CN107759637A - 一种磷腈及磷腈衍生物的氟化反应催化剂及其氟化物的合成方法 - Google Patents
一种磷腈及磷腈衍生物的氟化反应催化剂及其氟化物的合成方法 Download PDFInfo
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- CN107759637A CN107759637A CN201711137139.0A CN201711137139A CN107759637A CN 107759637 A CN107759637 A CN 107759637A CN 201711137139 A CN201711137139 A CN 201711137139A CN 107759637 A CN107759637 A CN 107759637A
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- phosphonitrile
- catalyst
- fluoride
- phosphazene derivative
- synthetic method
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- ZSTLPJLUQNQBDQ-UHFFFAOYSA-N azanylidyne(dihydroxy)-$l^{5}-phosphane Chemical compound OP(O)#N ZSTLPJLUQNQBDQ-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical class CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000010189 synthetic method Methods 0.000 title claims abstract description 20
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 title abstract description 8
- 238000004334 fluoridation Methods 0.000 title description 3
- -1 Chloro phosphonitrile Chemical compound 0.000 claims abstract description 56
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- 239000002608 ionic liquid Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 238000003682 fluorination reaction Methods 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 20
- 235000013024 sodium fluoride Nutrition 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 238000005660 chlorination reaction Methods 0.000 claims description 11
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 7
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical class CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N dichloromethane Natural products ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 5
- BVWCFOXBDSMXEP-UHFFFAOYSA-N 1-(5-acetyl-2-methoxyphenyl)-3-methylbutan-1-one Chemical compound COC1=CC=C(C(C)=O)C=C1C(=O)CC(C)C BVWCFOXBDSMXEP-UHFFFAOYSA-N 0.000 claims description 4
- WGVGZVWOOMIJRK-UHFFFAOYSA-N 1-hexyl-3-methyl-2h-imidazole Chemical compound CCCCCCN1CN(C)C=C1 WGVGZVWOOMIJRK-UHFFFAOYSA-N 0.000 claims description 4
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-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
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 4
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical class CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 claims description 3
- QZHCWVOOQUPXGE-UHFFFAOYSA-N OC[P] Chemical compound OC[P] QZHCWVOOQUPXGE-UHFFFAOYSA-N 0.000 claims description 3
- ZQAVAOYDHNUKHF-UHFFFAOYSA-N butan-1-amine;formic acid Chemical class [O-]C=O.CCCC[NH3+] ZQAVAOYDHNUKHF-UHFFFAOYSA-N 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- AHRQMWOXLCFNAV-UHFFFAOYSA-O ethylammonium nitrate Chemical compound CC[NH3+].[O-][N+]([O-])=O AHRQMWOXLCFNAV-UHFFFAOYSA-O 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 229940124530 sulfonamide Drugs 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- WZWSOGGTVQXXSN-UHFFFAOYSA-N cyclohexanone;toluene Chemical compound CC1=CC=CC=C1.O=C1CCCCC1 WZWSOGGTVQXXSN-UHFFFAOYSA-N 0.000 claims description 2
- 150000004816 dichlorobenzenes Chemical class 0.000 claims description 2
- 238000005530 etching Methods 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 235000003270 potassium fluoride Nutrition 0.000 claims description 2
- 239000011698 potassium fluoride Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- 229940090181 propyl acetate Drugs 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims 2
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 claims 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims 1
- OKSUCCKLAIZTQH-UHFFFAOYSA-N Cl[P] Chemical compound Cl[P] OKSUCCKLAIZTQH-UHFFFAOYSA-N 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- JZKFIPKXQBZXMW-UHFFFAOYSA-L beryllium difluoride Chemical compound F[Be]F JZKFIPKXQBZXMW-UHFFFAOYSA-L 0.000 claims 1
- 229910001633 beryllium fluoride Inorganic materials 0.000 claims 1
- 150000002460 imidazoles Chemical class 0.000 claims 1
- 150000002500 ions Chemical class 0.000 claims 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims 1
- 238000009835 boiling Methods 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 description 14
- 238000004090 dissolution Methods 0.000 description 14
- 238000005292 vacuum distillation Methods 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 125000001153 fluoro group Chemical group F* 0.000 description 7
- 239000002585 base Substances 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 150000003222 pyridines Chemical class 0.000 description 2
- BTAGRXWGMYTPBY-UHFFFAOYSA-N 1,2,3-trichloro-4-(2,3,4-trichlorophenyl)benzene Chemical compound ClC1=C(Cl)C(Cl)=CC=C1C1=CC=C(Cl)C(Cl)=C1Cl BTAGRXWGMYTPBY-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000004965 chloroalkyl group Chemical group 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- PMOIAJVKYNVHQE-UHFFFAOYSA-N phosphanium;bromide Chemical compound [PH4+].[Br-] PMOIAJVKYNVHQE-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920002627 poly(phosphazenes) Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- CMXPERZAMAQXSF-UHFFFAOYSA-M sodium;1,4-bis(2-ethylhexoxy)-1,4-dioxobutane-2-sulfonate;1,8-dihydroxyanthracene-9,10-dione Chemical compound [Na+].O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=CC=C2O.CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC CMXPERZAMAQXSF-UHFFFAOYSA-M 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
- C07F9/65812—Cyclic phosphazenes [P=N-]n, n>=3
- C07F9/65815—Cyclic phosphazenes [P=N-]n, n>=3 n = 3
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0279—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the cationic portion being acyclic or nitrogen being a substituent on a ring
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0287—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing atoms other than nitrogen as cationic centre
- B01J31/0288—Phosphorus
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B39/00—Halogenation
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
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Abstract
本发明公开了一种磷腈及磷腈衍生物的氟化反应的催化剂及其氟化物的合成方法,包括:将氯代磷腈或其衍生物溶解于有机溶剂中,加入氟化剂和催化剂反应1‑48 h,即得氟代磷腈及其衍生物,所述催化剂为原料总质量的1‑40%。本发明采用的催化剂为离子液体,具有高熔沸点、稳定、绿色环保、催化效率高等优点,并且极大地提高的产率,平均产率达到98%以上。
Description
技术领域
本发明涉及一种磷腈及磷腈衍生物的氟化反应催化剂及其氟化物的合成方法。
背景技术
磷腈化合物是一类骨架由磷和氮交替排列的无机-有机杂化化合物,可分为环磷腈和聚磷腈。其中,氯代磷腈是环磷腈化合物中最有代表性的化合物,由于氯原子具有很强的活性,很容易被各种亲核试剂所取代。因此,以氯代磷腈为中间体,可合成出具有各种有机官能团的氟代磷腈及其磷腈衍生物。氯原子在锂电池电解液中的兼容性较差,而氟代磷腈及其衍生物则具有很好的电化学兼容性。
目前,氟代磷腈及其衍生物的合成主要以氯代磷腈与氟盐进行氟化反应产率较低,其催化剂主要有四甲基氯化铵、四甲基溴化铵、18-冠-6和溴化鏻和聚乙二醇等,但是这些催化剂熔沸点低、易分解、对人体有害、污染环境;若不加催化剂,则大大降低了氯代磷腈与氟盐进行氟化反应的速度。
因此开发高熔沸点、稳定、高催化效率、绿色环保的氟化反应的催化剂具有重要的应用价值。
发明内容
为解决现有技术中存在的问题,本发明提供了一种磷腈及磷腈衍生物的氟化反应催化剂及其氟化物的合成方法,该催化剂活性高,能够同时保证氟化反应的高反应速率和高产率,并且降低成本。
本发明的目的之一是提供一种磷腈及磷腈衍生物的氟化反应的催化剂。
本发明的目的之二是提供一种磷腈及磷腈衍生物氟化物的合成方法。
本发明的目的之三是提供上述催化剂及合成方法的应用。
为了实现上述目的,本发明公开了以下技术方案:
首先,本发明公开了以离子液体作为磷腈及磷腈衍生物的氟化反应的催化剂。
具体的,所述离子液体为烷基季铵类离子液体、咪唑类离子液体、以及四羟甲基磷氯盐、1-丁基-3-甲基咪唑双三氟甲磺酰亚胺盐和双氟甲磺酰亚胺盐。
优选的,所述烷基季铵类离子液体为乙基胺硝酸盐、已基胺甲酸盐、丙基胺甲酸盐、丁基胺甲酸盐。
优选的,所述咪唑类离子液体为1-乙基-3-甲基咪唑四氟硼酸盐、1-丁基-3-甲基咪唑四氟硼酸盐、1-己基-3-甲基咪唑四氟硼酸盐、1-辛基-3-甲基咪唑四氟硼酸盐、1-丁基-3-甲基咪唑六氟硼酸盐、1-己基-3-甲基咪唑六氟硼酸盐、1-辛基-3-甲基咪唑六氟硼酸盐、氯化1-丁基-3-甲基咪唑、氯化1-乙基-3-甲基咪唑、氯化1-己基-3-甲基咪唑、氯化1-辛基-3-甲基咪唑。
其次,基于上述催化剂,本发明还公开了一种磷腈及磷腈衍生物的氟化物合成方法,具体包括:将磷腈或其衍生物溶解于有机溶剂中,加入氟化剂和催化剂反应,即得磷腈及磷腈衍生物的氟化物(即氟代磷腈及其衍生物)。
上述合成方法中,所述磷腈或其衍生物的通式为:
其中,R1-R6均可以为氯元素、烷基、氯代烷基、氯代烷氧基、氯代联苯、烷氧基、烷基硅、氯代烯烃基、联苯基苯基、氯代苯基、烷基磷酸酯、烷氧基硅、烷氧基硼或酰胺基。
上述合成方法中,所述磷腈或其衍生物与氟化剂的物质的量之比为1:1-1.8;当比例处在该范围内时,能够有效提高产品的转化率。
上述合成方法中,所述氟化剂为氟化钠、氟化钾、四丁基氟化铵(TBAF)、氟化铯、氟化铍、氟化钙、氟氢酸钾中的一种或其两种的混合物。
上述合成方法中,所述催化剂为原料总质量的1-40%。
上述合成方法中,所述反应温度为20-200℃。
上述合成方法中,所述反应时间为1-48h。
上述合成方法中,所述有机溶剂为苯、甲苯、二甲苯、戊烷、己烷、辛烷、环己烷、环己酮、甲苯环己酮、氯苯、二氯苯、二氯甲烷、甲醇、乙醇、异丙醇、乙醚、环氧丙烷、醋酸甲酯、醋酸乙酯、醋酸丙酯、丙酮、甲基丁酮、甲基异丁酮、乙二醇单甲醚、乙二醇单乙醚、乙二醇单丁醚、乙腈、吡啶、苯酚、N,N-二甲基甲酰胺(DMF)或苯甲腈中的一种或两种以上的混合物。
最后,本发明公开了上述磷腈及磷腈衍生物的氟化反应的催化剂及其氟化物的合成方法的应用,所述应用包括用于电池或电容器电解液的制备。
需要说明的是:本发明用离子液体催化磷腈及磷腈衍生物氟代反应,由于离子液体极易溶于有机溶剂中,且催化磷腈及磷腈衍生物氟代反应时具有高活性,氟代反应在常温下就能充分进行,且反应产率达到98%以上。离子液体既可以溶于极性溶剂也可以溶于非极性溶剂,不同结构的离子液体在不同溶剂中溶解度不同,通过选择相应溶剂即可将离子液体催化剂和氟代磷腈及其衍生物分离,无需酸洗、碱洗,并且通过降温可使离子液体从有机溶剂中析出,从而回收溶剂。本发明所述催化剂结构稳定不易分解,具有高熔沸点,不会对操作人员身体造成伤害。另外,本发明中的氟代磷腈及其衍生物生成后,其不易溶于有机溶剂,导致氟代磷腈及其衍生物与有机溶剂自动分离或分层,从而有利于氟代磷腈及其衍生物的直接分离,同时有机溶剂就可以直接回收接着利用。
本发明的有益效果
1.本发明采用的合成方法反应条件温和,反应可操控性好,便于工业化生产。
2.本发明合成方法的后处理只需对反应完物料进行抽滤,浓缩等简单操作即可得到较高质量和收率的产品,不需要经多次酸洗、碱洗,从而避免了因多次洗涤而造成的不必要损失,提高了收率。
3.本发明的工艺流程简单,耗能低,溶剂可回收,产率较高,所得产品纯度也较高。
4.本发明采用的催化剂具有高熔沸点、稳定、绿色环保、催化效率高等优点,并且极大地提高的产率。
5.本发明采用的催化剂具有高的熔沸点,因此可在较高的温度下蒸发有机溶剂,从而得到纯度较高的离子液体,因此本发明中的催化剂可以回收利用。
具体实施方式
应该指出,以下详细说明都是示例性的,旨在对本发明提供进一步的说明。除非另有指明,本文使用的所有技术和科学术语具有与本发明所属技术领域的普通技术人员通常理解的相同含义。
需要注意的是,这里所使用的术语仅是为了描述具体实施方式,而非意图限制根据本发明的示例性实施方式。如在这里所使用的,除非上下文另外明确指出,否则单数形式也意图包括复数形式,此外,还应当理解的是,当在本说明书中使用术语“包含”和/或“包括”时,其指明存在特征、步骤、操作和/或它们的组合。
正如背景技术所述,现有磷腈及磷腈衍生物氟代反应的催化剂大多存在熔沸点低、易分解、对人体有害、污染环境等问题,且活性一般,反应一般需要在高温环境下进行;此外,这些催化剂的回收也不易进行,增大了成本;现结合具体的实施例,对本发明做进一步的说明。
实施例1:
将34.7g六氯环三磷腈晶体溶解于200ml四氢呋喃中形成六氯环三磷腈溶液,向溶液中加入27g氟化钠作为氟化剂,加入2g乙基胺硝酸盐作为催化剂,并在30℃温度条件下反应1h,经过滤、减压蒸馏后得到磷腈衍生物六氟环三磷腈,产率98.8%。
实施例2
将27.5g乙氧基五氯环三磷腈晶体溶解于200ml四氢呋喃中形成乙氧基五氯环三磷腈溶液,向溶液中加入27g氟化钠作为氟化剂,加入2g 1-乙基-3-甲基咪唑四氟硼酸盐作为催化剂,并在30℃温度条件下反应3h,经过滤、减压蒸馏后得到磷腈衍生物乙氧基五氟环三磷腈,产率99%。
实施例3
将34.7g六氯环三磷腈晶体溶解于200ml DMF中形成六氯环三磷腈溶液,向溶液中加入27g氟化钠作为氟化剂,加入2g1-丁基-3-甲基咪唑四氟硼酸盐作为催化剂,并在50℃温度条件下反应5h,经过滤、减压蒸馏后得到磷腈衍生物六氟环三磷腈,产率99.8%。
实施例4
将27.5g乙氧基五氯环三磷腈晶体溶解于200ml DMF中形成乙氧基五氯环三磷腈溶液,向溶液中加入27g氟化钠作为氟化剂,加入2g 1-己基-3-甲基咪唑四氟硼酸盐作为催化剂,并在70℃温度条件下反应7h,经过滤、减压蒸馏后得到磷腈衍生物乙氧基五氟环三磷腈,产率99.3%。
实施例5
将34.7g六氯环三磷腈晶体溶解于200ml石油醚中形成六氯环三磷腈溶液,向溶液中加入27g氟化钠作为氟化剂,加入2g双氟甲磺酰亚胺盐作为催化剂,并在90℃温度条件下反应1h,经过滤、减压蒸馏后得到磷腈衍生物六氟环三磷腈,产率99.6%。
实施例6
将27.5g乙氧基五氯环三磷腈晶体溶解于200ml石油醚中形成乙氧基五氯环三磷腈溶液,向溶液中加入27g氟化钠作为氟化剂,加入2g 1-丁基-3-甲基咪唑双三氟甲磺酰亚胺盐作为催化剂,并在110℃温度条件下反应12h,经过滤、减压蒸馏后得到磷腈衍生物乙氧基五氟环三磷腈,产率98.9%。
实施例7
将34.7g六氯环三磷腈晶体溶解于200ml正己烷中形成六氯环三磷腈溶液,向溶液中加入27g氟化钠作为氟化剂,加入2g四羟甲基磷氯盐作为催化剂,并在130℃温度条件下反应15h,经过滤、减压蒸馏后得到磷腈衍生物六氟环三磷腈,产率98.2%。
实施例8
将27.5g乙氧基五氯环三磷腈晶体溶解于200ml正己烷中形成乙氧基五氯环三磷腈溶液,向溶液中加入27g氟化钠作为氟化剂,加入2g丁基胺甲酸盐作为催化剂,并在150℃温度条件下反应20h,经过滤、减压蒸馏后得到磷腈衍生物乙氧基五氟环三磷腈,产率99.6%。
实施例9
将34.7g六氯环三磷腈晶体溶解于200ml甲苯中形成六氯环三磷腈溶液,向溶液中加入27g氟化钠作为氟化剂,加入2g氯化1-丁基-3-甲基咪唑作为催化剂,并在170℃温度条件下反应25h,经过滤、减压蒸馏后得到磷腈衍生物六氟环三磷腈,产率99.3%。
实施例10
将27.5g乙氧基五氯环三磷腈晶体溶解于200ml甲苯中形成乙氧基五氯环三磷腈溶液,向溶液中加入27g氟化钠作为氟化剂,加入2g 1-辛基-3-甲基咪唑四氟硼酸盐作为催化剂,并在190℃温度条件下反应30h,经过滤、减压蒸馏后得到磷腈衍生物乙氧基五氟环三磷腈,产率98.4%。
实施例11
将34.7g六氯环三磷腈晶体溶解于200ml乙腈中形成六氯环三磷腈溶液,向溶液中加入27g氟化钠作为氟化剂,加入2g 1-辛基-3-甲基咪唑四氟硼酸盐作为催化剂,并在200℃温度条件下反应35h,经过滤、减压蒸馏后得到磷腈衍生物六氟环三磷腈,产率98.8%。
实施例12
将27.5g乙氧基五氯环三磷腈晶体溶解于200ml乙腈中形成乙氧基五氯环三磷腈溶液,向溶液中加入27g氟化钠作为氟化剂,加入2g氯化1-辛基-3-甲基咪唑作为催化剂,并在120℃温度条件下反应40h,经过滤、减压蒸馏后得到磷腈衍生物乙氧基五氟环三磷腈,产率99.1%。
实施例13
将34.7g六氯环三磷腈晶体溶解于200ml吡啶中形成六氯环三磷腈溶液,向溶液中加入27g氟化钠作为氟化剂,加入2g氯化1-乙基-3-甲基咪唑作为催化剂,并在80℃温度条件下反应45h,经过滤、减压蒸馏后得到磷腈衍生物六氟环三磷腈,产率98.3%。
实施例14
将27.5g乙氧基五氯环三磷腈晶体溶解于200ml吡啶中形成乙氧基五氯环三磷腈溶液,向溶液中加入27g氟化钠作为氟化剂,加入2g已基胺甲酸盐作为催化剂,并在20℃温度条件下反应48h,经过滤、减压蒸馏后得到磷腈衍生物乙氧基五氟环三磷腈,产率98.6%。
上述实施例虽然对本发明的具体实施方式进行了描述,但并非对发明保护范围的限制,所属领域技术人员应该明白,在发明的技术方案的基础上,本领域技术人员不需要付出创造性劳动即可做出的各种修改或变形仍在本发明的保护范围内。
Claims (10)
1.一种磷腈及磷腈衍生物的氟化反应的催化剂,其特征在于:所述催化剂为离子液体。
2.如权利要求1所述的磷腈及磷腈衍生物的氟化反应的催化剂,其特征在于:所述离子液体为烷基季铵类离子液体、咪唑类离子液体、以及四羟甲基磷氯盐、1-丁基-3-甲基咪唑双三氟甲磺酰亚胺盐和双氟甲磺酰亚胺盐。
3.如权利要求2所述的磷腈及磷腈衍生物的氟化反应的催化剂,其特征在于:所述烷基季铵类离子液体为乙基胺硝酸盐、已基胺甲酸盐、丙基胺甲酸盐、丁基胺甲酸盐。
4.如权利要求2所述的磷腈及磷腈衍生物的氟化反应的催化剂,其特征在于:所述咪唑类离子液体为1-乙基-3-甲基咪唑四氟硼酸盐、1-丁基-3-甲基咪唑四氟硼酸盐、1-己基-3-甲基咪唑四氟硼酸盐、1-辛基-3-甲基咪唑四氟硼酸盐、1-丁基-3-甲基咪唑六氟硼酸盐、1-己基-3-甲基咪唑六氟硼酸盐、1-辛基-3-甲基咪唑六氟硼酸盐、氯化1-丁基-3-甲基咪唑、氯化1-乙基-3-甲基咪唑、氯化1-己基-3-甲基咪唑、氯化1-辛基-3-甲基咪唑。
5.一种磷腈及磷腈衍生物氟化物的合成方法,其特征在于:所述方法包括:将磷腈或其衍生物溶解于有机溶剂中,加入氟化剂和权利要求1-4任一所述的催化剂反应,即得氟代磷腈及其衍生物。
6.如权利要求5所述的磷腈及磷腈衍生物氟化物的合成方法,其特征在于:所述催化剂为氯代磷腈或其衍生物总质量的1-40%。
7.如权利要求5所述的磷腈及磷腈衍生物氟化物的合成方法,其特征在于:所述有机溶剂为苯、甲苯、二甲苯、戊烷、己烷、辛烷、环己烷、环己酮、甲苯环己酮、氯苯、二氯苯、二氯甲烷、甲醇、乙醇、异丙醇、乙醚、环氧丙烷、醋酸甲酯、醋酸乙酯、醋酸丙酯、丙酮、甲基丁酮、甲基异丁酮、乙二醇单甲醚、乙二醇单乙醚、乙二醇单丁醚、乙腈、吡啶、苯酚、N,N-二甲基甲酰胺(DMF)或苯甲腈中的一种或两种以上的混合物。
8.如权利要求5所述的磷腈及磷腈衍生物氟化物的合成方法,其特征在于:所述氟化剂为氟化钠、氟化钾、四丁基氟化铵(TBAF)、氟化铯、氟化铍、氟化钙、氟氢酸钾中的一种或其两种的混合物。
9.如权利要求5所述的磷腈及磷腈衍生物氟化物的合成方法,其特征在于:所述氯代磷腈或其衍生物与氟化剂的物质的量之比为1:1-1.8。
10.如权利要求1-4所述的催化剂和/或如权利要求5-9所述的合成方法在电池或电容器电解液的制备中的应用。
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108314694A (zh) * | 2018-02-02 | 2018-07-24 | 苏州贺康新材料科技有限公司 | 一种锂电池电解液阻燃剂的制备方法 |
CN112175010A (zh) * | 2020-10-16 | 2021-01-05 | 南京师范大学 | 一种六氟环三磷腈的合成方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1524313A (zh) * | 2001-07-05 | 2004-08-25 | 株式会社普利司通 | 非水电解液电池、电极稳定剂、磷腈衍生物及其制造方法 |
CN1524839A (zh) * | 2003-02-27 | 2004-09-01 | 北京大学 | 一种合成直链烷基二苯醚的方法 |
CN101168493A (zh) * | 2006-10-26 | 2008-04-30 | 中国石油化工股份有限公司 | 一种氟代氯苯的制备方法 |
CN102050806A (zh) * | 2010-11-24 | 2011-05-11 | 李韡 | 一种由木质纤维素制备含5-羟甲基糠醛产物的方法 |
CN104788495A (zh) * | 2015-04-14 | 2015-07-22 | 淄博蓝印化工有限公司 | 一种六氯环三磷腈及其衍生物的氟化方法 |
-
2017
- 2017-11-16 CN CN201711137139.0A patent/CN107759637A/zh active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1524313A (zh) * | 2001-07-05 | 2004-08-25 | 株式会社普利司通 | 非水电解液电池、电极稳定剂、磷腈衍生物及其制造方法 |
CN1524839A (zh) * | 2003-02-27 | 2004-09-01 | 北京大学 | 一种合成直链烷基二苯醚的方法 |
CN101168493A (zh) * | 2006-10-26 | 2008-04-30 | 中国石油化工股份有限公司 | 一种氟代氯苯的制备方法 |
CN102050806A (zh) * | 2010-11-24 | 2011-05-11 | 李韡 | 一种由木质纤维素制备含5-羟甲基糠醛产物的方法 |
CN104788495A (zh) * | 2015-04-14 | 2015-07-22 | 淄博蓝印化工有限公司 | 一种六氯环三磷腈及其衍生物的氟化方法 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108314694A (zh) * | 2018-02-02 | 2018-07-24 | 苏州贺康新材料科技有限公司 | 一种锂电池电解液阻燃剂的制备方法 |
CN112175010A (zh) * | 2020-10-16 | 2021-01-05 | 南京师范大学 | 一种六氟环三磷腈的合成方法 |
CN112175010B (zh) * | 2020-10-16 | 2023-07-21 | 南京师范大学 | 一种六氟环三磷腈的合成方法 |
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