CN104788495A - 一种六氯环三磷腈及其衍生物的氟化方法 - Google Patents
一种六氯环三磷腈及其衍生物的氟化方法 Download PDFInfo
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- UBIJTWDKTYCPMQ-UHFFFAOYSA-N hexachlorophosphazene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 UBIJTWDKTYCPMQ-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000003682 fluorination reaction Methods 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims abstract description 15
- 239000002608 ionic liquid Substances 0.000 claims abstract description 16
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 239000000460 chlorine Substances 0.000 claims abstract description 6
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 6
- ZSTLPJLUQNQBDQ-UHFFFAOYSA-N azanylidyne(dihydroxy)-$l^{5}-phosphane Chemical compound OP(O)#N ZSTLPJLUQNQBDQ-UHFFFAOYSA-N 0.000 claims description 16
- 238000004821 distillation Methods 0.000 claims description 10
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 10
- -1 vinylidene, phenyl Chemical group 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000011775 sodium fluoride Substances 0.000 claims description 5
- 235000013024 sodium fluoride Nutrition 0.000 claims description 5
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- YMRICIZJOGQSBT-UHFFFAOYSA-N [N+](=O)([O-])O[N+](=O)[O-].[O] Chemical compound [N+](=O)([O-])O[N+](=O)[O-].[O] YMRICIZJOGQSBT-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 238000004334 fluoridation Methods 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 229910001914 chlorine tetroxide Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 150000002910 rare earth metals Chemical class 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 7
- PEJQKHLWXHKKGS-UHFFFAOYSA-N 2,2,4,4,6,6,8,8-octachloro-1,3,5,7-tetraza-2$l^{5},4$l^{5},6$l^{5},8$l^{5}-tetraphosphacycloocta-1,3,5,7-tetraene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 PEJQKHLWXHKKGS-UHFFFAOYSA-N 0.000 abstract 1
- DKQPXAWBVGCNHG-UHFFFAOYSA-N 2,2,4,4,6,6-hexafluoro-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound FP1(F)=NP(F)(F)=NP(F)(F)=N1 DKQPXAWBVGCNHG-UHFFFAOYSA-N 0.000 abstract 1
- 230000007547 defect Effects 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000003063 flame retardant Substances 0.000 description 9
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- GELMJFCSFUJEHB-UHFFFAOYSA-N ClC(C(OP1N=PN=P[N]1)=C(C(Cl)=C1Cl)Cl)=C1Cl Chemical compound ClC(C(OP1N=PN=P[N]1)=C(C(Cl)=C1Cl)Cl)=C1Cl GELMJFCSFUJEHB-UHFFFAOYSA-N 0.000 description 2
- MFWDFTZSKUUNLN-UHFFFAOYSA-N [O].FC=1C(=C(C(=C(C1)F)F)F)F Chemical compound [O].FC=1C(=C(C(=C(C1)F)F)F)F MFWDFTZSKUUNLN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 description 2
- PBIDWHVVZCGMAR-UHFFFAOYSA-N 1-methyl-3-prop-2-enyl-2h-imidazole Chemical compound CN1CN(CC=C)C=C1 PBIDWHVVZCGMAR-UHFFFAOYSA-N 0.000 description 1
- WWVMHGUBIOZASN-UHFFFAOYSA-N 1-methyl-3-prop-2-enylimidazol-1-ium Chemical compound CN1C=C[N+](CC=C)=C1 WWVMHGUBIOZASN-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 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 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012858 resilient material Substances 0.000 description 1
- 239000003340 retarding agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000010887 waste solvent Substances 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
- C07F9/659—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 having three phosphorus atoms as ring hetero atoms in the same ring
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- 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
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- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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Abstract
本发明涉及一种六氯环三磷腈及其衍生物的氟化方法，其特征是，以六氯磷腈或部分取代的六氯环三磷腈为原料，在离子液体中用氟化剂进行氟化，取代氯代环三磷腈分子中的氯。本发明采用难挥发、无污染的离子液体为溶剂，只需控制馏出温度就可以制备高纯的六氟环三磷腈或其衍生物，克服了普通溶剂体系溶剂容易与产物共沸的缺点，后处理简单，产物纯度和产率很高，离子液体可以重复利用。
Description
技术领域
本发明涉及一种六氯环三磷腈及其衍生物的氟化方法。
背景技术
磷腈类化合物不但具有磷系阻燃剂良好的阻燃性能，而且具备氮化合物的阻燃增效和协同阻燃的作用，阻燃效果好、且不需添加任何其他辅助阻燃剂，同时，热稳定性好、无毒、发烟量小、具有自熄性，被公认为是今后阻燃剂的发展方向之一。多种磷腈阻燃剂被合成并用于各种材料的阻燃研究。同时磷腈类化合物可用于制备耐高温、耐低温、抗氧化的军事和航空航天工业用特种橡胶和弹性材料。氯代环三磷腈具有良好的阻燃效果。但是这种阻燃剂容易水解，同时氯对电池体系具有很大的腐蚀作用。最近，研究发现当使用氟对氯进行取代，可以得到不易水解，黏度较低，兼容性更好的功能性磷腈衍生物。氟代磷腈类化合物还可以用作里锂离子电池的高效阻燃剂。目前磷腈的氟化方法通常是在有机小分子溶剂中进行氟化，生成氟化物进行蒸馏和分馏。由于有机小分子容易挥发，并且和氟代环三磷腈形成共沸物，难以提纯，同时浪费了溶剂，提高了成本。
发明内容
为了解决上述问题，本发明的提供一种高效、无挥发性的氟化反应体系，其采用离子液体作为其反应体系溶剂，本发明能够提高环三磷腈及其衍生物氟化反应效率，降低提纯成本。
本发明具体采用的技术方案是：
一种六氯环三磷腈及其衍生物的氟化方法，其特征是，包含以下步骤：
将六氯环三磷腈或其衍生物溶于离子液体，加入氟化剂，控制温度进行氟化反应，然后蒸馏，制的高纯六氟环三磷腈或其衍生物
所述六氯环三磷腈及其衍生物的化学式为：
其中，S1-S6中只少有一个氯，S1-S6独立选自C1-C20的烷基、烷氧基、氟代烷氧基、芳香基、羧基、羟基、氰基、硝基、醚氧基、卤素。
所述离子液体化学式为：
上述化学式中取代为一元、二元或三元取代，并且，R1、R2、R3分别独立选自碳原子在0-20间的烷基、烷氧基、芳香基、羧基、羟基、氰基、硝基、醚氧基、卤素。
优选的，取代基R1、R2、R3分别独立选自以下基团：甲基、乙基、丙基、丁基、乙烯基、烯丙基、丁烯基、亚乙烯基、苯基、苯甲基或苄基。
其中，阴离子X选自以下几种中的至少一种：F-、PF6 -、BF4 -、TFSI-、FSI-、BOB-、ClO4-。
所述的氟化剂为铵、锂、钠、钾、铷、钙、镁、铝、铬、铁、钴、锑、镍、铜、锌、钛或稀土氟化物的一种或多种组合，最优氟化物为氟化钠和氟化钾。
所述的氟化温度为10-300℃，最优温度为100-130℃。所述的反应时间为2-98小时，最优时间为12-15小时。所述的蒸馏温度为40-300℃。最优温度高于产物沸点10℃
与现有技术相比，本发明采用难挥发、无污染的离子液体为溶剂，只需控制馏出温度就可以制备高纯的六氟环三磷腈或其衍生物，克服了普通溶剂体系溶剂容易与产物共沸的缺点，后处理简单，产物纯度和产率很高，离子液体可以重复利用。
具体实施方式
实施例1
取0.1摩尔六氯环三磷腈，加入装有100毫升1-苄基-3-甲基吡啶六氟磷酸盐离子液体烧瓶中，然后加入1摩尔氟化钠，在130℃氟化10小时，然后在60℃蒸馏，得到高纯度的六氟环三磷腈。
实施例2
取0.1摩尔五氯乙氧基环三磷腈，加入装有100毫升1-烯丙-3-甲基咪唑四氟硼酸盐离子液体烧瓶中，然后加入1摩尔氟化钠，在130℃氟化12小时，然后在160℃蒸馏，得到高纯度的五氟乙氧基环三磷腈。
实施例3
取0.1摩尔五氯三氟乙氧基环三磷腈，加入装有100毫升1-苯基-3-甲基咪唑四氟硼酸盐离子液体的带回流装置烧瓶中，然后加入1摩尔氟化钾和0.5摩尔氟化钠，在200℃氟化20小时，然后在180℃蒸馏，得到高纯度的五氟乙氧基环三磷腈。
实施例4
取0.1摩尔2氯四丁氧基环三磷腈，加入装有100毫升1-甲基-3-甲基咪唑四氟硼酸盐离子液体的带回流装置烧瓶中，然后加入0.5摩尔氟化钾和0.5摩尔氟化钙，在280℃氟化16小时，然后在220℃蒸馏，得到高纯度的2氟四丁氧基环三磷腈。
实施例5
取0.1摩尔五氯苯氧基环三磷腈，加入装有100毫升1-乙烯-3-甲基咪唑四氟硼酸盐离子液体的带回流装置烧瓶中，然后加入0.8摩尔氟化钾，在50℃氟化16小时，然后在240℃蒸馏，得到高纯度的五氟苯氧基环三磷腈。
实施例6
取0.1摩尔五氯苯氧基环三磷腈，加入装有50毫升1-苯氧-3-甲基咪唑四氟硼酸盐和50毫升1-烯丙-3-甲基咪唑六氟磷酸盐离子液体的烧瓶中，然后加入0.8摩尔氟化钾和0.2摩尔氟化锌，在50℃氟化16小时，然后在240℃蒸馏，得到高纯度的五氟苯氧基环三磷腈。
Claims (8)
1.一种六氯环三磷腈及其衍生物的氟化方法，其特征是，包含以下步骤：
将六氯环三磷腈或其衍生物溶于离子液体，加入氟化剂，控制温度进行氟化反应，然后常压蒸馏，制的高纯六氟环三磷腈或其衍生物；
所述六氯环三磷腈及其衍生物的化学式为：
其中，S1‐S6中只少有一个氯，S1‐S6独立选自C1‐C20的烷基、烷氧基、氟代烷氧基、芳香基、羧基、羟基、氰基、硝基、醚氧基、卤素。
2.根据权利要求1所述的六氯环三磷腈及其衍生物的氟化方法，其特征是，所述离子液体化学式为：
上述化学式中取代为一元、二元或三元取代，并且，R1、R2、R3分别独立选自碳原子在0‐20间的烷基、烷氧基、芳香基、羧基、羟基、氰基、硝基、醚氧基、卤素。
3.根据权利要求2所述的六氯环三磷腈及其衍生物的氟化方法，其特征是，取代基R1、R2、R3分别独立选自以下基团：甲基、乙基、丙基、丁基、乙烯基、烯丙基、丁烯基、亚乙烯基、苯基、苯甲基或苄基。
4.根据权利要求2所述的六氯环三磷腈及其衍生物的氟化方法，其特征是，阴离子X选自以下几种中的至少一种：F‐、PF6 ‐、BF4 ‐、TFSI‐、FSI‐、BOB‐、ClO4‐。
5.根据权利要求1所述的六氯环三磷腈及其衍生物的氟化方法，其特征是，所述的氟化剂为铵、锂、钠、钾、铷、钙、镁、铝、铬、铁、钴、锑、镍、铜、锌、钛或稀土氟化物的一种或多种组合。
6.根据权利要求5所述的六氯环三磷腈及其衍生物的氟化方法，其特征是，所述的氟化剂为为氟化钠或/和氟化钾。
7.根据权利要求1所述的六氯环三磷腈及其衍生物的氟化方法，其特征是，所述的氟化温度为10‐300℃，所述的反应时间为2‐98小时，所述的蒸馏温度为40‐300℃。
8.根据权利要求1所述的六氯环三磷腈及其衍生物的氟化方法，其特征是，所述的氟化温度为00-130℃，所述的反应时间为12-15小时，所述的蒸馏温度高于产物沸点10℃。
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