of raw material is reached 99%.
Further, the step（2）Middle tertiary amine nitrogen oxides be acyclic straight or branched tertiary amine nitrogen oxides,
Morpholine nitrogen oxides, pyridine nitric oxide, piperidines nitrogen oxides, aniline nitrogen oxides, benzylamine nitrogen oxides or their mixing
Thing, preferably the alkyl tertiary amine nitrogen oxides from acyclic straight, such as (CH3CH2)3NO；Step（2）In N, N- dialkyl group hydroxyls
Alkyl in amine selects C1~C4 linear paraffin, preferably from (CH3CH2CH2)2NOH。
Further, the organic base is trimethylamine, triethylamine, tri-n-butylamine, piperidines, N- picolines, N, N- dimethyl
Aniline, N, N- dimethyl benzylamines, N- methyl cyclohexanes diamines, N-methylmorpholine, N- Benzvlmorpholins or their mixture；Preferably select
With triethylamine or N, N- dimethyl benzylamine.
Further, the crown ether is 18- crown-s 6,15- crown-s 5, dibenzo-18 crown-6 or their mixture, poly- second
Glycol is polyethylene glycol 400, Macrogol 600, polyethylene glycol-800, cetomacrogol 1000, Macrogol 4000, polyethylene glycol
6000 or their mixture；Preferably select 18- crown-s 6 or Macrogol 4000.
Further, the aprotic polar solvent be acetonitrile, DMA, sulfolane, dimethyl sulfoxide (DMSO),
Glycol dimethyl ether, diethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether or their mixture；Preferably select and glycol dinitrate
Ether.
Further, the quaternary ammonium salt is dodecyl benzyl dimethyl ammonium chloride, cetyl trimethylammonium bromide, ten
Six alkyltrimethylammonium hydroxides, tri-n-octyl methyl ammonium chloride, tetrabutyl ammonium halide, 4-butyl ammonium hydrogen sulfate or their mixing
Thing；Preferably select 4-butyl ammonium hydrogen sulfate.
Further, the quaternary alkylphosphonium salt be methyl triphenyl phosphonium chloride, tetrabutyl phosphonium bromide phosphine or it
Mixture.
Further, the lewis acid is any of antimony pentafluoride or fluorine aluminium chloride.
The advantage of the invention is that：
（1）The preparation method of perfluorethyl isopropyl ketone of the present invention, first step isoversion reaction can enter under solvent-free
OK, that realizes perfluor -4- methyl -2- amylene high yields is converted into perfluoro-2-methyl-2-amylene；Second step uses tertiary amine nitrogen
Oxide or N, N- dialkylhydroxyamines are epoxidation reagent, realize perfluoro-2-methyl-2-amylene it is quantitative be converted into perfluor-
2- methyl -2,3- epoxypentanes, it is to avoid existing process largely uses liquor natrii hypochloritis's severe corrosion equipment, use condition is severe
The problems such as quarter；The reaction of final step catalytically rearranging only needs the organic amine or lewis acid of catalytic amount, you can make perfluoro-ethyl
The yield of nezukone is up to more than 95%；
（2）The preparation method of perfluorethyl isopropyl ketone of the present invention, wherein, during second step epoxy reaction, phase transfer can be added
Catalyst, and then the efficiency of reaction can be improved, greatly save the time.
Embodiment
The following examples can make professional and technical personnel that the present invention is more fully understood, but therefore not send out this
It is bright to be limited among described scope of embodiments.
Embodiment 1
By 1g potassium cyanide, 5gN- picolines, 5g dibenzo-18 crown-6s and 50g acetonitriles add flask in, then by 300g perfluors-
4- methyl -2- amylenes are added in the reaction system, the stirring reaction 20h at 40 DEG C.Separate, after purification, analysis finds perfluor -4-
Inverted methyl -2- amylene second is perfluoro-2-methyl-2-amylene, and the conversion ratio of reaction is 97.5%.
By 0.3mol（CH3CH2CH2）2NOH, 18.5mL DMA and 0.05mol tetrabutyl phosphonium bromide phosphines add
Enter in three-necked flask, then add the above-mentioned perfluoro-2-methyl-2-amylenes of 0.1mol, at 40 DEG C and continue stirring reaction 2h.Point
From, after purification, analysis find perfluoro-2-methyl-2-amylene it is quantitative be converted into perfluor -2- methyl -2,3- epoxypentanes.
30mL glycol dimethyl ethers, 0.2mol N, N- dimethyl benzylamines and 0.1mol methyl triphenyls phosphonium chloride are added
In flask, 1mol perfluor -2- methyl -2,3- epoxypentanes of above-mentioned preparation are then added, continue stirring reaction 2h at 20 DEG C.
Separate, after purification, analysis finds that Quantitative yield is perfluorethyl isopropyl ketone to perfluor -2- methyl -2,3- epoxypentane.
Embodiment 2
2g potassium rhodanates, 0.7g N, N- dimethyl benzylamine, 2g Macrogol 4000s and 30g diethylene glycol dimethyl ethers are added and burnt
In bottle, then 300g perfluor -4- methyl -2- amylenes are added in the reaction system, at 90 DEG C, stirring reaction 6h under 0.3MPa.Point
From, after purification, analysis find perfluor -4- methyl -2- amylene second it is inverted be perfluoro-2-methyl-2-amylene, the conversion ratio of reaction
For 99.7%.
By 0.1mol（CH3CH2）2NOH, 15mL DMA are added in three-necked flask, are then added above-mentioned
0.1mol perfluoro-2-methyl-2-amylenes, continue stirring reaction 8h at 70 DEG C.Separate, after purification, analysis finds perfluor -2- first
Base -2- amylenes have been converted into perfluor -2- methyl -2,3- epoxypentanes, and the conversion ratio of reaction is 98.9%.
40mL glycol dimethyl ethers, 0.06mol triethylamines and 0.05mol18- crown-s 6 are added in flask, then added
1mol perfluor -2- methyl -2,3- epoxypentanes of preparation are stated, continue stirring reaction 5h at 20 DEG C.Separate, after purification, analysis
It was found that Quantitative yield is perfluorethyl isopropyl ketone to perfluor -2- methyl -2,3- epoxypentanes.
Embodiment 3
1g antimony pentafluorides, 3g N- picolines and 1g18- crown-s 6 are added in flask, then by 300g perfluor -4- methyl -2- penta
Alkene is added in the reaction system, the stirring reaction 25h at 120 DEG C.Separate, after purification, analysis finds perfluor -4- methyl -2- penta
Inverted alkene second is perfluoro-2-methyl-2-amylene, and the conversion ratio of reaction is 98.1%.
By 0.3mol（CH3）2NOH, 40mL DMA and 0.03mol tetrabutyl phosphonium bromides phosphine add three mouthfuls of burnings
In bottle, the above-mentioned perfluoro-2-methyl-2-amylenes of above-mentioned 0.1mol are then added, continue stirring reaction 8h at 20 DEG C.Separation, it is pure
After change, analysis finds that perfluoro-2-methyl-2-amylene has been converted into perfluor -2- methyl -2,3- epoxypentanes.
8mL tetraethyleneglycol dimethyl ethers, 0.1mol tri-n-butylamines and 0.08mol Macrogol 4000s are added in flask, then
1mol perfluor -2- methyl -2,3- epoxypentanes of above-mentioned preparation are added, 8h is persistently stirred at 30 DEG C.Separate, after purification, point
Analysis finds that Quantitative yield is perfluorethyl isopropyl ketone to perfluor -2- methyl -2,3- epoxypentanes.
Embodiment 4
By 10g tetra-（N, N- dimethylamino）Ethene, 1g trimethylamines, 5g Macrogol 4000s and 100g sulfolane add flask
In, then 300g perfluor -4- methyl -2- amylenes are added in the reaction system, the stirring reaction 5h at 40 DEG C.Separate, after purification,
Analysis find perfluor -4- methyl -2- amylene second it is inverted be perfluoro-2-methyl-2-amylene, the conversion ratio of reaction is 99.6%.
By 0.1mol（CH3CH2）3NO, 8 mL glycol dimethyl ethers and 0.01mol Macrogol 600s add three-necked flask
In, above-mentioned 0.1mol perfluoro-2-methyl-2-amylenes are then added, continue stirring reaction 5h at 50 DEG C.Separate, after purification, point
Analysis finds that perfluoro-2-methyl-2-amylene has been converted into perfluor -2- methyl -2,3- epoxypentanes, and the conversion ratio of reaction is 98.9%.
50mL sulfolane, 0.06molN- Benzvlmorpholins and 0.05mol methyl triphenyls phosphonium chloride are added in flask, so
1mol perfluor -2- methyl -2,3- epoxypentanes of above-mentioned preparation are added afterwards, continue stirring reaction 8h at 60 DEG C.Separation, purifying
Afterwards, analysis finds that Quantitative yield is perfluorethyl isopropyl ketone to perfluor -2- methyl -2,3- epoxypentane.
Embodiment 5
By 1g magnesium fluorides and fluorination aluminium mixture, 0.2gN- Benzvlmorpholins, 0.7g cetomacrogol 1000s and 20g glycol dimethyl ethers
Add in flask, then 300g perfluor -4- methyl -2- amylenes are added in the reaction system, the stirring reaction 24h at 60 DEG C.Point
From, after purification, analysis find perfluor -4- methyl -2- amylene second it is inverted be perfluoro-2-methyl-2-amylene, the conversion ratio of reaction
For 98.5%.
By 0.1mol（CH3CH2 CH2）3NO, 18mL diethylene glycol dimethyl ether and 0.01mol18- crown-s 6 add three-necked flask
In, above-mentioned 0.1mol perfluoro-2-methyl-2-amylenes are then added, continue stirring reaction 8h at 0 DEG C.Separate, after purification, point
Analysis finds that perfluoro-2-methyl-2-amylene has been converted into perfluor -2- methyl -2,3- epoxypentanes, and the conversion ratio of reaction is 98.9%.
80mL dimethyl sulfoxide (DMSO)s, 0.06molN- methyl cyclohexylamines and 0.05mol15- crown-s 5 are added in flask, Ran Houjia
Enter 1mol perfluor -2- methyl -2,3- epoxypentanes of above-mentioned preparation, continue stirring reaction 12h at 70 DEG C.Separate, after purification,
Analysis finds that Quantitative yield is perfluorethyl isopropyl ketone to perfluor -2- methyl -2,3- epoxypentanes.
Embodiment 6
By 10g cesium fluorides, 2gN, accelerine and 5g15- crown-s 5 are added in flask, then by 300g perfluor -4- methyl -2-
Amylene is added in the reaction system, the stirring reaction 29h at 50 DEG C.Separate, after purification, analysis finds perfluor -4- methyl -2- penta
Inverted alkene second is perfluoro-2-methyl-2-amylene, and the conversion ratio of reaction is 99.8%.
By 0.1mol（CH3CH2 CH2 CH2）3NO, 13mL tetraethyleneglycol dimethyl ether and 0.01mol methyl triphenyl phosphonium chlorides
Add in three-necked flask, then add above-mentioned 0.1mol perfluoro-2-methyl-2-amylenes, continue stirring reaction 3h at -5 DEG C.Point
From, after purification, analysis finds that perfluoro-2-methyl-2-amylene has been converted into perfluor -2- methyl -2,3- epoxypentanes, and reaction turns
Rate is 98.9%.
60mL acetonitriles, 0.06mol antimony pentafluorides and 0.05mol methyl triphenyls phosphonium chloride are added in flask, Ran Houjia
Enter 1mol perfluor -2- methyl -2,3- epoxypentanes of above-mentioned preparation, the stirring reaction 12h at 110 DEG C.Separate, after purification, point
Analysis finds that Quantitative yield is perfluorethyl isopropyl ketone to perfluor -2- methyl -2,3- epoxypentanes.
The general principle and principal character and advantages of the present invention of the present invention has been shown and described above.The skill of the industry
Art personnel are it should be appreciated that the present invention is not limited to the above embodiments, and described in above-described embodiment and specification is explanation
The principle of the present invention, without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are possible, these
Changes and improvements all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and
Its equivalent thereof.
Claims (10)
1. a kind of preparation method of perfluorethyl isopropyl ketone, it is characterised in that：The preparation method comprises the following steps：With complete
The mixture of fluoro- 4- methyl -2- amylenes or perfluor -4- methyl -2- amylenes and perfluoro-2-methyl-2-amylene is raw material, first will
Perfluor -4- methyl -2- amylenes are converted into perfluoro-2-methyl-2-amylene by olefin isomerization, then by perfluor -2- methyl -
2- amylene epoxies turn to perfluor -2- methyl -2,3- epoxypentanes, finally by perfluor -2- methyl -2,3- epoxypentane catalytically rearrangings
For perfluorethyl isopropyl ketone；Comprise the following steps：
（1）The isomerization reaction of perfluor -4- methyl -2- amylenes
Using the mixture of perfluor -4- methyl -2- amylenes or perfluor -4- methyl -2- amylenes and perfluoro-2-methyl-2-amylene as
Raw material, by perfluor -4- methyl -2- amylenes in solvent-free or aprotic polar solvent, carries out catalytic isomerization at 20~150 DEG C
Change 4~30h of reaction, be converted into perfluoro-2-methyl-2-amylene；Wherein, isoversion reaction passes through major catalyst, co-catalysis
Agent and catalyst promoting agent carry out concerted catalysis, and major catalyst, co-catalyst, catalyst promoting agent and aprotic polar solvent
Mass ratio is：1:0.1~5:0.5~5:10~50；The mol ratio of major catalyst and raw material is：0.01~0.2；The main catalytic
Agent selects four（N, N- dialkyl amido）Ethene, cyanide salt, cyanate, thiocyanate, alkali metal fluoride, alkaline-earth metal fluorine
Compound, lewis acid or their mixture, the co-catalyst select organic base, the catalyst promoting agent from crown ether,
Polyethylene glycol, quaternary ammonium salt or their mixture；
（2）The epoxidation reaction of perfluoro-2-methyl-2-amylene
The mol ratio of oxidant and perfluoro-2-methyl-2-amylene is 1~5；The volume ratio of solvent and perfluoro-2-methyl-2-amylene
For 0.2~5；At -20 ~ 60 DEG C, 0.1~8h is reacted, it is perfluor -2- methyl -2 to make perfluoro-2-methyl-2-amylene Quantitative yield,
3- epoxypentanes；Wherein, the oxidant is tertiary amine nitrogen oxides, N, and N- dialkylhydroxyamines or their mixture are described molten
Agent is aprotic polar solvent；
（3）The rearrangement reaction of perfluor -2- methyl -2,3- epoxypentanes
The volume ratio of solvent and perfluor -2- methyl -2,3- epoxypentanes is 0.1~10, catalyst and perfluor -2- methyl -2,3-
The mol ratio of epoxypentane is 0.01~0.2, and the mol ratio of catalyst and phase transfer catalyst is 0. 05~0.15, reaction temperature
Spend for 10 ~ 250 DEG C, the reaction time is 0.5~12h, perfluor -2- methyl -2,3- epoxypentanes is converted into perfluoro-ethyl isopropyl
Base ketone；Wherein, the solvent is aprotic polar solvent, and the catalyst is organic base or lewis acid, described phase transfer
Catalyst is crown ether, polyethylene glycol, quaternary ammonium salt or quaternary alkylphosphonium salt or their mixture.
2. the preparation method of perfluorethyl isopropyl ketone according to claim 1, it is characterised in that：In step（2）Epoxy
When changing reaction, phase transfer catalyst can be also added, the mol ratio of the phase transfer catalyst and perfluoro-2-methyl-2-amylene is
0.01~0.5, and phase transfer catalyst is crown ether, polyethylene glycol, quaternary alkylphosphonium salts or their mixture.
3. the preparation method of perfluorethyl isopropyl ketone according to claim 1, it is characterised in that：The step（1）In
Four（N, N- dialkyl amido）Ethene is four（N, N- dimethylamino）Ethene or four（N, N- lignocaine）Ethene, cyanide salt is cyanogen
Change potassium, cyanate is potassium cyanate, and thiocyanate is potassium thiocyanate, and alkali metal fluoride is cesium fluoride, alkaline-earth metal fluorination
Thing is magnesium fluoride.
4. the preparation method of perfluorethyl isopropyl ketone according to claim 1, it is characterised in that：The step（2）In
Tertiary amine nitrogen oxides is acyclic straight or branched tertiary amine nitrogen oxides, morpholine nitrogen oxides, pyridine nitric oxide, piperidines
Nitrogen oxides, aniline nitrogen oxides, benzylamine nitrogen oxides or their mixture, step（2）In N, in N- dialkylhydroxyamines
Alkyl select C1~C4 linear paraffin.
5. the preparation method of perfluorethyl isopropyl ketone according to claim 1, it is characterised in that：
The organic base is trimethylamine, triethylamine, tri-n-butylamine, piperidines, N- picolines, N, accelerine, N, N- diformazans
Base benzylamine, N- methyl cyclohexanes diamines, N-methylmorpholine, N- Benzvlmorpholins or their mixture.
6. the preparation method of perfluorethyl isopropyl ketone according to claim 1 or 2, it is characterised in that：The crown ether is
18- crown-s 6,15- crown-s 5, dibenzo-18 crown-6 or their mixture, polyethylene glycol are polyethylene glycol 400, polyethylene glycol
600th, polyethylene glycol-800, cetomacrogol 1000, Macrogol 4000, Macrogol 6000 or their mixture.
7. the preparation method of perfluorethyl isopropyl ketone according to claim 1, it is characterised in that：The aprotonic polar
Solvent is acetonitrile, DMA, sulfolane, dimethyl sulfoxide (DMSO), glycol dimethyl ether, diethylene glycol dimethyl ether, four
Glycol dimethyl ether or their mixture.
8. the preparation method of perfluorethyl isopropyl ketone according to claim 1, it is characterised in that：The quaternary ammonium salt is ten
Dialkyl dimethyl benzyl ammonium chloride, cetyl trimethylammonium bromide, cetyltrimethylammonium hydroxide, tricaprylmethyl
Ammonium chloride, tetrabutyl ammonium halide, 4-butyl ammonium hydrogen sulfate or their mixture.
9. the preparation method of perfluorethyl isopropyl ketone according to claim 1 or 2, it is characterised in that：The quaternary alkylphosphonium salt
For methyl triphenyl phosphonium chloride, tetrabutyl phosphonium bromide phosphine or their mixture.
10. the preparation method of perfluorethyl isopropyl ketone according to claim 1, it is characterised in that：The lewis acid
For any of antimony pentafluoride or fluorine aluminium chloride.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019006993A1 (en) * | 2017-06-28 | 2019-01-10 | 江苏科技大学 | Method for preparing perfluoroethyl isopropyl ketone |
| CN111484398A (en) * | 2019-04-22 | 2020-08-04 | 北京航天神禾防务技术有限公司 | Method for preparing perfluorohexanone |
| CN111848444A (en) * | 2020-08-14 | 2020-10-30 | 福建省漳平市九鼎氟化工有限公司 | Synthesis method of perfluoroisobutyronitrile |
| CN116273164A (en) * | 2023-03-16 | 2023-06-23 | 浙江锦华新材料股份有限公司 | Isomerization reaction catalyst of perfluoro-4-methyl-2-pentene |
| CN116514642A (en) * | 2023-05-06 | 2023-08-01 | 多氟多新材料股份有限公司 | Preparation method and application of perfluoro-hexanone |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1095367A (en) * | 1992-12-28 | 1994-11-23 | 美国3M公司 | The preparation of hexafluoropropene oligomers |
| CN103483139A (en) * | 2012-06-15 | 2014-01-01 | 中化蓝天集团有限公司 | Perfluoro-2-methyl-2-pentene preparation method |
| CN102992986B (en) * | 2012-09-29 | 2016-02-03 | 中国人民武装警察部队学院 | The preparation method of perfluorethyl isopropyl ketone |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105198719B (en) * | 2015-09-06 | 2017-08-01 | 浙江工业大学 | A kind of preparation method of the pentanone of 2 methyl of perfluor 3 |
| CN106542984A (en) * | 2016-10-13 | 2017-03-29 | 巨化集团技术中心 | A kind of preparation method of 2 methyl of perfluor, 3 pentanone |
| CN107235834B (en) * | 2017-06-28 | 2020-09-08 | 江苏科技大学 | Preparation method of perfluoroethyl isopropyl ketone |
-
2017
- 2017-07-07 CN CN201710551049.XA patent/CN107235834B/en active Active
- 2017-12-15 WO PCT/CN2017/116479 patent/WO2019006993A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1095367A (en) * | 1992-12-28 | 1994-11-23 | 美国3M公司 | The preparation of hexafluoropropene oligomers |
| CN103483139A (en) * | 2012-06-15 | 2014-01-01 | 中化蓝天集团有限公司 | Perfluoro-2-methyl-2-pentene preparation method |
| CN102992986B (en) * | 2012-09-29 | 2016-02-03 | 中国人民武装警察部队学院 | The preparation method of perfluorethyl isopropyl ketone |
Non-Patent Citations (2)
| Title |
|---|
| TAIZO ONO 等: "Novel epoxidation reaction of perfluoroalkenes with trimethylamine N-oxide and iodosylbenzene", 《TETRAHEDRON LETTERS》 * |
| XING WEI CAI 等: "Epoxidation reaction of perfluoroalkenes with tert-amine N-oxide", 《CHINESE CHEMICAL LETTERS》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019006993A1 (en) * | 2017-06-28 | 2019-01-10 | 江苏科技大学 | Method for preparing perfluoroethyl isopropyl ketone |
| CN111484398A (en) * | 2019-04-22 | 2020-08-04 | 北京航天神禾防务技术有限公司 | Method for preparing perfluorohexanone |
| CN111848444A (en) * | 2020-08-14 | 2020-10-30 | 福建省漳平市九鼎氟化工有限公司 | Synthesis method of perfluoroisobutyronitrile |
| CN116273164A (en) * | 2023-03-16 | 2023-06-23 | 浙江锦华新材料股份有限公司 | Isomerization reaction catalyst of perfluoro-4-methyl-2-pentene |
| CN116514642A (en) * | 2023-05-06 | 2023-08-01 | 多氟多新材料股份有限公司 | Preparation method and application of perfluoro-hexanone |
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| WO2019006993A1 (en) | 2019-01-10 |
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